organic compounds

= 86.338 (2)
= 89.299 (1)
= 75.128 (2)
3
V = 2170.93 (14) A
Z=6

Acta Crystallographica Section E

Structure Reports
Online
ISSN 1600-5368

Mo K radiation
= 0.24 mm1
T = 296 K
0.28 0.22 0.20 mm

Data collection

4-(3-Fluorophenyl)-1-(2-oxoindolin-3-ylidene)thiosemicarbazide
Muhammad Ramzan,a Humayun Pervez,a M. Nawaz
Tahirb* and Muhammad Yaquba
a

Department of Chemistry, Bahauddin Zakariya University, Multan 60800, Pakistan,

and bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
Correspondence e-mail: [email protected]

Bruker Kappa APEXII CCD

diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
Tmin = 0.942, Tmax = 0.950

31845 measured reflections

7851 independent reflections
4225 reflections with I > 2(I)
Rint = 0.059

Refinement
R[F 2 > 2(F 2)] = 0.063
wR(F 2) = 0.178
S = 1.02
7851 reflections
573 parameters

3 restraints
H-atom parameters constrained
3
max = 0.31 e A
3
min = 0.30 e A

Received 6 August 2010; accepted 30 August 2010

;
Key indicators: single-crystal X-ray study; T = 296 K; mean (CC) = 0.006 A
disorder in main residue; R factor = 0.063; wR factor = 0.178; data-to-parameter
ratio = 13.7.

Table 1
, ).
Hydrogen-bond geometry (A
DH A

In the title compound, C15H11FN4OS, there are three

independent molecules, each with a disordered 3-fluorophenyl
group [occupancy ratios = 0.547 (17):0.453 (17), 0.645 (5):
0.355 (5) and 0.626 (15):0.374 (15)] and displaying dihedral
angles of 4.2 (3), 25.2 (6) and 32.4 (5) between the 2oxoindoline and fluoro-substituted phenyl rings. Strong intramolecular NH N and NH O and weak intramolecular
CH S hydrogen bonds complete S(5) and S(6) ring motifs,
while strong intermolecular NH O hydrogen bonds
interconnect the three independent molecules through
R33(12) ring motifs. The three-molecule units are in turn linked
into polymeric sheets via CH F and CH S hydrogen
bonds and interactions [centroidcentroid distances in the
].
range 3.520 (2)3.820 (9) A

Related literature
For our work on the synthesis of biologically important isatin
(systematic name 1H-indole-2,3-dione) derivatives, see:
Pervez et al. (2007, 2008, 2009). For related structures, see:
Pervez et al. (2010). For graph-set notation, see: Bernstein et
al. (1995).

N1H1 O3
N3H3A O1
N4H4A N2
N5H5A O1ii
N7H7 O2
N8H8 N6
N9H9 O2iii
N11H11C O3
N12H12C N10
C4H4 F2Aiv
C15AH15A S1
C30AH30A S2
C42AH42A S2v
C45AH45A S3

DH

H A

D A

DH A

0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.93
0.93
0.93
0.93
0.93

2.03
2.11
2.13
2.05
2.11
2.14
2.06
2.09
2.13
2.48
2.57
2.54
2.87
2.72

2.837
2.778
2.596
2.881
2.785
2.599
2.871
2.767
2.590
3.215
3.223
3.208
3.763
3.260

155
134
114
164
135
113
157
135
113
136
127
129
162
118

(3)
(4)
(4)
(4)
(4)
(4)
(3)
(3)
(4)
(7)
(18)
(6)
(12)
(13)

Symmetry
codes:
(i)
x 1; y; z;
(ii)
x 1; y 1; z 1;
x 2; y 1; z 1; (iv) x; y 1; z; (v) x; y 1; z.

(iii)

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT

(Bruker, 2009); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009);
software used to prepare material for publication: WinGX (Farrugia,
1999) and PLATON.

HP, MY and MR thank the Ministry of Science & Technology (MoST), Government of Pakistan, for partial financial
assistance under Projects for the Strengthening of S & T
Education in Universities (project No. P&D/S&T/2001/231).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: BG2363).

References
Experimental
Crystal data
C15H11FN4OS
Mr = 314.34
Triclinic, P1

o2494

Ramzan et al.

a = 8.0582 (3) A

b = 14.3640 (5) A

c = 19.4456 (8) A

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 15551573.
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837838.

doi:10.1107/S1600536810034951

Acta Cryst. (2010). E66, o2494o2495

organic compounds
Pervez, H., Chohan, Z. H., Ramzan, M., Nasim, F. H. & Khan, K. M. (2009). J.
Enz. Inhib. Med. Chem. 24, 437446.
Pervez, H., Iqbal, M. S., Tahir, M. Y., Choudhary, M. I. & Khan, K. M. (2007).
Nat. Prod. Res. 21, 11781186.
Pervez, H., Iqbal, M. S., Tahir, M. Y., Nasim, F. H., Choudhary, M. I. & Khan,
K. M. (2008). J. Enz. Inhib. Med. Chem. 23, 848854.

Acta Cryst. (2010). E66, o2494o2495

Pervez, H., Yaqub, M., Ramzan, M., Iqbal, M. S. & Tahir, M. N. (2010). Acta
Cryst. E66, o1018.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112122.
Spek, A. L. (2009). Acta Cryst. D65, 148155.

Ramzan et al.

C15H11FN4OS

o2495

supplementary materials

supplementary materials
Acta Cryst. (2010). E66, o2494-o2495

[ doi:10.1107/S1600536810034951 ]

4-(3-Fluorophenyl)-1-(2-oxoindolin-3-ylidene)thiosemicarbazide
M. Ramzan, H. Pervez, M. N. Tahir and M. Yaqub
Comment
In continuation of our work on the synthesis of biologically important isatin derivatives (Pervez et al., 2007, 2008, 2009),
we report herein the structure and preparation of the title compound (I, Fig. 1). When compared with the crystal structure of
i.e. 4-(2-fluorophenyl)-1-(2-oxoindolin-3-ylidene) thiosemicarbazide (II) (Pervez et al., 2010), it can be noticed they differ
in the position of the fluoro function at the phenyl ring bound to N4 in the thiosemicarbazone moiety.
There are three independent molecules in (I). The 3-fluorophenyl moiety is disordered in each one with different site
occupancy ratios (0.547 (17):0.453 (17), 0.645 (5):0.355 (5) and 0.626 (15):0.374 (15), respectively. In all three molecules,
the 2-oxoindolin A (C1C8/N1/O1), B (C16C23/N5/O2) and C (C31C38/N9/O3) groups are planar with r. m. s. deviations
of 0.0054, 0.0100 and 0.0036 , respectively. The thiosemicarbazide D (N2/N3/C9/S1/N4), E (N6/N7/C24/S2/N8) and F
(N10/N11/C39/S3/N12) groups, in turn, are also planar with r. m. s. deviations of 0.0060, 0.0336 and 0.0192 , respectively.
The dihedral angles between A/D, B/E, C/F are 9.24 (15), 7.67 (14), 6.13 (17).
Due to strong intramolecular H-bondings of NHN and NHO type, there exist one S(5) and one S(6) (Bernstein et
al., 1995) ring motif, respectively (Table 1, Fig. 2). A weak intramolecular CHS H-bond is also present in each molecule
(Table 1). The three molecules are interconnected through strong intermolecular H-bonds of NHO type (Table 1, Fig.
2) and complete R33(12) ring motifs. The molecules are stabilized in the form of polymeric sheets which are finally formed
due to CHF and CHS interactions (Table 1, Fig. 2). In the stabilization of molecules, interactions present play
a relevant role.
Experimental
To a hot solution of isatin (0.74 g, 5.0 mmol) in ethanol (10 ml) containing a few drops of glacial acetic acid was added
4-(3-fluorophenyl)thiosemicarbazide (0.93 g, 5.0 mmol) dissolved in ethanol (10 ml) under stirring. The reaction mixture
was then heated under reflux for 2 h. The yellow crystalline solid formed during heating was collected by suction filtration.
Thorough washing with hot ethanol followed by ether afforded the target compound (I) in pure form (1.12 g, 71%), m. p.
513 K (d). The single crystals of (I) were grown in acetone-ethanol (1:4) by diffusion method at room temperature.
Refinement
The 3-fluorophenyl moiety is disordered in all three independent structures and their phenyl rings have been fitted into
regular hexagons (CC = 1.39.). The occupancy ratio of disordered groups is 0.547 (17):0.453 (17), 0.645 (5):0.355 (5)
and 0.626 (15):0.374 (15), respectively.
The H-atoms were positioned geometrically (NH = 0.86, CH = 0.93 ) and refined as riding with Uiso(H) = xUeq(C,
N), where x = 1.2 for all H-atoms.

sup-1

supplementary materials
Figures

Fig. 1. View of the title compound with the atom numbering scheme. The thermal ellipsoids
are drawn at the 30% probability level. H-atoms are shown by small circles of arbitrary radii.

Fig. 2. The partial packing (PLATON; Spek, 2009) which shows that molecules form poly-

meric sheets with central R33(12) ring motifs. The H-atoms not involved in H-bondings have
been omitted for clarity.

4-(3-Fluorophenyl)-1-(2-oxoindolin-3-ylidene)thiosemicarbazide
Crystal data
C15H11FN4OS

Z=6

Mr = 314.34

F(000) = 972

Triclinic, P1

Dx = 1.443 Mg m3

Hall symbol: -P 1
a = 8.0582 (3)
b = 14.3640 (5)

Mo K radiation, = 0.71073
Cell parameters from 4225 reflections
= 2.125.3

c = 19.4456 (8)

= 0.24 mm1
T = 296 K
Prisms, yellow
0.28 0.22 0.20 mm

= 86.338 (2)
= 89.299 (1)
= 75.128 (2)
V = 2170.93 (14) 3

Data collection
Bruker Kappa APEXII CCD
diffractometer
Radiation source: fine-focus sealed tube
graphite
Detector resolution: 8.10 pixels mm-1
scans
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
Tmin = 0.942, Tmax = 0.950
31845 measured reflections

sup-2

7851 independent reflections

4225 reflections with I > 2(I)
Rint = 0.059
max = 25.3, min = 2.1
h = 99
k = 1617
l = 2323

supplementary materials
Refinement
Refinement on F2

Secondary atom site location: difference Fourier map

Least-squares matrix: full

Hydrogen site location: inferred from neighbouring

sites

R[F2 > 2(F2)] = 0.063

H-atom parameters constrained

w = 1/[2(Fo2) + (0.0739P)2 + 0.9447P]

wR(F2) = 0.178

where P = (Fo2 + 2Fc2)/3

S = 1.02

(/)max = 0.001

7851 reflections

max = 0.31 e 3

573 parameters

min = 0.30 e 3

3 restraints

Extinction correction: SHELXL97 (Sheldrick, 2008),

Fc*=kFc[1+0.001xFc23/sin(2)]-1/4

Primary atom site location: structure-invariant direct

Extinction coefficient: 0.0055 (13)
methods

Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the
variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > (F2) is used only for calculating Rfactors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (2)
S1
F1A
O1
N1
N2
N3
N4
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10A

Uiso*/Ueq

0.26523 (19)
0.286 (9)
0.1679 (4)
0.0699 (4)
0.1031 (4)
0.1585 (4)
0.1882 (4)
0.1113 (5)
0.0125 (5)
0.0410 (5)
0.0925 (6)
0.0896 (6)
0.0350 (5)
0.0155 (5)
0.0788 (4)
0.2032 (5)
0.2262 (19)

0.98975 (8)
1.302 (7)
0.68968 (18)
0.5919 (2)
0.8231 (2)
0.8620 (2)
0.9854 (2)
0.6730 (3)
0.5970 (3)
0.5294 (3)
0.5520 (3)
0.6393 (3)
0.7081 (3)
0.6861 (3)
0.7381 (2)
0.9476 (2)
1.0704 (11)

0.34158 (6)
0.217 (8)
0.35500 (15)
0.28535 (17)
0.22575 (16)
0.27979 (16)
0.20740 (16)
0.3007 (2)
0.2173 (2)
0.1832 (3)
0.1160 (3)
0.0833 (3)
0.1178 (2)
0.1854 (2)
0.23583 (19)
0.27259 (19)
0.1760 (10)

0.0868 (5)
0.109 (6)
0.0677 (11)
0.0604 (11)
0.0538 (11)
0.0576 (11)
0.0596 (11)
0.0543 (16)
0.0567 (16)
0.0733 (19)
0.086 (2)
0.0860 (19)
0.0703 (16)
0.0524 (14)
0.0501 (12)
0.0532 (16)
0.0534 (18)

Occ. (<1)
0.547 (17)

0.547 (17)

sup-3

supplementary materials
C11A
C12A
C13A
C14A
C15A
C13B
C14B
C15B
C11B
F1B
C10B
C12B
S2
F2A
O2
N5
N6
N7
N8
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25A
C26A
C27A
C28A
C29A
C30A
C28B
C29B
C30B
C26B
F2B
C25B
C27B
S3
F3A
O3
N9
N10
N11
N12
C31

sup-4

0.246 (2)
0.263 (2)
0.2589 (19)
0.2389 (18)
0.2225 (18)
0.272 (2)
0.3003 (18)
0.267 (2)
0.178 (2)
0.285 (11)
0.206 (2)
0.211 (3)
0.57526 (16)
0.2702 (6)
0.7099 (3)
0.6913 (4)
0.5561 (4)
0.5872 (4)
0.5036 (4)
0.6704 (4)
0.6293 (4)
0.6306 (5)
0.5656 (6)
0.5044 (5)
0.5038 (5)
0.5672 (4)
0.5922 (4)
0.5525 (5)
0.4523 (6)
0.3903 (5)
0.3384 (4)
0.3485 (7)
0.4105 (9)
0.4624 (7)
0.3502 (8)
0.4134 (9)
0.4662 (8)
0.3926 (4)
0.4266 (11)
0.4558 (5)
0.3398 (5)
0.73951 (16)
0.683 (2)
1.0173 (2)
1.1234 (3)
0.9445 (4)
0.8890 (4)
0.8135 (4)
1.0500 (4)

1.0776 (12)
1.1637 (14)
1.2426 (11)
1.2354 (11)
1.1493 (13)
1.2310 (14)
1.2194 (13)
1.1406 (16)
1.0849 (16)
1.299 (9)
1.0733 (14)
1.1638 (19)
0.71997 (8)
0.4925 (3)
0.51552 (17)
0.3622 (2)
0.4643 (2)
0.5516 (2)
0.5648 (2)
0.4392 (3)
0.2887 (3)
0.1991 (3)
0.1399 (3)
0.1674 (3)
0.2575 (3)
0.3181 (3)
0.4138 (2)
0.6092 (3)
0.5959 (3)
0.5317 (3)
0.5553 (3)
0.6432 (3)
0.7074 (3)
0.6837 (3)
0.64587 (14)
0.70940 (11)
0.68490 (10)
0.53333 (17)
0.79699 (12)
0.59686 (14)
0.55784 (16)
0.32405 (7)
0.0464 (13)
0.42029 (11)
0.36096 (15)
0.2242 (2)
0.2813 (2)
0.1556 (2)
0.3568 (3)

0.1049 (10)
0.0722 (9)
0.1105 (10)
0.1816 (10)
0.2143 (9)
0.1052 (13)
0.1760 (13)
0.2134 (11)
0.1092 (13)
0.212 (10)
0.1800 (13)
0.0718 (11)
0.27758 (6)
0.0210 (2)
0.47192 (12)
0.50827 (15)
0.34248 (16)
0.33703 (16)
0.22516 (16)
0.46365 (19)
0.48129 (19)
0.5113 (2)
0.4723 (3)
0.4063 (3)
0.3766 (2)
0.41468 (19)
0.40045 (18)
0.2761 (2)
0.15770 (19)
0.12122 (16)
0.05302 (16)
0.0213 (2)
0.0578 (3)
0.1260 (3)
0.0212 (2)
0.0579 (2)
0.1259 (2)
0.12057 (16)
0.0362 (3)
0.15726 (19)
0.05254 (18)
0.17558 (5)
0.0360 (7)
0.35189 (7)
0.46050 (8)
0.35231 (15)
0.29489 (15)
0.25218 (15)
0.3997 (2)

0.061 (4)
0.103 (4)
0.095 (3)
0.047 (4)
0.047 (3)
0.095 (3)
0.047 (4)
0.047 (3)
0.061 (4)
0.109 (6)
0.0534 (18)
0.103 (4)
0.0787 (5)
0.141 (2)
0.0573 (10)
0.0536 (11)
0.0518 (11)
0.0582 (11)
0.0603 (11)
0.0476 (12)
0.0496 (14)
0.0643 (17)
0.0753 (19)
0.0730 (19)
0.0590 (16)
0.0480 (12)
0.0448 (12)
0.0546 (14)
0.0605 (17)
0.0715 (17)
0.093 (2)
0.113 (3)
0.112 (3)
0.087 (2)
0.113 (3)
0.112 (3)
0.087 (2)
0.0715 (17)
0.141 (2)
0.0605 (17)
0.093 (2)
0.0755 (5)
0.164 (6)
0.0627 (10)
0.0523 (11)
0.0479 (11)
0.0504 (11)
0.0553 (11)
0.0491 (12)

0.547 (17)
0.547 (17)
0.547 (17)
0.547 (17)
0.547 (17)
0.453 (17)
0.453 (17)
0.453 (17)
0.453 (17)
0.453 (17)
0.453 (17)
0.453 (17)
0.645 (5)

0.645 (5)
0.645 (5)
0.645 (5)
0.645 (5)
0.645 (5)
0.645 (5)
0.355 (5)
0.355 (5)
0.355 (5)
0.355 (5)
0.355 (5)
0.355 (5)
0.355 (5)
0.626 (15)

supplementary materials
C32
C33
C34
C35
C36
C37
C38
C39
C40A
C41A
C42A
C43A
C44A
C45A
C43B
C44B
C45B
C41B
F3B
C40B
C42B
H4
H12A
H13A
H15A
H4A
H5
H6
H11A
H1
H3
H3A
H11B
H12B
H13B
H15B
H18
H28A
H29A
H30A
H19
H20
H21
H26A
H5A
H7
H8
H26B
H27B

1.1409 (4)
1.2072 (5)
1.2097 (6)
1.1458 (6)
1.0786 (5)
1.0759 (4)
1.0161 (4)
0.8147 (4)
0.7514 (15)
0.6868 (14)
0.6494 (15)
0.6766 (16)
0.7412 (16)
0.7786 (16)
0.641 (3)
0.664 (3)
0.729 (3)
0.749 (2)
0.782 (4)
0.771 (3)
0.684 (3)
0.13029
0.27593
0.26982
0.20914
0.14832
0.12456
0.03279
0.24864
0.07771
0.04221
0.16572
0.13650
0.19239
0.29483
0.28549
0.67319
0.31381
0.41731
0.50390
0.56280
0.46299
0.46179
0.38350
0.73701
0.62914
0.50367
0.38560
0.29747

0.2743 (3)
0.2516 (3)
0.1617 (3)
0.0964 (3)
0.1204 (3)
0.2105 (2)
0.2592 (2)
0.2479 (3)
0.0966 (8)
0.0235 (9)
0.0458 (8)
0.0420 (10)
0.0311 (12)
0.1004 (9)
0.0376 (18)
0.047 (2)
0.1105 (16)
0.0064 (15)
0.046 (2)
0.0904 (15)
0.0576 (14)
0.50738
1.16848
1.30018
1.14453
0.95257
0.65252
0.76712
1.02481
0.54271
0.46996
0.83200
1.03989
1.17151
1.28376
1.13279
0.17959
0.65903
0.76618
0.72670
0.07915
0.12487
0.27647
0.47289
0.35805
0.57234
0.50580
0.47443
0.51533

0.50170 (19)
0.5665 (2)
0.5956 (2)
0.5617 (2)
0.4960 (2)
0.46541 (18)
0.39974 (18)
0.24190 (18)
0.2117 (7)
0.2428 (6)
0.2032 (8)
0.1324 (8)
0.1013 (6)
0.1409 (7)
0.1348 (14)
0.1009 (11)
0.1364 (13)
0.2397 (10)
0.0301 (12)
0.2058 (13)
0.2042 (14)
0.09189
0.02460
0.08863
0.26189
0.17929
0.03751
0.09572
0.07922
0.31394
0.20489
0.31979
0.08691
0.02446
0.08015
0.26075
0.55553
0.02433
0.03655
0.15038
0.49123
0.38146
0.33220
0.14244
0.54846
0.37167
0.23587
0.14153
0.02799

0.0474 (12)
0.0618 (17)
0.0728 (17)
0.0702 (16)
0.0585 (16)
0.0451 (12)
0.0443 (12)
0.0495 (12)
0.0510 (19)
0.051 (3)
0.087 (3)
0.096 (3)
0.080 (4)
0.079 (4)
0.096 (3)
0.080 (4)
0.079 (4)
0.051 (3)
0.164 (6)
0.0510 (19)
0.087 (3)
0.1033*
0.1229*
0.1141*
0.0564*
0.0714*
0.1029*
0.0840*
0.0737*
0.0724*
0.0877*
0.0690*
0.0737*
0.1229*
0.1141*
0.0564*
0.0771*
0.1356*
0.1343*
0.1040*
0.0901*
0.0875*
0.0708*
0.0855*
0.0642*
0.0700*
0.0725*
0.0855*
0.1120*

0.626 (15)
0.626 (15)
0.626 (15)
0.626 (15)
0.626 (15)
0.626 (15)
0.374 (15)
0.374 (15)
0.374 (15)
0.374 (15)
0.374 (15)
0.374 (15)
0.374 (15)
0.547 (17)
0.547 (17)
0.547 (17)

0.547 (17)

0.453 (17)
0.453 (17)
0.453 (17)
0.453 (17)
0.645 (5)
0.645 (5)
0.645 (5)

0.645 (5)

0.355 (5)
0.355 (5)

sup-5

supplementary materials
H28B
H30B
H33
H42A
H43A
H45A
H34
H35
H36
H41A
H9
H11C
H12C
H41B
H42B
H43B
H45B

0.31484
0.50850
1.24910
0.60619
0.65156
0.82182
1.25590
1.14792
1.03606
0.66864
1.15574
0.90053
0.85904
0.77744
0.66883
0.59776
0.74390

0.66227
0.72741
0.29524
0.09474
0.08833
0.14934
0.14401
0.03636
0.07680
0.02090
0.41003
0.33935
0.12812
0.00707
0.11383
0.08034
0.16667

0.02430
0.15048
0.59002
0.22400
0.10594
0.12009
0.63954
0.58319
0.47270
0.29011
0.47285
0.29157
0.29047
0.28610
0.22689
0.11108
0.11369

0.1356*
0.1040*
0.0740*
0.1041*
0.1151*
0.0948*
0.0870*
0.0843*
0.0701*
0.0610*
0.0628*
0.0602*
0.0662*
0.0610*
0.1041*
0.1151*
0.0948*

0.355 (5)
0.355 (5)
0.626 (15)
0.626 (15)
0.626 (15)

0.626 (15)

0.374 (15)
0.374 (15)
0.374 (15)
0.374 (15)

Atomic displacement parameters (2)

S1
F1A
O1
N1
N2
N3
N4
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10A
C11A
C12A
C13A
C14A
C15A
C13B
C14B
C15B
C11B
F1B

sup-6

U11
0.1630 (13)
0.171 (3)
0.095 (2)
0.079 (2)
0.063 (2)
0.087 (2)
0.081 (2)
0.065 (3)
0.058 (3)
0.085 (3)
0.101 (4)
0.106 (4)
0.083 (3)
0.053 (2)
0.058 (2)
0.072 (3)
0.060 (4)
0.064 (11)
0.166 (11)
0.143 (5)
0.017 (8)
0.036 (7)
0.143 (5)
0.017 (8)
0.036 (7)
0.064 (11)
0.171 (3)

U22
0.0644 (7)
0.073 (6)
0.0627 (17)
0.0498 (18)
0.0453 (18)
0.0456 (17)
0.0515 (18)
0.048 (2)
0.051 (2)
0.061 (3)
0.078 (3)
0.084 (3)
0.057 (2)
0.051 (2)
0.040 (2)
0.039 (2)
0.057 (2)
0.070 (4)
0.101 (4)
0.080 (4)
0.042 (5)
0.051 (4)
0.080 (4)
0.042 (5)
0.051 (4)
0.070 (4)
0.073 (6)

U33
0.0472 (7)
0.098 (18)
0.0505 (18)
0.056 (2)
0.052 (2)
0.043 (2)
0.049 (2)
0.050 (3)
0.065 (3)
0.081 (4)
0.092 (4)
0.073 (3)
0.072 (3)
0.052 (3)
0.052 (2)
0.048 (3)
0.043 (3)
0.054 (4)
0.057 (3)
0.069 (5)
0.073 (5)
0.050 (3)
0.069 (5)
0.073 (5)
0.050 (3)
0.054 (4)
0.098 (18)

U12
0.0563 (8)
0.060 (3)
0.0313 (15)
0.0262 (16)
0.0125 (15)
0.0233 (16)
0.0227 (16)
0.0154 (19)
0.0217 (18)
0.033 (2)
0.044 (3)
0.034 (3)
0.021 (2)
0.0123 (18)
0.0130 (17)
0.0150 (18)
0.016 (2)
0.026 (8)
0.070 (7)
0.049 (4)
0.007 (6)
0.005 (5)
0.049 (4)
0.007 (6)
0.005 (5)
0.026 (8)
0.060 (3)

U13
0.0142 (7)
0.026 (4)
0.0056 (16)
0.0075 (18)
0.0083 (16)
0.0071 (17)
0.0092 (17)
0.001 (2)
0.004 (2)
0.013 (3)
0.028 (3)
0.036 (3)
0.020 (3)
0.0080 (19)
0.0042 (19)
0.001 (2)
0.001 (3)
0.007 (8)
0.007 (5)
0.011 (4)
0.001 (7)
0.004 (4)
0.011 (4)
0.001 (7)
0.004 (4)
0.007 (8)
0.026 (4)

U23
0.0052 (5)
0.009 (3)
0.0048 (14)
0.0103 (15)
0.0004 (15)
0.0037 (14)
0.0012 (15)
0.0001 (19)
0.0005 (19)
0.003 (2)
0.008 (3)
0.004 (3)
0.003 (2)
0.0025 (18)
0.0025 (17)
0.0048 (17)
0.003 (2)
0.002 (3)
0.021 (3)
0.025 (4)
0.000 (4)
0.004 (2)
0.025 (4)
0.000 (4)
0.004 (2)
0.002 (3)
0.009 (3)

supplementary materials
C10B
C12B
S2
F2A
O2
N5
N6
N7
N8
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25A
C26A
C27A
C28A
C29A
C30A
C28B
C29B
C30B
C26B
F2B
C25B
C27B
S3
F3A
O3
N9
N10
N11
N12
C31
C32
C33
C34
C35
C36
C37
C38
C39
C40A
C41A

0.060 (4)
0.166 (11)
0.1054 (9)
0.187 (5)
0.0734 (18)
0.065 (2)
0.059 (2)
0.081 (2)
0.083 (2)
0.046 (2)
0.048 (2)
0.078 (3)
0.088 (3)
0.080 (3)
0.063 (3)
0.046 (2)
0.049 (2)
0.057 (2)
0.066 (3)
0.074 (3)
0.096 (4)
0.126 (5)
0.136 (5)
0.106 (4)
0.126 (5)
0.136 (5)
0.106 (4)
0.074 (3)
0.187 (5)
0.066 (3)
0.096 (4)
0.1131 (10)
0.292 (18)
0.088 (2)
0.063 (2)
0.0542 (19)
0.067 (2)
0.077 (2)
0.053 (2)
0.045 (2)
0.072 (3)
0.095 (3)
0.098 (3)
0.074 (3)
0.049 (2)
0.046 (2)
0.053 (2)
0.057 (4)
0.025 (7)

0.057 (2)
0.101 (4)
0.0536 (6)
0.156 (4)
0.0495 (15)
0.0560 (19)
0.0531 (18)
0.0503 (18)
0.0583 (19)
0.049 (2)
0.055 (2)
0.061 (3)
0.060 (3)
0.064 (3)
0.063 (2)
0.050 (2)
0.049 (2)
0.053 (2)
0.070 (3)
0.082 (3)
0.112 (4)
0.141 (6)
0.100 (4)
0.100 (4)
0.141 (6)
0.100 (4)
0.100 (4)
0.082 (3)
0.156 (4)
0.070 (3)
0.112 (4)
0.0550 (6)
0.175 (4)
0.0521 (15)
0.0483 (18)
0.0480 (17)
0.0447 (16)
0.0442 (17)
0.049 (2)
0.053 (2)
0.065 (3)
0.076 (3)
0.057 (2)
0.053 (2)
0.044 (2)
0.046 (2)
0.054 (2)
0.047 (3)
0.045 (5)

0.043 (3)
0.057 (3)
0.0806 (9)
0.081 (3)
0.0530 (17)
0.0413 (19)
0.046 (2)
0.047 (2)
0.043 (2)
0.047 (2)
0.047 (3)
0.058 (3)
0.086 (4)
0.087 (4)
0.058 (3)
0.050 (2)
0.037 (2)
0.053 (3)
0.042 (3)
0.049 (3)
0.062 (4)
0.052 (3)
0.091 (5)
0.055 (3)
0.052 (3)
0.091 (5)
0.055 (3)
0.049 (3)
0.081 (3)
0.042 (3)
0.062 (4)
0.0586 (8)
0.063 (3)
0.0539 (18)
0.051 (2)
0.0428 (19)
0.0403 (19)
0.046 (2)
0.047 (2)
0.046 (2)
0.053 (3)
0.048 (3)
0.057 (3)
0.053 (3)
0.044 (2)
0.042 (2)
0.042 (2)
0.047 (3)
0.076 (3)

0.016 (2)
0.070 (7)
0.0286 (6)
0.042 (4)
0.0211 (13)
0.0184 (16)
0.0181 (15)
0.0237 (16)
0.0247 (17)
0.0100 (17)
0.0150 (17)
0.028 (2)
0.035 (2)
0.036 (2)
0.026 (2)
0.0155 (17)
0.0123 (17)
0.0131 (18)
0.013 (2)
0.001 (2)
0.004 (3)
0.001 (4)
0.023 (4)
0.034 (3)
0.001 (4)
0.023 (4)
0.034 (3)
0.001 (2)
0.042 (4)
0.013 (2)
0.004 (3)
0.0233 (6)
0.122 (11)
0.0302 (14)
0.0230 (15)
0.0165 (14)
0.0158 (14)
0.0190 (15)
0.0159 (17)
0.0153 (17)
0.025 (2)
0.025 (2)
0.025 (2)
0.0247 (19)
0.0145 (16)
0.0139 (16)
0.0142 (18)
0.008 (2)
0.002 (5)

0.001 (3)
0.007 (5)
0.0264 (7)
0.040 (3)
0.0128 (13)
0.0111 (16)
0.0037 (16)
0.0203 (17)
0.0149 (17)
0.0018 (18)
0.0027 (19)
0.005 (2)
0.009 (3)
0.014 (3)
0.002 (2)
0.0051 (19)
0.0034 (18)
0.006 (2)
0.002 (2)
0.014 (2)
0.019 (3)
0.001 (3)
0.001 (4)
0.007 (3)
0.001 (3)
0.001 (4)
0.007 (3)
0.014 (2)
0.040 (3)
0.002 (2)
0.019 (3)
0.0331 (7)
0.021 (8)
0.0128 (14)
0.0094 (16)
0.0097 (15)
0.0100 (16)
0.0147 (16)
0.0005 (19)
0.0051 (18)
0.014 (2)
0.024 (2)
0.018 (2)
0.010 (2)
0.0085 (18)
0.0029 (18)
0.0074 (18)
0.010 (3)
0.006 (5)

0.003 (2)
0.021 (3)
0.0083 (5)
0.010 (3)
0.0081 (12)
0.0009 (15)
0.0072 (15)
0.0018 (15)
0.0008 (16)
0.0051 (18)
0.0054 (18)
0.007 (2)
0.001 (2)
0.025 (3)
0.017 (2)
0.0066 (18)
0.0076 (17)
0.001 (2)
0.005 (2)
0.009 (2)
0.024 (3)
0.014 (3)
0.030 (3)
0.021 (3)
0.014 (3)
0.030 (3)
0.021 (3)
0.009 (2)
0.010 (3)
0.005 (2)
0.024 (3)
0.0093 (5)
0.038 (3)
0.0043 (13)
0.0048 (15)
0.0037 (14)
0.0016 (14)
0.0039 (14)
0.0039 (18)
0.0034 (18)
0.006 (2)
0.009 (2)
0.010 (2)
0.0001 (19)
0.0027 (17)
0.0028 (17)
0.0043 (17)
0.008 (2)
0.001 (3)

sup-7

supplementary materials
C42A
C43A
C44A
C45A
C43B
C44B
C45B
C41B
F3B
C40B
C42B

0.087 (6)
0.099 (7)
0.090 (10)
0.115 (9)
0.099 (7)
0.090 (10)
0.115 (9)
0.025 (7)
0.292 (18)
0.057 (4)
0.087 (6)

0.056 (4)
0.071 (4)
0.082 (6)
0.065 (4)
0.071 (4)
0.082 (6)
0.065 (4)
0.045 (5)
0.175 (4)
0.047 (3)
0.056 (4)

0.122 (5)
0.118 (5)
0.060 (4)
0.058 (4)
0.118 (5)
0.060 (4)
0.058 (4)
0.076 (3)
0.063 (3)
0.047 (3)
0.122 (5)

0.026 (4)
0.013 (4)
0.004 (8)
0.025 (5)
0.013 (4)
0.004 (8)
0.025 (5)
0.002 (5)
0.122 (11)
0.008 (2)
0.026 (4)

0.022 (5)
0.040 (5)
0.035 (6)
0.025 (5)
0.040 (5)
0.035 (6)
0.025 (5)
0.006 (5)
0.021 (8)
0.010 (3)
0.022 (5)

0.006 (3)
0.034 (3)
0.017 (4)
0.006 (3)
0.034 (3)
0.017 (4)
0.006 (3)
0.001 (3)
0.038 (3)
0.008 (2)
0.006 (3)

Geometric parameters (, )
S1C9
S2C24
S3C39
F1AC14A
F1BC14B
F2AC27A
F2BC29B
F3AC44A
F3BC44B
O1C1
O2C16
O3C31
N1C1
N1C2
N2C8
N2N3
N3C9
N4C9
N4C10B
N4C10A
N1H1
N3H3A
N4H4A
N5C16
N5C17
N6C23
N6N7
N7C24
N8C25B
N8C24
N8C25A
N5H5A
N7H7
N8H8
N9C31

sup-8

1.641 (4)
1.650 (4)
1.651 (4)
1.35 (12)
1.36 (16)
1.356 (6)
1.331 (5)
1.344 (18)
1.66 (4)
1.217 (5)
1.238 (5)
1.241 (4)
1.343 (5)
1.398 (5)
1.288 (4)
1.353 (4)
1.366 (4)
1.341 (5)
1.38 (2)
1.432 (16)
0.8600
0.8600
0.8600
1.338 (5)
1.410 (5)
1.295 (5)
1.338 (4)
1.390 (5)
1.396 (5)
1.328 (5)
1.391 (5)
0.8600
0.8600
0.8600
1.340 (4)

C12AH12A
C12BH12B
C13AH13A
C13BH13B
C15AH15A
C15BH15B
C16C23
C17C18
C17C22
C18C19
C19C20
C20C21
C21C22
C22C23
C25AC30A
C25AC26A
C25BC26B
C25BC30B
C26AC27A
C26BC27B
C27AC28A
C27BC28B
C28AC29A
C28BC29B
C29AC30A
C29BC30B
C18H18
C19H19
C20H20
C21H21
C26AH26A
C26BH26B
C27BH27B
C28AH28A
C28BH28B

0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
1.495 (5)
1.376 (6)
1.394 (5)
1.376 (6)
1.377 (8)
1.382 (6)
1.374 (6)
1.449 (5)
1.389 (6)
1.390 (6)
1.390 (4)
1.390 (4)
1.390 (5)
1.390 (5)
1.390 (6)
1.390 (4)
1.390 (7)
1.390 (6)
1.390 (8)
1.390 (6)
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300

supplementary materials
N9C32
N10C38
N10N11
N11C39
N12C40B
N12C39
N12C40A
N9H9
N11H11C
N12H12C
C1C8
C2C3
C2C7
C3C4
C4C5
C5C6
C6C7
C7C8
C10AC15A
C10AC11A
C10BC15B
C10BC11B
C11AC12A
C11BC12B
C12AC13A
C12BC13B
C13AC14A
C13BC14B
C14AC15A
C14BC15B
C3H3
C4H4
C5H5
C6H6
C11AH11A
C11BH11B

1.413 (4)
1.287 (4)
1.351 (4)
1.370 (5)
1.45 (2)
1.331 (5)
1.379 (13)
0.8600
0.8600
0.8600
1.505 (5)
1.368 (6)
1.392 (6)
1.369 (8)
1.375 (7)
1.391 (6)
1.374 (6)
1.443 (5)
1.39 (2)
1.39 (3)
1.39 (3)
1.39 (4)
1.39 (3)
1.39 (3)
1.39 (3)
1.39 (3)
1.39 (3)
1.39 (4)
1.39 (2)
1.39 (3)
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300

C29AH29A
C30AH30A
C30BH30B
C31C38
C32C37
C32C33
C33C34
C34C35
C35C36
C36C37
C37C38
C40AC41A
C40AC45A
C40BC41B
C40BC45B
C41AC42A
C41BC42B
C42AC43A
C42BC43B
C43AC44A
C43BC44B
C44AC45A
C44BC45B
C33H33
C34H34
C35H35
C36H36
C41AH41A
C41BH41B
C42AH42A
C42BH42B
C43AH43A
C43BH43B
C45AH45A
C45BH45B

0.9300
0.9300
0.9300
1.496 (5)
1.397 (5)
1.362 (5)
1.372 (6)
1.384 (6)
1.382 (6)
1.385 (5)
1.442 (5)
1.390 (17)
1.391 (19)
1.39 (3)
1.39 (4)
1.390 (18)
1.39 (3)
1.39 (2)
1.39 (4)
1.39 (2)
1.40 (4)
1.39 (2)
1.39 (3)
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300
0.9300

S1C15A
S1C15B
S2C30A
S2N3
S2C30B

3.223 (18)
3.20 (2)
3.208 (6)
3.454 (3)
3.195 (4)

C23C38
C23N11
C23C31
C24O1
C24C1

3.565 (4)
3.406 (4)
3.568 (5)
3.401 (5)
3.471 (6)

S2C33i
S3C26A
S3C26B
S3C45B
S3C45A

3.618 (4)

C25AC7

3.473 (6)

3.646 (4)
3.653 (3)
3.23 (2)
3.260 (13)

C25AC8
C25BC8
C25BC7
C26AC2

3.559 (6)
3.577 (5)
3.498 (6)
3.501 (6)

S1H20ii

2.9500

C26AC7

3.524 (6)

iii

2.9900

C26AS3

3.646 (4)

S1H18

sup-9

supplementary materials
S1H15B
S1H15A

2.5400
2.5700

C26BC7
C26BC2

3.532 (5)
3.521 (5)

S2H42Aii

2.8700

C26BS3

3.653 (3)

2.9200

C27AC6

S2H33

ii

2.8000

S2H42B
S2H30B
i

S2H34
S2H30A

C27AC27A
C27AC5

3.424 (5)

2.5300
3.1800

C27BC5

3.415 (6)

2.5400

C27BC6

S3H26B

3.1500

S3H45A
iv

S3H3
S3H45B
S3H28A

3.511 (6)
v

3.406 (6)
3.507 (5)

3.421 (5)

2.7200

C27BC27B
C28AC6

3.1400

3.314 (7)

2.6200

C28AF2A
C28BC6

2.9600

C30AS2

3.542 (7)
3.551 (7)
3.208 (6)

iv

3.597 (8)

iv

3.588 (7)

S3H8

3.1000

S3H26A

3.1500

C30BC4

S3H28Bv

2.9700

C30BS2

3.195 (4)

F2AC4vi

3.215 (7)

C30BC5iv

3.567 (8)

F2AC28Av

3.314 (7)

C31C23

3.568 (5)

F2BF3Av

2.534 (17)

C31C16

3.247 (5)

2.534 (17)

C32C20iv

3.507 (6)

iv

3.531 (6)

iv

F3AF2Bv
v

F3BC11A
F1AH21

ii

ii

F1BH21
F2AH4

vi

3.30 (3)

F2BH12A

C32C19

2.6200

C33C19

3.484 (7)

2.7100

iii

3.305 (5)

2.4800
vii

C30AC5

2.8000

C33O1

iv

3.472 (6)

C33C18
C33S2

3.618 (4)

iii

3.405 (5)

F3BH11A
O1C24
O1N3

2.4600
3.401 (5)
2.778 (4)

C34O1
C36C18
C37N5

O1C34iii

3.405 (5)

C37C20iv

3.539 (5)

O1N5iii
O1N2

2.881 (4)

C37C17

3.500 (5)

3.028 (4)

C38C16

3.552 (5)

3.305 (5)

C38C22

3.510 (5)

3.032 (4)
2.785 (4)

C38N5
C38C23

3.431 (4)
3.565 (4)

3.220 (4)

C38C17

3.420 (5)

2.871 (3)

C39C21

O1C33
O2N6
O2N7

iii

O2C16iii
i

O2N9

O3N11
O3N1

O3N10
iii

O1H5A
O1H3A
O2H7

sup-10

3.587 (5)

C39C15A

3.280 (16)

2.837 (3)

C39C14A

3.565 (16)

3.020 (3)

C40BN4

3.31 (2)

C41BN2

3.37 (2)

3.594 (18)

3.39 (2)

2.767 (3)

iv

3.510 (6)
3.428 (4)

2.0500
2.1100
2.1100

C41BC9

C42BN2

supplementary materials
O2H9i
O3H11C
iv

2.0600

C43BC10Axi

3.41 (3)

2.0900

xi

3.23 (3)

xi

3.28 (3)

xi

2.0300

O3H1

C43BC11A
C44BC11A

iv

2.9200

C44BC12A

3.27 (3)

viii

N1O3
N2O1
N2N4

2.837 (3)

C45AS3

3.260 (13)

3.028 (4)
2.596 (4)

C45BS3
C1H3A

3.23 (2)
2.4800

N2C41Bix

3.37 (2)

C9H15A

2.8400

N2C42Bix
N3O1
N3S2

3.39 (2)

C9H15B

2.9000

2.778 (4)
3.454 (3)

C16H7
C24H30A

2.4900
2.8500

N4C40Bix
N4N2

3.31 (2)

C24H30B

2.8600

2.596 (4)

C31H11C

N5C38

3.431 (4)

C34H41B

iii

N5O1
N5C37

2.881 (4)

C39H45B

3.428 (4)

C39H45A

N6O2

3.032 (4)

C41BH34

N6N8

2.599 (4)

H1O3viii

2.0300

N7O2

2.785 (4)

H3O3viii

2.9200

N8N6

2.599 (4)

H3S3viii

O3H3

N9O2
N10N12
N10C22

2.871 (3)

N10O3

3.020 (3)

N11C22
N11O3

2.4900
xii

3.0800
2.9400
2.8300

xii

3.0900

3.1400
viii

H3H11C
H3AC1
H3AO1

2.5700

2.4800

3.426 (5)
2.767 (3)

H4F2Avi
H4AH11A
H4AH11B

N11C15Ax

3.307 (17)

H4AN2

2.1300

N11C23

3.406 (4)

H5AO1iii

2.0500

2.590 (4)
3.248 (5)

N12N10

2.3800
2.1100

2.590 (4)

H7H33

2.5100

3.348 (16)

H7O2

2.1100

3.399 (19)

H7C16

2.4900

2.1300
2.1400

H8S3
H8N6

3.1000
2.1400

2.8000

H8H26B

2.2000

2.1300

H8H26A

2.2000

N12C15A
N12C10B
N2H4A
N6H8

2.4800
2.1100

N10H15Ax
N10H12C
x

N11H15A
C1C24

2.9100

C2C26A

3.501 (6)

C2C26B
vi

H9O2
H11AH4A

2.0600
2.4600

3.521 (5)

H11AF3Bv
H11BH4A

C4F2A

3.215 (7)

H11CC31

2.4900

C4C30Bviii
C5C27A

3.588 (7)

H11CH3iv
H11CO3

2.5700

viii

C5C30B

3.471 (6)

3.406 (6)
3.567 (8)

H12AF2B

vii

2.3800
2.1100

2.0900
2.8000

sup-11

supplementary materials
C5C30Aviii
C5C27B
C6C27A

3.597 (8)

H12CH41A

2.4400

3.415 (6)
3.511 (6)

H12CH41B
H12CN10

2.2100
2.1300

C6C27B

3.507 (5)

2.9100

C6C28B
C6C28A

3.551 (7)
3.542 (7)

H15AN11ix
H15AS1
H15AC9

C7C26B

3.532 (5)

2.8000

C7C26A
C7C25A

3.524 (6)
3.473 (6)

H15AN10ix
H15BC9
H15BS1

C7C25B

3.498 (6)

H18S1iii

2.9900

3.559 (6)

xi

C8C25A
C8C25B

3.577 (5)

ix

2.5700
2.8400
2.9000
2.5400
2.9500

H20S1

xi

2.7100

xi

H21F1B

3.594 (18)

H21F1A

2.6200

3.41 (3)

H26AH8

2.2000

3.399 (19)

H26AS3

3.1500

C11AC43Bii

3.23 (3)

H26BS3

3.1500

C11AF3Bv

3.30 (3)

H26BH8

2.2000

C11AC44Bii

3.28 (3)

H28AS3v

2.9600

C12AC44Bii

3.27 (3)

H28BS3v

2.9700

C14AC39ix

3.565 (16)

H30AC24

2.8500

ix

3.280 (16)

H30AS2

2.5400

ix

3.348 (16)

H30BC24

2.8600

3.223 (18)

H30BS2

2.5300

C9C41B

ii

C10AC43B
C10BN12

C15AC39

ix

C15AN12
C15AS1

ix

C15AN11

3.307 (17)

H33H7

2.5100

C15BS1

3.20 (2)

H33S2i

2.9200

C16O2iii

3.220 (4)

H34S2i

3.1800

C16C38

3.552 (5)

H34H41Axii

2.5900

3.247 (5)

xii

3.0900

xii

2.4400

C16C31
iii

C16C16
C17C38
C17C37

viii

C18C33
C18C36

H34C41B

3.217 (5)

H34H41B

3.420 (5)

xii

H36H36

3.500 (5)

H41AH34

2.5900

3.472 (6)

H41AH12C

2.4400

3.510 (6)

xii

3.0800

xii

2.4400
2.2100

H41BC34

viii

3.531 (6)

H41BH34

viii

3.484 (7)

H41BH12C

C19C32
C19C33

viii

C20C32

viii

2.5800

xii

3.507 (6)

xi

2.8700

xi

H42AS2

C20C37
C21C39
C22C38
C22N10
C22N11

3.539 (5)

H42BS2
H45AS3
H45AC39
H45BS3
H45BC39

2.8000

3.587 (5)
3.510 (5)
3.248 (5)
3.426 (5)

C1N1C2
N3N2C8

111.9 (3)
117.6 (3)

C16C23C22
N6C23C22

107.0 (3)
124.8 (3)

sup-12

2.7200
2.8300
2.6200
2.9400

supplementary materials
N2N3C9
C9N4C10A
C9N4C10B
C1N1H1
C2N1H1
N2N3H3A
C9N3H3A
C10BN4H4A
C9N4H4A
C10AN4H4A
C16N5C17
N7N6C23
N6N7C24
C24N8C25A
C24N8C25B
C17N5H5A
C16N5H5A
C24N7H7
N6N7H7
C24N8H8
C25AN8H8
C25BN8H8
C31N9C32
N11N10C38
N10N11C39
C39N12C40B
C39N12C40A
C31N9H9
C32N9H9
C39N11H11C
N10N11H11C
C40BN12H12C
C39N12H12C
C40AN12H12C
O1C1N1
O1C1C8
N1C1C8
C3C2C7
N1C2C3
N1C2C7
C2C3C4
C3C4C5
C4C5C6
C5C6C7
C2C7C8
C2C7C6
C6C7C8
N2C8C7
N2C8C1

121.8 (3)
131.9 (8)
130.5 (10)
124.00
124.00
119.00
119.00
115.00
114.00
114.00
111.7 (3)
117.9 (3)
120.8 (3)
132.0 (3)
131.1 (3)
124.00
124.00
120.00
120.00
114.00
114.00
115.00
111.3 (3)
117.8 (3)
120.8 (3)
130.4 (10)
130.8 (6)
124.00
124.00
120.00
120.00
114.00
115.00
115.00
127.4 (4)
126.9 (4)
105.6 (3)
121.7 (4)
128.9 (4)
109.3 (3)
117.9 (4)
121.4 (5)
120.9 (5)
118.0 (4)
106.8 (3)
120.2 (4)
133.1 (4)
125.7 (3)
127.9 (3)

S2C24N7
S2C24N8
N7C24N8
N8C25AC30A
N8C25AC26A
C26AC25AC30A
C26BC25BC30B
N8C25BC26B
N8C25BC30B
C25AC26AC27A
C25BC26BC27B
F2AC27AC26A
C26AC27AC28A
F2AC27AC28A
C26BC27BC28B
C27AC28AC29A
C27BC28BC29B
C28AC29AC30A
F2BC29BC30B
F2BC29BC28B
C28BC29BC30B
C25AC30AC29A
C25BC30BC29B
C19C18H18
C17C18H18
C18C19H19
C20C19H19
C21C20H20
C19C20H20
C20C21H21
C22C21H21
C27AC26AH26A
C25AC26AH26A
C27BC26BH26B
C25BC26BH26B
C28BC27BH27B
C26BC27BH27B
C29AC28AH28A
C27AC28AH28A
C27BC28BH28B
C29BC28BH28B
C28AC29AH29A
C30AC29AH29A
C29AC30AH30A
C25AC30AH30A
C25BC30BH30B
C29BC30BH30B
O3C31N9
O3C31C38

116.8 (3)
130.1 (3)
113.1 (3)
124.4 (4)
115.6 (3)
120.0 (4)
120.0 (3)
114.9 (2)
125.2 (3)
120.0 (4)
120.0 (3)
117.6 (4)
120.0 (4)
122.3 (3)
120.0 (3)
120.0 (4)
120.0 (3)
120.0 (4)
112.7 (4)
127.3 (4)
120.0 (3)
120.0 (5)
120.0 (4)
122.00
122.00
119.00
119.00
120.00
120.00
121.00
121.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
127.5 (3)
126.0 (3)

sup-13

supplementary materials
C1C8C7
S1C9N4
N3C9N4
S1C9N3
C11AC10AC15A
N4C10AC11A
N4C10AC15A
N4C10BC11B
C11BC10BC15B
N4C10BC15B
C10AC11AC12A
C10BC11BC12B
C11AC12AC13A
C11BC12BC13B
C12AC13AC14A
C12BC13BC14B
F1AC14AC15A
F1AC14AC13A
C13AC14AC15A
F1BC14BC13B
C13BC14BC15B
F1BC14BC15B
C10AC15AC14A
C10BC15BC14B
C4C3H3
C2C3H3
C3C4H4
C5C4H4
C4C5H5
C6C5H5
C7C6H6
C5C6H6
C10AC11AH11A
C12AC11AH11A
C10BC11BH11B
C12BC11BH11B
C11AC12AH12A
C13AC12AH12A
C13BC12BH12B
C11BC12BH12B
C14AC13AH13A
C12AC13AH13A
C14BC13BH13B
C12BC13BH13B
C10AC15AH15A
C14AC15AH15A
C14BC15BH15B
C10BC15BH15B
N5C16C23

sup-14

106.4 (3)
129.3 (3)
112.6 (3)
118.1 (3)
120.0 (15)
118.8 (14)
120.7 (15)
112.3 (17)
120.1 (19)
127 (2)
120.0 (16)
120 (2)
120.0 (17)
120 (2)
120.0 (15)
120.1 (19)
121 (6)
116 (6)
120.0 (15)
119 (7)
120.0 (18)
115 (7)
120.1 (16)
120 (2)
121.00
121.00
119.00
119.00
120.00
120.00
121.00
121.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
105.9 (3)

N9C31C38
N9C32C33
N9C32C37
C33C32C37
C32C33C34
C33C34C35
C34C35C36
C35C36C37
C32C37C36
C36C37C38
C32C37C38
N10C38C37
C31C38C37
N10C38C31
S3C39N11
S3C39N12
N11C39N12
N12C40AC41A
N12C40AC45A
C41AC40AC45A
N12C40BC45B
N12C40BC41B
C41BC40BC45B
C40AC41AC42A
C40BC41BC42B
C41AC42AC43A
C41BC42BC43B
C42AC43AC44A
C42BC43BC44B
C43AC44AC45A
F3AC44AC43A
F3AC44AC45A
F3BC44BC45B
F3BC44BC43B
C43BC44BC45B
C40AC45AC44A
C40BC45BC44B
C32C33H33
C34C33H33
C33C34H34
C35C34H34
C34C35H35
C36C35H35
C35C36H36
C37C36H36
C40AC41AH41A
C42AC41AH41A
C42BC41BH41B
C40BC41BH41B

106.6 (3)
128.5 (3)
108.9 (3)
122.6 (4)
117.2 (4)
122.2 (4)
120.0 (4)
118.8 (4)
119.2 (3)
133.8 (3)
107.0 (3)
125.5 (3)
106.4 (3)
128.2 (3)
117.9 (3)
128.8 (3)
113.3 (3)
119.5 (11)
119.7 (10)
120.0 (11)
126.4 (18)
112.7 (19)
120 (2)
120.0 (12)
120 (2)
120.0 (12)
120 (2)
120.0 (12)
120 (2)
120.0 (12)
107.4 (14)
125.4 (15)
98 (2)
122 (2)
120 (2)
120.0 (12)
120 (2)
121.00
121.00
119.00
119.00
120.00
120.00
121.00
121.00
120.00
120.00
120.00
120.00

supplementary materials
O2C16N5
O2C16C23
N5C17C22
N5C17C18
C18C17C22
C17C18C19
C18C19C20
C19C20C21
C20C21C22
C21C22C23
C17C22C23
C17C22C21
N6C23C16

127.6 (3)
126.5 (3)
109.3 (3)
128.6 (3)
122.1 (4)
116.5 (4)
122.3 (4)
120.8 (4)
118.0 (4)
133.5 (4)
106.1 (3)
120.4 (4)
128.2 (3)

C43AC42AH42A
C41AC42AH42A
C43BC42BH42B
C41BC42BH42B
C44AC43AH43A
C42AC43AH43A
C44BC43BH43B
C42BC43BH43B
C44AC45AH45A
C40AC45AH45A
C40BC45BH45B
C44BC45BH45B

120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00
120.00

C2N1C1O1
C2N1C1C8
C1N1C2C3
C1N1C2C7
C8N2N3C9
N3N2C8C1
N3N2C8C7
N2N3C9S1
N2N3C9N4
C10AN4C9S1
C10AN4C9N3
C9N4C10AC11A
C9N4C10AC15A
C16N5C17C18
C16N5C17C22
C17N5C16C23
C17N5C16O2
N7N6C23C16
C23N6N7C24
N7N6C23C22
N6N7C24N8
N6N7C24S2
C24N8C25AC26A
C24N8C25AC30A
C25AN8C24S2
C25AN8C24N7
C31N9C32C37
C31N9C32C33
C32N9C31O3
C32N9C31C38
N11N10C38C31
C38N10N11C39
N11N10C38C37
N10N11C39S3
N10N11C39N12
C40AN12C39S3

178.5 (4)
0.4 (4)
179.8 (4)
0.0 (5)
173.8 (3)
2.7 (5)
178.0 (3)
178.8 (3)
1.0 (5)
2.8 (10)
177.4 (9)
161.3 (10)
26.6 (19)
179.0 (4)
1.2 (4)
1.8 (4)
179.4 (4)
1.7 (5)
179.6 (3)
179.7 (3)
6.0 (5)
173.4 (3)
172.7 (4)
8.5 (8)
1.6 (7)
177.7 (4)
0.3 (4)
179.2 (4)
179.6 (3)
0.3 (4)
1.1 (5)
178.7 (3)
177.1 (3)
176.3 (3)
3.4 (5)
0.2 (9)

C11AC12AC13AC14A
C12AC13AC14AF1A
C12AC13AC14AC15A
C13AC14AC15AC10A
F1AC14AC15AC10A
O2C16C23N6
N5C16C23N6
N5C16C23C22
O2C16C23C22
N5C17C18C19
C18C17C22C23
N5C17C22C21
N5C17C22C23
C22C17C18C19
C18C17C22C21
C17C18C19C20
C18C19C20C21
C19C20C21C22
C20C21C22C17
C20C21C22C23
C17C22C23N6
C17C22C23C16
C21C22C23C16
C21C22C23N6
C30AC25AC26AC27A
N8C25AC26AC27A
C26AC25AC30AC29A
N8C25AC30AC29A
C25AC26AC27AF2A
C25AC26AC27AC28A
C26AC27AC28AC29A
F2AC27AC28AC29A
C27AC28AC29AC30A
C28AC29AC30AC25A
O3C31C38N10
O3C31C38C37

0(2)
161 (4)
0(2)
0(2)
160 (4)
2.3 (6)
176.6 (3)
1.7 (4)
179.5 (3)
178.1 (4)
178.0 (3)
178.2 (3)
0.1 (4)
0.6 (6)
0.3 (6)
0.9 (7)
0.9 (7)
0.5 (6)
0.2 (6)
177.6 (4)
177.4 (3)
0.9 (4)
178.9 (4)
0.6 (7)
0.0 (7)
178.9 (4)
0.0 (8)
178.9 (5)
176.5 (4)
0.0 (6)
0.0 (7)
176.3 (5)
0.0 (9)
0.0 (9)
1.9 (6)
179.6 (3)

sup-15

supplementary materials
C39N12C40AC45A
41.9 (14)
N9C31C38N10
178.8 (3)
C40AN12C39N11
180.0 (8)
N9C31C38C37
0.3 (4)
C39N12C40AC41A
148.3 (8)
N9C32C33C34
180.0 (4)
N1C1C8C7
0.6 (4)
C37C32C33C34
0.6 (6)
N1C1C8N2
178.7 (4)
N9C32C37C36
179.6 (3)
O1C1C8N2
0.6 (7)
N9C32C37C38
0.1 (4)
O1C1C8C7
178.8 (4)
C33C32C37C36
0.1 (6)
C7C2C3C4
0.1 (7)
C33C32C37C38
179.5 (3)
N1C2C3C4
179.7 (4)
C32C33C34C35
0.9 (7)
N1C2C7C6
179.8 (4)
C33C34C35C36
0.8 (7)
N1C2C7C8
0.4 (5)
C34C35C36C37
0.4 (6)
C3C2C7C8
179.8 (4)
C35C36C37C32
0.0 (6)
C3C2C7C6
0.4 (6)
C35C36C37C38
179.4 (4)
C2C3C4C5
0.5 (7)
C32C37C38N10
178.7 (3)
C3C4C5C6
0.4 (7)
C32C37C38C31
0.1 (4)
C4C5C6C7
0.1 (7)
C36C37C38N10
0.8 (6)
C5C6C7C8
179.6 (4)
C36C37C38C31
179.3 (4)
C5C6C7C2
0.5 (6)
N12C40AC41AC42A
169.7 (10)
C2C7C8N2
178.8 (4)
C45AC40AC41AC42A
0.0 (18)
C6C7C8C1
179.9 (5)
N12C40AC45AC44A
169.7 (11)
C6C7C8N2
0.5 (7)
C41AC40AC45AC44A
0.0 (19)
C2C7C8C1
0.7 (4)
C40AC41AC42AC43A
0.0 (18)
C11AC10AC15AC14A
0(2)
C41AC42AC43AC44A
0(2)
N4C10AC15AC14A
172.1 (13)
C42AC43AC44AF3A
152.0 (14)
C15AC10AC11AC12A
0(2)
C42AC43AC44AC45A
0(2)
N4C10AC11AC12A
172.5 (14)
F3AC44AC45AC40A
146.6 (15)
C10AC11AC12AC13A
1(3)
C43AC44AC45AC40A
0(2)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x, y+1, z; (iii) x+1, y+1, z+1; (iv) x+1, y, z; (v) x+1, y+1, z; (vi) x, y+1, z; (vii)
x+1, y+2, z; (viii) x1, y, z; (ix) x1, y+1, z; (x) x+1, y1, z; (xi) x, y1, z; (xii) x+2, y, z+1.

Hydrogen-bond geometry (, )
DHA

DH

HA

DA

DHA

N1H1O3
N3H3AO1
N4H4AN2

0.86

2.03

2.837 (3)

155

0.86
0.86

2.11
2.13

2.778 (4)
2.596 (4)

134
114

N5H5AO1iii
N7H7O2
N8H8N6

0.86

2.05

2.881 (4)

164

0.86
0.86

2.11
2.14

2.785 (4)
2.599 (4)

135
113

N9H9O2i
N11H11CO3
N12H12CN10

0.86

2.06

2.871 (3)

157

0.86
0.86

2.09
2.13

2.767 (3)
2.590 (4)

135
113

C4H4F2Avi
C15AH15AS1
C30AH30AS2

0.93

2.48

3.215 (7)

136

0.93
0.93

2.57
2.54

3.223 (18)
3.208 (6)

127
129

viii

0.93
2.87
3.763 (12)
C42AH42AS2xi
C45AH45AS3
0.93
2.72
3.260 (13)
Symmetry codes: (viii) x1, y, z; (iii) x+1, y+1, z+1; (i) x+2, y+1, z+1; (vi) x, y+1, z; (xi) x, y1, z.

sup-16

162
118

supplementary materials
Fig. 1

sup-17

supplementary materials
Fig. 2

sup-18