Crystal structure of S-hexyl (E)-3-(2-hy­droxy­benzyl­idene)di­thio­carbazate

The title compound crystallizes with four independent mol­ecules in the asymmetric unit, which have very comparable geometries. In the crystal, mol­ecules are connected in pairs through N—H...S hydrogen bonds, forming dimers.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.065
• wR factor = 0.176
• Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT073_ALERT_1_A H-atoms ref, but _hydrogen_treatment reported as     constr Check

Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    N1     --  C7      ..        8.0 s.u.

Alert level C
THETM01_ALERT_3_C  The value of sine(theta_max)/wavelength is less than 0.590
            Calculated sin(theta_max)/wavelength =    0.5814
PLAT023_ALERT_3_C Resolution (too) Low [sin(theta)/Lambda < 0.6]..      63.69 Degree
PLAT057_ALERT_3_C Correction for Absorption Required   RT(exp) ...       1.11 Do !
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.22 Report
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S2     --  C9      ..        5.3 s.u.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     --  C1      ..        7.0 s.u.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N2     --  C8      ..        7.0 s.u.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C2     --  C3      ..        5.7 s.u.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O4     --  C43     ..        6.5 s.u.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C44    --  C45     ..        6.0 s.u.
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............    0.00431 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1 Note
              C14 H20 N2 O S2
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      7.719 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.581         24 Report

Alert level G
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT  Unusually Large       0.11 Report
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) Still          38 %
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          2 Report
PLAT954_ALERT_1_G Reported (CIF) and Actual (FCF) Kmax Differ by .          1 Units
PLAT955_ALERT_1_G Reported (CIF) and Actual (FCF) Lmax Differ by .          1 Units

   1 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
  14 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 ALERT type 2 Indicator that the structure model may be wrong or deficient
   8 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Chemical context

Bidentate Schiff bases of S-methyl or S-benzyl di­thio­carbaza­tes and their metal complexes have received considerable attention for their possible bioactivities (Chan et al., 2008; How et al., 2008; Zangrando et al., 2015; Ali et al., 2002; Chew et al., 2004; Crouse et al., 2004). As part of our ongoing structural studies of S-containing Schiff bases, we report herein on the structure of a molecule having a hexyl alkyl chain, similar to other ligands reported by our group (Begum, Zangrando et al., 2015; Begum, Howlader, Miyatake et al., 2015; Howlader et al., 2015) but differing in their ability to act as tridentate ligands in metal coordination (Begum, Howlader, Sheikh et al., 2015).

S2. Structural commentary

The four independent molecules (A--D) of the title compound are shown in Figs. 1 and 2. The Schiff base exists in its thione tautomeric form with the di­thio­carbazate fragment adopting an E conformation with respect to the C═N bond of the benzyl­idene moiety. The β-nitro­gen and the thio­keto sulfur are trans located with respect to bond C8—N2 bond in molecule A (and similarly for molecules B, C and D). All non-H atoms in the molecules are almost co-planar indicating, except for the alkyl chain, electron delocalization within them. The maximum deviation from the mean plane is shown by the thio­ketone atoms S1, S3, S5 and S7 in the four independent molecules (r.m.s deviations of 0.086, 0.118, 0.138 and 0.183 Å, respectively). The bond lengths and angles are comparable to those reported for S-hexyl (E)-3-(4-methyl­benzyl­idene)di­thio­carbazate (Howlader et al., 2015) and S-hexyl (E)-3-(4-meth­oxy­benzyl­idene)di­thio­carbazate (Begum, Howlader, Miyatake et al., 2015). The hexyl chain in all four molecules has an extended anti-zigzag conformation. This compound in its deprotonated imino thiol­ate form has been reported to act as a tridentate ligand through N–, S– and O-donors to form a binuclear copper(II) complex (Begum, Howlader, Sheikh et al., 2015).

S3. Supra­molecular features

The crystal packing of the title compound (Fig. 2), indicates that the molecules are connected by pairs of N—H···S hydrogen bonds (Table 1) to form A–D dimers, and B–B and C–C inversion dimers, all with R₂²(8) ring motifs.

S4. Synthesis and crystallization

To an ethano­lic solution of KOH (2.81 g, 0.05 mol), hydrazine hydrate (2.50 g, 0.05 mol, 99%) was added and the mixture stirred at 273 K. To this solution carbon di­sulfide (3.81 g, 0.05 mol) was added drop wise with constant stirring for 1 h. Then 1-bromo­hexane (8.25 g, 0.05 mol) was added drop wise with vigorous stirring at 273 K for an additional hour. Finally, 2-hy­droxy­benzaldehyde (6.10 g, 0.05 mol) in ethanol was added and the mixture refluxed for 30 min. The mixture was filtered while hot and then the filtrate was cooled to 273 K giving a precipitate of the Schiff base product. It was recrystallized from ethanol at room temperature and dried in a vacuum desiccator over anhydrous CaCl₂. Colourless crystals of the title compound were obtained by slow evaporation of a solution in methanol/aceto­nitrile (3:1) [m.p. 364 K].

S5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were located geometrically and treated as riding atoms: C—H = 0.95–0.99 Å with U_iso(H) = 1.2U_eq(C). The NH and OH H atoms were located in a difference Fourier map and refined with U_iso(H) = 1.2U_eq(N,O).

Structure description

Bidentate Schiff bases of S-methyl or S-benzyl di­thio­carbaza­tes and their metal complexes have received considerable attention for their possible bioactivities (Chan et al., 2008; How et al., 2008; Zangrando et al., 2015; Ali et al., 2002; Chew et al., 2004; Crouse et al., 2004). As part of our ongoing structural studies of S-containing Schiff bases, we report herein on the structure of a molecule having a hexyl alkyl chain, similar to other ligands reported by our group (Begum, Zangrando et al., 2015; Begum, Howlader, Miyatake et al., 2015; Howlader et al., 2015) but differing in their ability to act as tridentate ligands in metal coordination (Begum, Howlader, Sheikh et al., 2015).

The four independent molecules (A--D) of the title compound are shown in Figs. 1 and 2. The Schiff base exists in its thione tautomeric form with the di­thio­carbazate fragment adopting an E conformation with respect to the C═N bond of the benzyl­idene moiety. The β-nitro­gen and the thio­keto sulfur are trans located with respect to bond C8—N2 bond in molecule A (and similarly for molecules B, C and D). All non-H atoms in the molecules are almost co-planar indicating, except for the alkyl chain, electron delocalization within them. The maximum deviation from the mean plane is shown by the thio­ketone atoms S1, S3, S5 and S7 in the four independent molecules (r.m.s deviations of 0.086, 0.118, 0.138 and 0.183 Å, respectively). The bond lengths and angles are comparable to those reported for S-hexyl (E)-3-(4-methyl­benzyl­idene)di­thio­carbazate (Howlader et al., 2015) and S-hexyl (E)-3-(4-meth­oxy­benzyl­idene)di­thio­carbazate (Begum, Howlader, Miyatake et al., 2015). The hexyl chain in all four molecules has an extended anti-zigzag conformation. This compound in its deprotonated imino thiol­ate form has been reported to act as a tridentate ligand through N–, S– and O-donors to form a binuclear copper(II) complex (Begum, Howlader, Sheikh et al., 2015).

The crystal packing of the title compound (Fig. 2), indicates that the molecules are connected by pairs of N—H···S hydrogen bonds (Table 1) to form A–D dimers, and B–B and C–C inversion dimers, all with R₂²(8) ring motifs.

Synthesis and crystallization

To an ethano­lic solution of KOH (2.81 g, 0.05 mol), hydrazine hydrate (2.50 g, 0.05 mol, 99%) was added and the mixture stirred at 273 K. To this solution carbon di­sulfide (3.81 g, 0.05 mol) was added drop wise with constant stirring for 1 h. Then 1-bromo­hexane (8.25 g, 0.05 mol) was added drop wise with vigorous stirring at 273 K for an additional hour. Finally, 2-hy­droxy­benzaldehyde (6.10 g, 0.05 mol) in ethanol was added and the mixture refluxed for 30 min. The mixture was filtered while hot and then the filtrate was cooled to 273 K giving a precipitate of the Schiff base product. It was recrystallized from ethanol at room temperature and dried in a vacuum desiccator over anhydrous CaCl₂. Colourless crystals of the title compound were obtained by slow evaporation of a solution in methanol/aceto­nitrile (3:1) [m.p. 364 K].

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were located geometrically and treated as riding atoms: C—H = 0.95–0.99 Å with U_iso(H) = 1.2U_eq(C). The NH and OH H atoms were located in a difference Fourier map and refined with U_iso(H) = 1.2U_eq(N,O).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures

	Fig. 1. The molecular structure of molecules A and C of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of molecules B and D of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. Crystal packing of the title compound, viewed along the c axis, showing pairs of molecules connected by N—H.·S hydrogen bonds (dashed lines; see Table 1). H atoms not involved in hydrogen bonds have been omitted for clarity.

S-Hexyl (E)-3-(2-hydroxybenzylidene)dithiocarbazate

Crystal data

C14H20N2OS2	F(000) = 2528
Mr = 296.44	Dx = 1.249 Mg m^−3
Monoclinic, P2/c	Cu Kα radiation, λ = 1.54187 Å
a = 18.9744 (4) Å	Cell parameters from 48491 reflections
b = 16.0269 (3) Å	θ = 3.5–68.2°
c = 21.1146 (4) Å	µ = 3.01 mm^−1
β = 100.808 (1)°	T = 173 K
V = 6307.1 (2) Å^3	Block, colourless
Z = 16	0.50 × 0.35 × 0.34 mm

Data collection

Rigaku R-AXIS RAPID diffractometer	Rint = 0.072
Detector resolution: 10.000 pixels mm^-1	θmax = 63.7°, θmin = 3.5°
ω scans	h = −22→22
10367 measured reflections	k = −19→19
10367 independent reflections	l = −25→25
6152 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: mixed
wR(F^2) = 0.176	H-atom parameters constrained
S = 0.93	w = 1/[σ^2(Fo^2) + (0.1083P)^2] where P = (Fo^2 + 2Fc^2)/3
10367 reflections	(Δ/σ)max = 0.001
713 parameters	Δρmax = 1.01 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.25358 (4)	0.59787 (5)	1.25919 (4)	0.0533 (2)
S2	0.10299 (4)	0.66115 (5)	1.21116 (4)	0.0461 (2)
O1	−0.06852 (11)	0.53508 (15)	1.15318 (11)	0.0557 (6)
H1O	−0.0321 (17)	0.550 (2)	1.1640 (16)	0.067*
N1	0.06892 (12)	0.49125 (15)	1.19459 (10)	0.0410 (6)
N2	0.14075 (12)	0.50536 (15)	1.21817 (11)	0.0417 (6)
H2N	0.1694 (15)	0.4634 (17)	1.2249 (13)	0.050*
C1	−0.08129 (16)	0.4524 (2)	1.14951 (13)	0.0447 (7)
C2	−0.15168 (17)	0.4254 (2)	1.13090 (14)	0.0570 (9)
H2	−0.1893	0.4651	1.1212	0.068*
C3	−0.16709 (17)	0.3420 (2)	1.12649 (15)	0.0617 (9)
H3	−0.2155	0.3247	1.1136	0.074*
C4	−0.11444 (17)	0.2829 (2)	1.14023 (14)	0.0584 (9)
H4	−0.1261	0.2252	1.1369	0.070*
C5	−0.04406 (16)	0.30837 (19)	1.15911 (13)	0.0508 (8)
H5	−0.0073	0.2675	1.1688	0.061*
C6	−0.02564 (15)	0.39267 (19)	1.16431 (12)	0.0418 (7)
C7	0.04852 (14)	0.41577 (18)	1.18721 (12)	0.0409 (7)
H7	0.0833	0.3728	1.1971	0.049*
C8	0.16649 (15)	0.58236 (18)	1.22957 (13)	0.0410 (7)
C9	0.15769 (15)	0.75494 (17)	1.22512 (14)	0.0445 (7)
H9A	0.1819	0.7579	1.2709	0.053*
H9B	0.1949	0.7542	1.1979	0.053*
C10	0.10842 (14)	0.83027 (17)	1.20813 (13)	0.0434 (7)
H10A	0.0840	0.8264	1.1625	0.052*
H10B	0.0712	0.8300	1.2353	0.052*
C11	0.15059 (15)	0.91139 (17)	1.21864 (13)	0.0420 (7)
H11A	0.1756	0.9143	1.2642	0.050*
H11B	0.1875	0.9115	1.1911	0.050*
C12	0.10336 (14)	0.98812 (18)	1.20317 (13)	0.0437 (7)
H12A	0.0643	0.9857	1.2283	0.052*
H12B	0.0811	0.9871	1.1568	0.052*
C13	0.14401 (15)	1.06987 (18)	1.21809 (14)	0.0474 (8)
H13A	0.1664	1.0710	1.2644	0.057*
H13B	0.1830	1.0726	1.1928	0.057*
C14	0.09630 (16)	1.14567 (19)	1.20269 (16)	0.0633 (10)
H14A	0.0737	1.1448	1.1570	0.095*
H14B	0.1252	1.1964	1.2119	0.095*
H14C	0.0591	1.1449	1.2292	0.095*
S3	−0.00414 (4)	0.86442 (5)	0.98657 (4)	0.0615 (3)
S4	0.14581 (4)	0.80245 (5)	1.04021 (4)	0.0527 (2)
O2	0.31627 (12)	0.92929 (17)	1.09819 (11)	0.0628 (7)
H2O	0.2772 (18)	0.913 (2)	1.0877 (17)	0.075*
N3	0.17915 (13)	0.97231 (16)	1.05390 (10)	0.0453 (6)
N4	0.10796 (14)	0.95825 (16)	1.02840 (12)	0.0483 (7)
H4N	0.0804 (16)	0.997 (2)	1.0216 (14)	0.058*
C15	0.32870 (17)	1.0119 (2)	1.10127 (13)	0.0511 (8)
C16	0.39934 (17)	1.0388 (3)	1.12158 (15)	0.0620 (10)
H16	0.4367	0.9990	1.1329	0.074*
C17	0.41471 (19)	1.1219 (3)	1.12517 (15)	0.0678 (10)
H17	0.4632	1.1390	1.1384	0.081*
C18	0.36200 (18)	1.1823 (2)	1.11015 (15)	0.0640 (10)
H18	0.3736	1.2400	1.1139	0.077*
C19	0.29206 (18)	1.1563 (2)	1.08951 (14)	0.0581 (9)
H19	0.2555	1.1970	1.0784	0.070*
C20	0.27352 (16)	1.0720 (2)	1.08446 (13)	0.0461 (8)
C21	0.19920 (16)	1.0485 (2)	1.06038 (13)	0.0467 (8)
H21	0.1644	1.0912	1.0491	0.056*
C22	0.08232 (16)	0.8808 (2)	1.01810 (14)	0.0484 (8)
C23	0.09183 (16)	0.70822 (19)	1.02657 (14)	0.0519 (8)
H23A	0.0551	0.7084	1.0543	0.062*
H23B	0.0670	0.7055	0.9810	0.062*
C24	0.14087 (15)	0.63370 (19)	1.04250 (14)	0.0509 (8)
H24A	0.1650	0.6365	1.0883	0.061*
H24B	0.1783	0.6350	1.0156	0.061*
C25	0.09880 (15)	0.55256 (19)	1.03051 (14)	0.0516 (8)
H25A	0.0633	0.5504	1.0594	0.062*
H25B	0.0720	0.5522	0.9855	0.062*
C26	0.14574 (16)	0.4750 (2)	1.04161 (15)	0.0540 (8)
H26A	0.1696	0.4730	1.0875	0.065*
H26B	0.1836	0.4791	1.0152	0.065*
C27	0.10385 (17)	0.3945 (2)	1.02465 (16)	0.0613 (9)
H27A	0.0652	0.3912	1.0502	0.074*
H27B	0.0810	0.3960	0.9785	0.074*
C28	0.15007 (18)	0.3170 (2)	1.03720 (17)	0.0776 (11)
H28A	0.1879	0.3192	1.0114	0.116*
H28B	0.1203	0.2674	1.0253	0.116*
H28C	0.1719	0.3143	1.0830	0.116*
S5	0.50812 (4)	0.86393 (5)	1.02000 (4)	0.0560 (3)
S6	0.36038 (4)	0.79983 (5)	0.96181 (4)	0.0481 (2)
O3	0.19255 (11)	0.91698 (14)	0.90094 (10)	0.0553 (6)
H3O	0.2367 (16)	0.913 (2)	0.9149 (15)	0.066*
N5	0.32576 (12)	0.96786 (14)	0.94728 (10)	0.0384 (6)
N6	0.39644 (12)	0.95587 (15)	0.97387 (11)	0.0425 (6)
H6N	0.4245 (15)	0.9962 (19)	0.9840 (13)	0.051*
C29	0.17628 (15)	0.9992 (2)	0.89769 (12)	0.0433 (7)
C30	0.10555 (16)	1.0218 (2)	0.87630 (14)	0.0541 (8)
H30	0.0703	0.9797	0.8640	0.065*
C31	0.08572 (17)	1.1037 (2)	0.87262 (14)	0.0573 (9)
H31	0.0365	1.1176	0.8590	0.069*
C32	0.13576 (17)	1.1674 (2)	0.88835 (14)	0.0565 (9)
H32	0.1215	1.2243	0.8848	0.068*
C33	0.20673 (16)	1.14573 (19)	0.90922 (13)	0.0476 (8)
H33	0.2414	1.1886	0.9202	0.057*
C34	0.22898 (15)	1.06259 (19)	0.91474 (12)	0.0399 (7)
C35	0.30375 (15)	1.04327 (18)	0.94067 (12)	0.0397 (7)
H35	0.3368	1.0875	0.9529	0.048*
C36	0.42271 (15)	0.87873 (19)	0.98566 (13)	0.0428 (7)
C37	0.41480 (15)	0.70616 (18)	0.97630 (14)	0.0460 (7)
H37A	0.4535	0.7076	0.9508	0.055*
H37B	0.4370	0.7020	1.0225	0.055*
C38	0.36595 (15)	0.63222 (17)	0.95638 (13)	0.0446 (7)
H38A	0.3448	0.6369	0.9100	0.053*
H38B	0.3262	0.6332	0.9808	0.053*
C39	0.40588 (14)	0.54952 (17)	0.96853 (13)	0.0433 (7)
H39A	0.4275	0.5451	1.0149	0.052*
H39B	0.4453	0.5483	0.9437	0.052*
C40	0.35648 (15)	0.47508 (18)	0.94918 (14)	0.0456 (7)
H40A	0.3358	0.4792	0.9026	0.055*
H40B	0.3164	0.4775	0.9731	0.055*
C41	0.39454 (16)	0.39093 (18)	0.96230 (15)	0.0525 (8)
H41A	0.4325	0.3868	0.9361	0.063*
H41B	0.4179	0.3881	1.0083	0.063*
C42	0.34353 (17)	0.31711 (19)	0.94668 (16)	0.0638 (9)
H42A	0.3058	0.3208	0.9725	0.096*
H42B	0.3703	0.2650	0.9567	0.096*
H42C	0.3218	0.3182	0.9008	0.096*
S7	0.24114 (4)	0.67360 (5)	0.72575 (4)	0.0532 (2)
S8	0.38731 (4)	0.73717 (5)	0.78991 (4)	0.0467 (2)
O4	0.55528 (11)	0.61947 (14)	0.85012 (11)	0.0557 (6)
H4O	0.5165 (16)	0.625 (2)	0.8343 (15)	0.067*
N7	0.42251 (12)	0.56890 (14)	0.80139 (10)	0.0384 (6)
N8	0.35164 (13)	0.58122 (15)	0.77368 (11)	0.0406 (6)
H8N	0.3267 (15)	0.5403 (17)	0.7596 (13)	0.049*
C43	0.57105 (15)	0.5377 (2)	0.85318 (12)	0.0423 (7)
C44	0.64194 (16)	0.5149 (2)	0.87552 (14)	0.0518 (8)
H44	0.6771	0.5569	0.8880	0.062*
C45	0.66183 (17)	0.4330 (2)	0.87981 (15)	0.0579 (9)
H45	0.7107	0.4190	0.8952	0.069*
C46	0.61212 (17)	0.3694 (2)	0.86216 (14)	0.0534 (8)
H46	0.6265	0.3125	0.8652	0.064*
C47	0.54122 (16)	0.39123 (19)	0.84007 (13)	0.0465 (8)
H47	0.5066	0.3485	0.8283	0.056*
C48	0.51916 (15)	0.47465 (18)	0.83465 (12)	0.0384 (7)
C49	0.44460 (14)	0.49335 (18)	0.80773 (12)	0.0385 (7)
H49	0.4119	0.4490	0.7947	0.046*
C50	0.32545 (15)	0.65816 (17)	0.76239 (13)	0.0406 (7)
C51	0.33330 (15)	0.83076 (17)	0.77494 (14)	0.0448 (7)
H51A	0.3105	0.8341	0.7288	0.054*
H51B	0.2950	0.8301	0.8010	0.054*
C52	0.38231 (15)	0.90513 (18)	0.79341 (13)	0.0445 (7)
H52A	0.4035	0.9018	0.8399	0.053*
H52B	0.4220	0.9030	0.7690	0.053*
C53	0.34310 (14)	0.98712 (17)	0.77993 (13)	0.0424 (7)
H53A	0.3051	0.9904	0.8061	0.051*
H53B	0.3196	0.9889	0.7339	0.051*
C54	0.39254 (15)	1.06271 (19)	0.79491 (14)	0.0503 (8)
H54A	0.4157	1.0610	0.8410	0.060*
H54B	0.4308	1.0590	0.7690	0.060*
C55	0.35385 (16)	1.14549 (18)	0.78102 (16)	0.0558 (8)
H55A	0.3290	1.1464	0.7354	0.067*
H55B	0.3170	1.1504	0.8083	0.067*
C56	0.40366 (17)	1.2195 (2)	0.79334 (17)	0.0731 (11)
H56A	0.4289	1.2187	0.8383	0.110*
H56B	0.3758	1.2711	0.7851	0.110*
H56C	0.4386	1.2168	0.7646	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0338 (4)	0.0394 (5)	0.0820 (6)	0.0012 (3)	−0.0012 (4)	−0.0004 (4)
S2	0.0352 (4)	0.0406 (5)	0.0594 (5)	0.0030 (3)	0.0010 (4)	0.0001 (3)
O1	0.0457 (14)	0.0542 (16)	0.0627 (15)	0.0107 (12)	−0.0012 (12)	0.0022 (11)
N1	0.0363 (14)	0.0479 (16)	0.0359 (13)	0.0039 (12)	−0.0004 (10)	0.0023 (11)
N2	0.0328 (15)	0.0369 (16)	0.0521 (15)	0.0001 (11)	−0.0009 (12)	0.0001 (12)
C1	0.0446 (19)	0.0429 (19)	0.0439 (17)	0.0016 (15)	0.0013 (14)	−0.0036 (14)
C2	0.0351 (19)	0.085 (3)	0.0477 (19)	0.0163 (18)	−0.0011 (15)	0.0004 (17)
C3	0.043 (2)	0.079 (3)	0.060 (2)	−0.012 (2)	0.0005 (16)	−0.0065 (19)
C4	0.050 (2)	0.062 (2)	0.059 (2)	−0.0170 (18)	−0.0012 (16)	−0.0047 (17)
C5	0.0436 (19)	0.0424 (19)	0.063 (2)	−0.0008 (15)	0.0013 (16)	−0.0044 (15)
C6	0.0374 (17)	0.052 (2)	0.0343 (15)	0.0055 (15)	0.0029 (13)	0.0006 (13)
C7	0.0365 (17)	0.0345 (17)	0.0490 (17)	−0.0019 (14)	0.0010 (14)	−0.0019 (13)
C8	0.0379 (17)	0.048 (2)	0.0360 (15)	0.0048 (14)	0.0049 (13)	0.0039 (13)
C9	0.0395 (17)	0.0316 (16)	0.0600 (18)	−0.0020 (13)	0.0028 (14)	−0.0030 (14)
C10	0.0420 (18)	0.0375 (18)	0.0498 (17)	0.0052 (14)	0.0063 (14)	−0.0042 (13)
C11	0.0392 (17)	0.0379 (18)	0.0473 (17)	0.0023 (14)	0.0042 (14)	−0.0006 (13)
C12	0.0376 (17)	0.0402 (18)	0.0507 (18)	0.0040 (14)	0.0014 (14)	0.0000 (14)
C13	0.0400 (18)	0.0416 (19)	0.0580 (19)	−0.0014 (14)	0.0026 (15)	−0.0004 (14)
C14	0.060 (2)	0.040 (2)	0.084 (2)	0.0006 (17)	0.0009 (19)	−0.0033 (17)
S3	0.0391 (5)	0.0544 (6)	0.0868 (6)	0.0014 (4)	0.0009 (4)	0.0056 (4)
S4	0.0424 (5)	0.0528 (6)	0.0598 (5)	0.0060 (4)	0.0017 (4)	0.0058 (4)
O2	0.0508 (15)	0.0648 (18)	0.0687 (16)	0.0107 (14)	0.0011 (13)	0.0046 (12)
N3	0.0386 (15)	0.0561 (18)	0.0402 (14)	0.0042 (13)	0.0048 (11)	0.0042 (12)
N4	0.0410 (17)	0.0464 (18)	0.0548 (16)	0.0038 (13)	0.0021 (13)	0.0060 (13)
C15	0.048 (2)	0.065 (2)	0.0386 (17)	0.0035 (18)	0.0051 (15)	−0.0020 (16)
C16	0.040 (2)	0.088 (3)	0.054 (2)	0.0099 (19)	0.0001 (16)	−0.0031 (19)
C17	0.049 (2)	0.094 (3)	0.057 (2)	−0.015 (2)	0.0015 (17)	−0.013 (2)
C18	0.053 (2)	0.070 (3)	0.066 (2)	−0.010 (2)	0.0029 (18)	−0.0135 (18)
C19	0.053 (2)	0.059 (2)	0.060 (2)	−0.0014 (18)	0.0036 (17)	−0.0041 (17)
C20	0.0395 (18)	0.059 (2)	0.0387 (16)	0.0057 (16)	0.0040 (14)	0.0013 (14)
C21	0.0424 (19)	0.053 (2)	0.0440 (17)	0.0034 (16)	0.0072 (14)	0.0014 (15)
C22	0.0444 (19)	0.056 (2)	0.0442 (17)	0.0032 (16)	0.0061 (14)	0.0035 (15)
C23	0.0451 (19)	0.054 (2)	0.0563 (19)	0.0072 (16)	0.0082 (15)	0.0068 (15)
C24	0.045 (2)	0.055 (2)	0.0524 (19)	0.0034 (16)	0.0092 (15)	0.0016 (15)
C25	0.0440 (19)	0.060 (2)	0.0486 (18)	0.0092 (17)	0.0041 (15)	0.0039 (15)
C26	0.045 (2)	0.057 (2)	0.059 (2)	0.0062 (17)	0.0073 (16)	0.0005 (16)
C27	0.048 (2)	0.065 (2)	0.070 (2)	0.0042 (18)	0.0062 (17)	0.0011 (18)
C28	0.073 (3)	0.062 (3)	0.093 (3)	0.005 (2)	0.004 (2)	−0.007 (2)
S5	0.0355 (5)	0.0451 (5)	0.0812 (6)	−0.0009 (4)	−0.0053 (4)	−0.0014 (4)
S6	0.0391 (5)	0.0375 (5)	0.0627 (5)	−0.0030 (3)	−0.0036 (4)	−0.0002 (3)
O3	0.0466 (13)	0.0426 (13)	0.0691 (15)	−0.0093 (11)	−0.0084 (12)	0.0045 (10)
N5	0.0343 (14)	0.0380 (15)	0.0404 (13)	−0.0031 (11)	0.0002 (11)	−0.0025 (10)
N6	0.0307 (15)	0.0404 (16)	0.0518 (15)	−0.0038 (11)	−0.0043 (12)	−0.0035 (12)
C29	0.0376 (18)	0.052 (2)	0.0373 (16)	−0.0075 (15)	−0.0005 (13)	0.0028 (14)
C30	0.0400 (19)	0.063 (2)	0.0559 (19)	−0.0093 (17)	−0.0001 (15)	0.0054 (16)
C31	0.0375 (19)	0.076 (3)	0.056 (2)	0.0070 (18)	0.0017 (15)	0.0084 (18)
C32	0.050 (2)	0.058 (2)	0.058 (2)	0.0107 (18)	0.0020 (16)	0.0035 (16)
C33	0.0447 (19)	0.043 (2)	0.0521 (18)	0.0003 (15)	0.0022 (15)	−0.0013 (14)
C34	0.0355 (17)	0.0462 (19)	0.0357 (15)	−0.0020 (14)	0.0010 (13)	0.0014 (13)
C35	0.0367 (17)	0.0412 (19)	0.0401 (16)	−0.0071 (14)	0.0045 (13)	−0.0032 (13)
C36	0.0389 (18)	0.0433 (19)	0.0444 (16)	0.0014 (14)	0.0030 (13)	−0.0003 (14)
C37	0.0410 (18)	0.0420 (18)	0.0518 (18)	0.0007 (14)	0.0008 (14)	0.0037 (14)
C38	0.0439 (18)	0.0402 (18)	0.0466 (17)	0.0000 (14)	0.0007 (14)	0.0054 (13)
C39	0.0371 (17)	0.047 (2)	0.0438 (17)	−0.0035 (14)	0.0030 (14)	0.0008 (14)
C40	0.0393 (18)	0.0438 (19)	0.0519 (18)	−0.0031 (14)	0.0041 (14)	−0.0016 (14)
C41	0.0446 (19)	0.048 (2)	0.064 (2)	0.0002 (16)	0.0060 (16)	−0.0003 (16)
C42	0.058 (2)	0.043 (2)	0.088 (2)	−0.0056 (17)	0.0053 (19)	−0.0039 (17)
S7	0.0354 (5)	0.0434 (5)	0.0758 (6)	0.0005 (3)	−0.0025 (4)	0.0030 (4)
S8	0.0410 (5)	0.0362 (5)	0.0580 (5)	−0.0009 (3)	−0.0035 (4)	−0.0021 (3)
O4	0.0502 (14)	0.0400 (13)	0.0693 (15)	−0.0074 (12)	−0.0082 (12)	0.0024 (11)
N7	0.0349 (14)	0.0360 (14)	0.0420 (13)	−0.0009 (11)	0.0015 (11)	−0.0006 (10)
N8	0.0346 (15)	0.0361 (16)	0.0475 (14)	−0.0028 (11)	−0.0016 (12)	−0.0048 (11)
C43	0.0374 (18)	0.054 (2)	0.0348 (15)	−0.0084 (15)	0.0040 (13)	0.0003 (13)
C44	0.0380 (18)	0.059 (2)	0.0554 (19)	−0.0058 (16)	0.0021 (15)	0.0042 (16)
C45	0.0395 (19)	0.083 (3)	0.0508 (19)	0.0036 (19)	0.0078 (15)	0.0061 (18)
C46	0.048 (2)	0.053 (2)	0.057 (2)	0.0119 (17)	0.0044 (16)	0.0045 (16)
C47	0.0459 (19)	0.046 (2)	0.0471 (17)	−0.0016 (15)	0.0068 (15)	−0.0045 (14)
C48	0.0350 (16)	0.0413 (17)	0.0385 (16)	−0.0005 (14)	0.0056 (13)	0.0019 (13)
C49	0.0366 (17)	0.0423 (18)	0.0357 (15)	−0.0079 (14)	0.0048 (13)	−0.0045 (13)
C50	0.0388 (17)	0.0366 (17)	0.0461 (16)	0.0003 (14)	0.0068 (13)	0.0013 (13)
C51	0.0382 (17)	0.0439 (19)	0.0482 (17)	0.0006 (14)	−0.0023 (14)	0.0003 (14)
C52	0.0456 (18)	0.0446 (19)	0.0408 (16)	−0.0044 (15)	0.0014 (14)	−0.0005 (13)
C53	0.0424 (18)	0.0390 (18)	0.0439 (16)	−0.0013 (14)	0.0031 (14)	−0.0011 (13)
C54	0.0434 (19)	0.044 (2)	0.061 (2)	−0.0043 (15)	0.0049 (16)	−0.0016 (15)
C55	0.046 (2)	0.0397 (19)	0.081 (2)	−0.0017 (15)	0.0100 (17)	−0.0015 (16)
C56	0.063 (2)	0.044 (2)	0.111 (3)	−0.0017 (18)	0.012 (2)	0.006 (2)

Geometric parameters (Å, º)

S1—C8	1.672 (3)	S5—C36	1.664 (3)
S2—C8	1.738 (3)	S6—C36	1.740 (3)
S2—C9	1.819 (3)	S6—C37	1.815 (3)
O1—C1	1.347 (4)	O3—C29	1.353 (4)
O1—H1O	0.73 (3)	O3—H3O	0.84 (3)
N1—C7	1.271 (3)	N5—C35	1.278 (3)
N1—N2	1.379 (3)	N5—N6	1.367 (3)
N2—C8	1.332 (3)	N6—C36	1.339 (4)
N2—H2N	0.86 (3)	N6—H6N	0.84 (3)
C1—C2	1.389 (4)	C29—C30	1.381 (4)
C1—C6	1.416 (4)	C29—C34	1.423 (4)
C2—C3	1.368 (5)	C30—C31	1.364 (4)
C2—H2	0.9500	C30—H30	0.9500
C3—C4	1.368 (4)	C31—C32	1.392 (4)
C3—H3	0.9500	C31—H31	0.9500
C4—C5	1.382 (4)	C32—C33	1.380 (4)
C4—H4	0.9500	C32—H32	0.9500
C5—C6	1.395 (4)	C33—C34	1.396 (4)
C5—H5	0.9500	C33—H33	0.9500
C6—C7	1.448 (4)	C34—C35	1.455 (4)
C7—H7	0.9500	C35—H35	0.9500
C9—C10	1.528 (4)	C37—C38	1.515 (4)
C9—H9A	0.9900	C37—H37A	0.9900
C9—H9B	0.9900	C37—H37B	0.9900
C10—C11	1.521 (4)	C38—C39	1.524 (4)
C10—H10A	0.9900	C38—H38A	0.9900
C10—H10B	0.9900	C38—H38B	0.9900
C11—C12	1.521 (4)	C39—C40	1.525 (4)
C11—H11A	0.9900	C39—H39A	0.9900
C11—H11B	0.9900	C39—H39B	0.9900
C12—C13	1.523 (4)	C40—C41	1.530 (4)
C12—H12A	0.9900	C40—H40A	0.9900
C12—H12B	0.9900	C40—H40B	0.9900
C13—C14	1.513 (4)	C41—C42	1.525 (4)
C13—H13A	0.9900	C41—H41A	0.9900
C13—H13B	0.9900	C41—H41B	0.9900
C14—H14A	0.9800	C42—H42A	0.9800
C14—H14B	0.9800	C42—H42B	0.9800
C14—H14C	0.9800	C42—H42C	0.9800
S3—C22	1.672 (3)	S7—C50	1.660 (3)
S4—C22	1.742 (3)	S8—C50	1.750 (3)
S4—C23	1.817 (3)	S8—C51	1.811 (3)
O2—C15	1.344 (4)	O4—C43	1.343 (4)
O2—H2O	0.78 (3)	O4—H4O	0.76 (3)
N3—C21	1.278 (3)	N7—C49	1.280 (3)
N3—N4	1.376 (3)	N7—N8	1.376 (3)
N4—C22	1.336 (4)	N8—C50	1.334 (3)
N4—H4N	0.81 (3)	N8—H8N	0.83 (3)
C15—C16	1.397 (4)	C43—C44	1.388 (4)
C15—C20	1.418 (4)	C43—C48	1.414 (4)
C16—C17	1.363 (5)	C44—C45	1.364 (4)
C16—H16	0.9500	C44—H44	0.9500
C17—C18	1.385 (5)	C45—C46	1.391 (4)
C17—H17	0.9500	C45—H45	0.9500
C18—C19	1.381 (4)	C46—C47	1.384 (4)
C18—H18	0.9500	C46—H46	0.9500
C19—C20	1.395 (4)	C47—C48	1.399 (4)
C19—H19	0.9500	C47—H47	0.9500
C20—C21	1.456 (4)	C48—C49	1.453 (4)
C21—H21	0.9500	C49—H49	0.9500
C23—C24	1.513 (4)	C51—C52	1.517 (4)
C23—H23A	0.9900	C51—H51A	0.9900
C23—H23B	0.9900	C51—H51B	0.9900
C24—C25	1.522 (4)	C52—C53	1.511 (4)
C24—H24A	0.9900	C52—H52A	0.9900
C24—H24B	0.9900	C52—H52B	0.9900
C25—C26	1.521 (4)	C53—C54	1.529 (4)
C25—H25A	0.9900	C53—H53A	0.9900
C25—H25B	0.9900	C53—H53B	0.9900
C26—C27	1.522 (4)	C54—C55	1.518 (4)
C26—H26A	0.9900	C54—H54A	0.9900
C26—H26B	0.9900	C54—H54B	0.9900
C27—C28	1.515 (4)	C55—C56	1.509 (4)
C27—H27A	0.9900	C55—H55A	0.9900
C27—H27B	0.9900	C55—H55B	0.9900
C28—H28A	0.9800	C56—H56A	0.9800
C28—H28B	0.9800	C56—H56B	0.9800
C28—H28C	0.9800	C56—H56C	0.9800
C8—S2—C9	102.33 (13)	C36—S6—C37	102.60 (14)
C1—O1—H1O	119 (3)	C29—O3—H3O	107 (2)
C7—N1—N2	117.3 (2)	C35—N5—N6	116.9 (2)
C8—N2—N1	121.4 (2)	C36—N6—N5	120.6 (2)
C8—N2—H2N	119.8 (19)	C36—N6—H6N	118 (2)
N1—N2—H2N	118.8 (19)	N5—N6—H6N	122 (2)
O1—C1—C2	118.4 (3)	O3—C29—C30	118.0 (3)
O1—C1—C6	122.3 (3)	O3—C29—C34	122.7 (3)
C2—C1—C6	119.3 (3)	C30—C29—C34	119.3 (3)
C3—C2—C1	120.4 (3)	C31—C30—C29	120.7 (3)
C3—C2—H2	119.8	C31—C30—H30	119.6
C1—C2—H2	119.8	C29—C30—H30	119.6
C2—C3—C4	121.6 (3)	C30—C31—C32	121.6 (3)
C2—C3—H3	119.2	C30—C31—H31	119.2
C4—C3—H3	119.2	C32—C31—H31	119.2
C3—C4—C5	118.9 (3)	C33—C32—C31	118.2 (3)
C3—C4—H4	120.5	C33—C32—H32	120.9
C5—C4—H4	120.5	C31—C32—H32	120.9
C4—C5—C6	121.6 (3)	C32—C33—C34	121.9 (3)
C4—C5—H5	119.2	C32—C33—H33	119.0
C6—C5—H5	119.2	C34—C33—H33	119.0
C5—C6—C1	118.2 (3)	C33—C34—C29	118.2 (3)
C5—C6—C7	119.2 (3)	C33—C34—C35	119.5 (3)
C1—C6—C7	122.6 (3)	C29—C34—C35	122.2 (3)
N1—C7—C6	122.6 (3)	N5—C35—C34	121.2 (3)
N1—C7—H7	118.7	N5—C35—H35	119.4
C6—C7—H7	118.7	C34—C35—H35	119.4
N2—C8—S1	120.6 (2)	N6—C36—S5	120.7 (2)
N2—C8—S2	114.7 (2)	N6—C36—S6	114.1 (2)
S1—C8—S2	124.79 (18)	S5—C36—S6	125.18 (18)
C10—C9—S2	108.02 (19)	C38—C37—S6	107.53 (19)
C10—C9—H9A	110.1	C38—C37—H37A	110.2
S2—C9—H9A	110.1	S6—C37—H37A	110.2
C10—C9—H9B	110.1	C38—C37—H37B	110.2
S2—C9—H9B	110.1	S6—C37—H37B	110.2
H9A—C9—H9B	108.4	H37A—C37—H37B	108.5
C11—C10—C9	111.0 (2)	C37—C38—C39	112.0 (2)
C11—C10—H10A	109.4	C37—C38—H38A	109.2
C9—C10—H10A	109.4	C39—C38—H38A	109.2
C11—C10—H10B	109.4	C37—C38—H38B	109.2
C9—C10—H10B	109.4	C39—C38—H38B	109.2
H10A—C10—H10B	108.0	H38A—C38—H38B	107.9
C12—C11—C10	112.8 (2)	C38—C39—C40	112.0 (2)
C12—C11—H11A	109.0	C38—C39—H39A	109.2
C10—C11—H11A	109.0	C40—C39—H39A	109.2
C12—C11—H11B	109.0	C38—C39—H39B	109.2
C10—C11—H11B	109.0	C40—C39—H39B	109.2
H11A—C11—H11B	107.8	H39A—C39—H39B	107.9
C11—C12—C13	113.3 (2)	C39—C40—C41	113.3 (2)
C11—C12—H12A	108.9	C39—C40—H40A	108.9
C13—C12—H12A	108.9	C41—C40—H40A	108.9
C11—C12—H12B	108.9	C39—C40—H40B	108.9
C13—C12—H12B	108.9	C41—C40—H40B	108.9
H12A—C12—H12B	107.7	H40A—C40—H40B	107.7
C14—C13—C12	112.7 (2)	C42—C41—C40	112.7 (2)
C14—C13—H13A	109.0	C42—C41—H41A	109.1
C12—C13—H13A	109.0	C40—C41—H41A	109.1
C14—C13—H13B	109.0	C42—C41—H41B	109.1
C12—C13—H13B	109.0	C40—C41—H41B	109.1
H13A—C13—H13B	107.8	H41A—C41—H41B	107.8
C13—C14—H14A	109.5	C41—C42—H42A	109.5
C13—C14—H14B	109.5	C41—C42—H42B	109.5
H14A—C14—H14B	109.5	H42A—C42—H42B	109.5
C13—C14—H14C	109.5	C41—C42—H42C	109.5
H14A—C14—H14C	109.5	H42A—C42—H42C	109.5
H14B—C14—H14C	109.5	H42B—C42—H42C	109.5
C22—S4—C23	102.46 (15)	C50—S8—C51	102.66 (13)
C15—O2—H2O	119 (3)	C43—O4—H4O	109 (3)
C21—N3—N4	116.7 (3)	C49—N7—N8	117.1 (2)
C22—N4—N3	121.1 (3)	C50—N8—N7	120.7 (2)
C22—N4—H4N	119 (2)	C50—N8—H8N	120 (2)
N3—N4—H4N	120 (2)	N7—N8—H8N	119 (2)
O2—C15—C16	117.9 (3)	O4—C43—C44	117.8 (3)
O2—C15—C20	122.8 (3)	O4—C43—C48	123.1 (3)
C16—C15—C20	119.2 (3)	C44—C43—C48	119.1 (3)
C17—C16—C15	120.1 (3)	C45—C44—C43	121.0 (3)
C17—C16—H16	119.9	C45—C44—H44	119.5
C15—C16—H16	119.9	C43—C44—H44	119.5
C16—C17—C18	122.2 (3)	C44—C45—C46	121.5 (3)
C16—C17—H17	118.9	C44—C45—H45	119.3
C18—C17—H17	118.9	C46—C45—H45	119.3
C19—C18—C17	118.1 (3)	C47—C46—C45	118.2 (3)
C19—C18—H18	120.9	C47—C46—H46	120.9
C17—C18—H18	120.9	C45—C46—H46	120.9
C18—C19—C20	122.0 (3)	C46—C47—C48	121.8 (3)
C18—C19—H19	119.0	C46—C47—H47	119.1
C20—C19—H19	119.0	C48—C47—H47	119.1
C19—C20—C15	118.4 (3)	C47—C48—C43	118.6 (3)
C19—C20—C21	119.4 (3)	C47—C48—C49	118.9 (3)
C15—C20—C21	122.2 (3)	C43—C48—C49	122.5 (3)
N3—C21—C20	122.3 (3)	N7—C49—C48	120.8 (3)
N3—C21—H21	118.9	N7—C49—H49	119.6
C20—C21—H21	118.9	C48—C49—H49	119.6
N4—C22—S3	120.7 (2)	N8—C50—S7	121.0 (2)
N4—C22—S4	114.4 (2)	N8—C50—S8	113.9 (2)
S3—C22—S4	124.8 (2)	S7—C50—S8	125.07 (17)
C24—C23—S4	108.4 (2)	C52—C51—S8	107.84 (19)
C24—C23—H23A	110.0	C52—C51—H51A	110.1
S4—C23—H23A	110.0	S8—C51—H51A	110.1
C24—C23—H23B	110.0	C52—C51—H51B	110.1
S4—C23—H23B	110.0	S8—C51—H51B	110.1
H23A—C23—H23B	108.4	H51A—C51—H51B	108.5
C23—C24—C25	110.9 (2)	C53—C52—C51	112.2 (2)
C23—C24—H24A	109.5	C53—C52—H52A	109.2
C25—C24—H24A	109.5	C51—C52—H52A	109.2
C23—C24—H24B	109.5	C53—C52—H52B	109.2
C25—C24—H24B	109.5	C51—C52—H52B	109.2
H24A—C24—H24B	108.1	H52A—C52—H52B	107.9
C26—C25—C24	113.5 (2)	C52—C53—C54	112.9 (2)
C26—C25—H25A	108.9	C52—C53—H53A	109.0
C24—C25—H25A	108.9	C54—C53—H53A	109.0
C26—C25—H25B	108.9	C52—C53—H53B	109.0
C24—C25—H25B	108.9	C54—C53—H53B	109.0
H25A—C25—H25B	107.7	H53A—C53—H53B	107.8
C25—C26—C27	113.0 (3)	C55—C54—C53	113.4 (2)
C25—C26—H26A	109.0	C55—C54—H54A	108.9
C27—C26—H26A	109.0	C53—C54—H54A	108.9
C25—C26—H26B	109.0	C55—C54—H54B	108.9
C27—C26—H26B	109.0	C53—C54—H54B	108.9
H26A—C26—H26B	107.8	H54A—C54—H54B	107.7
C28—C27—C26	113.2 (3)	C56—C55—C54	112.9 (2)
C28—C27—H27A	108.9	C56—C55—H55A	109.0
C26—C27—H27A	108.9	C54—C55—H55A	109.0
C28—C27—H27B	108.9	C56—C55—H55B	109.0
C26—C27—H27B	108.9	C54—C55—H55B	109.0
H27A—C27—H27B	107.8	H55A—C55—H55B	107.8
C27—C28—H28A	109.5	C55—C56—H56A	109.5
C27—C28—H28B	109.5	C55—C56—H56B	109.5
H28A—C28—H28B	109.5	H56A—C56—H56B	109.5
C27—C28—H28C	109.5	C55—C56—H56C	109.5
H28A—C28—H28C	109.5	H56A—C56—H56C	109.5
H28B—C28—H28C	109.5	H56B—C56—H56C	109.5
C7—N1—N2—C8	−177.6 (2)	C35—N5—N6—C36	176.3 (2)
O1—C1—C2—C3	179.9 (3)	O3—C29—C30—C31	179.3 (3)
C6—C1—C2—C3	−0.4 (4)	C34—C29—C30—C31	−1.3 (4)
C1—C2—C3—C4	0.2 (5)	C29—C30—C31—C32	1.8 (5)
C2—C3—C4—C5	0.1 (5)	C30—C31—C32—C33	−1.2 (5)
C3—C4—C5—C6	−0.1 (5)	C31—C32—C33—C34	0.1 (4)
C4—C5—C6—C1	−0.1 (4)	C32—C33—C34—C29	0.5 (4)
C4—C5—C6—C7	177.1 (3)	C32—C33—C34—C35	−176.3 (3)
O1—C1—C6—C5	−180.0 (3)	O3—C29—C34—C33	179.5 (2)
C2—C1—C6—C5	0.4 (4)	C30—C29—C34—C33	0.1 (4)
O1—C1—C6—C7	2.9 (4)	O3—C29—C34—C35	−3.8 (4)
C2—C1—C6—C7	−176.8 (3)	C30—C29—C34—C35	176.8 (2)
N2—N1—C7—C6	178.5 (2)	N6—N5—C35—C34	−178.1 (2)
C5—C6—C7—N1	−178.3 (3)	C33—C34—C35—N5	179.0 (2)
C1—C6—C7—N1	−1.2 (4)	C29—C34—C35—N5	2.3 (4)
N1—N2—C8—S1	179.09 (18)	N5—N6—C36—S5	−178.17 (19)
N1—N2—C8—S2	−1.0 (3)	N5—N6—C36—S6	2.1 (3)
C9—S2—C8—N2	−174.8 (2)	C37—S6—C36—N6	174.1 (2)
C9—S2—C8—S1	5.1 (2)	C37—S6—C36—S5	−5.6 (2)
C8—S2—C9—C10	177.90 (19)	C36—S6—C37—C38	−179.37 (19)
S2—C9—C10—C11	−179.99 (19)	S6—C37—C38—C39	−178.21 (19)
C9—C10—C11—C12	−179.2 (2)	C37—C38—C39—C40	179.3 (2)
C10—C11—C12—C13	175.8 (2)	C38—C39—C40—C41	−178.6 (2)
C11—C12—C13—C14	−179.8 (2)	C39—C40—C41—C42	176.4 (2)
C21—N3—N4—C22	178.1 (3)	C49—N7—N8—C50	−176.6 (2)
O2—C15—C16—C17	179.7 (3)	O4—C43—C44—C45	−179.9 (3)
C20—C15—C16—C17	0.1 (4)	C48—C43—C44—C45	−0.1 (4)
C15—C16—C17—C18	1.0 (5)	C43—C44—C45—C46	−0.1 (5)
C16—C17—C18—C19	−1.5 (5)	C44—C45—C46—C47	−0.2 (4)
C17—C18—C19—C20	1.0 (5)	C45—C46—C47—C48	0.7 (4)
C18—C19—C20—C15	0.1 (4)	C46—C47—C48—C43	−0.8 (4)
C18—C19—C20—C21	−178.0 (3)	C46—C47—C48—C49	176.6 (2)
O2—C15—C20—C19	179.8 (3)	O4—C43—C48—C47	−179.7 (2)
C16—C15—C20—C19	−0.6 (4)	C44—C43—C48—C47	0.5 (4)
O2—C15—C20—C21	−2.2 (4)	O4—C43—C48—C49	3.0 (4)
C16—C15—C20—C21	177.4 (3)	C44—C43—C48—C49	−176.8 (2)
N4—N3—C21—C20	−177.6 (2)	N8—N7—C49—C48	178.1 (2)
C19—C20—C21—N3	179.1 (3)	C47—C48—C49—N7	−179.3 (2)
C15—C20—C21—N3	1.1 (4)	C43—C48—C49—N7	−1.9 (4)
N3—N4—C22—S3	−179.53 (19)	N7—N8—C50—S7	176.98 (18)
N3—N4—C22—S4	0.6 (4)	N7—N8—C50—S8	−3.4 (3)
C23—S4—C22—N4	175.2 (2)	C51—S8—C50—N8	−174.4 (2)
C23—S4—C22—S3	−4.7 (2)	C51—S8—C50—S7	5.2 (2)
C22—S4—C23—C24	178.7 (2)	C50—S8—C51—C52	−176.75 (19)
S4—C23—C24—C25	−178.71 (19)	S8—C51—C52—C53	177.41 (19)
C23—C24—C25—C26	176.4 (2)	C51—C52—C53—C54	−176.9 (2)
C24—C25—C26—C27	−175.7 (2)	C52—C53—C54—C55	179.5 (2)
C25—C26—C27—C28	−178.6 (3)	C53—C54—C55—C56	−177.6 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···N1	0.73 (3)	2.13 (3)	2.684 (3)	135 (3)
O2—H2O···N3	0.78 (3)	2.09 (3)	2.685 (3)	133 (3)
O3—H3O···N5	0.84 (3)	1.91 (3)	2.662 (3)	148 (3)
O4—H4O···N7	0.75 (3)	2.00 (3)	2.663 (3)	146 (3)
N2—H2N···S7^i	0.86 (3)	2.58 (3)	3.430 (3)	169 (3)
N4—H4N···S3^ii	0.81 (3)	2.64 (3)	3.439 (3)	171 (2)
N6—H6N···S5^iii	0.84 (3)	2.59 (3)	3.398 (3)	162 (2)
N8—H8N···S1^iv	0.83 (3)	2.61 (3)	3.403 (3)	160 (2)

Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x, −y+2, −z+2; (iii) −x+1, −y+2, −z+2; (iv) x, −y+1, z−1/2.