3-Benzoyl-1,1-dibenzyl-thio-urea.

Two independent thio-urea mol-ecules comprise the asymmetric unit of the title compound, C(22)H(20)N(2)OS. The central N-C(=S)N(H)C(=O) atoms in each mol-ecule are virtually superimposable and each is twisted [C-N-C-S torsion angles = 121.3 (3) and -62.3 (4)°]. The mol-ecules differ only in terms of the relative orientations of the benzyl benzene rings [major difference between the C-N-C-C torsion angles of -146.6 (3) and -132.9 (3)°]. The presence of N-H⋯S hydrogen bonding leads to the formation of supra-molecular chains along the a axis. These are consolidated in the crystal packing by C-H⋯O inter-actions. The crystal was found to be a combined non-merohedral and racemic twin (twin law 00/00/001), with the fractional contribution of the minor components being approximately 9 and 28%.

Related literature

For our studies of thio­urea and its derivatives, see: Gunasekaran et al. (2010 ▶). For the biological activity of thio­urea derivatives, see: Venkatachalam et al. (2004 ▶); Yuan et al. (2001 ▶); Zhou et al. (2004 ▶). For additional geometric analysis, see: Spek (2009 ▶).

Experimental

Crystal data

C22H20N2OS

M = 360.46

Monoclinic,

a = 7.7338 (5) Å

b = 24.3478 (16) Å

c = 9.8593 (6) Å

β = 90.074 (1)°

V = 1856.5 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 100 K

0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.946, T max = 0.982

17536 measured reflections

8469 independent reflections

7807 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.157

S = 1.03

8469 reflections

470 parameters

1 restraint

H-atom parameters constrained

Δρmax = 1.27 e Å−3

Δρmin = −0.36 e Å−3

Absolute structure: Flack (1983 ▶), 4101 Friedel pairs

Flack parameter: 0.25 (8)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 (Farrugia, 1997 ▶), DIAMOND (Brandenburg, 2006 ▶) and Qmol (Gans & Shalloway, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036226/lh5120sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036226/lh5120Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H20N2OS	F(000) = 760
Mr = 360.46	Dx = 1.290 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 6510 reflections
a = 7.7338 (5) Å	θ = 2.2–28.1°
b = 24.3478 (16) Å	µ = 0.19 mm−1
c = 9.8593 (6) Å	T = 100 K
β = 90.074 (1)°	Block, colourless
V = 1856.5 (2) Å3	0.30 × 0.20 × 0.10 mm
Z = 4

Bruker SMART APEX diffractometer	8469 independent reflections
Radiation source: fine-focus sealed tube	7807 reflections with I > 2σ(I)
graphite	Rint = 0.055
ω scans	θmax = 27.5°, θmin = 0.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.946, Tmax = 0.982	k = −31→31
17536 measured reflections	l = −12→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058	H-atom parameters constrained
wR(F2) = 0.157	w = 1/[σ2(Fo2) + (0.0934P)2 + 0.2767P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
8469 reflections	Δρmax = 1.27 e Å−3
470 parameters	Δρmin = −0.36 e Å−3
1 restraint	Absolute structure: Flack (1983), 4101 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.25 (8)

	x	y	z	Uiso*/Ueq
S1	1.52015 (10)	0.49995 (3)	0.21954 (8)	0.01637 (17)
S2	1.02727 (11)	0.46914 (3)	0.10081 (9)	0.01665 (17)
O1	1.3589 (3)	0.66362 (10)	0.2194 (3)	0.0228 (6)
O2	0.8629 (3)	0.30856 (10)	0.0894 (3)	0.0239 (6)
N1	1.5083 (4)	0.58006 (11)	0.0339 (3)	0.0157 (6)
N2	1.2782 (4)	0.57501 (10)	0.1861 (3)	0.0140 (5)
H2	1.1911	0.5531	0.1843	0.017*
N3	1.0001 (4)	0.38816 (12)	0.2845 (3)	0.0179 (6)
N4	0.7766 (4)	0.39659 (11)	0.1265 (3)	0.0162 (6)
H4	0.6899	0.4187	0.1277	0.019*
C1	1.0820 (4)	0.63713 (13)	0.3027 (3)	0.0154 (6)
C2	0.9587 (5)	0.59635 (14)	0.3240 (4)	0.0204 (7)
H2A	0.9822	0.5597	0.2969	0.024*
C3	0.8020 (5)	0.60887 (16)	0.3846 (4)	0.0242 (8)
H3	0.7183	0.5809	0.3986	0.029*
C4	0.7672 (5)	0.66233 (15)	0.4247 (4)	0.0239 (8)
H4A	0.6601	0.6708	0.4668	0.029*
C5	0.8880 (5)	0.70339 (15)	0.4038 (4)	0.0240 (8)
H5	0.8635	0.7400	0.4310	0.029*
C6	1.0446 (5)	0.69113 (14)	0.3431 (4)	0.0208 (7)
H6	1.1273	0.7194	0.3287	0.025*
C7	1.2514 (4)	0.62775 (13)	0.2336 (3)	0.0151 (6)
C8	1.4372 (4)	0.55502 (13)	0.1409 (3)	0.0139 (6)
C9	1.6810 (4)	0.56209 (14)	−0.0142 (4)	0.0195 (7)
H9A	1.6654	0.5336	−0.0849	0.023*
H9B	1.7441	0.5451	0.0624	0.023*
C10	1.7895 (4)	0.60781 (13)	−0.0715 (4)	0.0176 (7)
C11	1.8660 (5)	0.60174 (15)	−0.1997 (4)	0.0214 (7)
H11	1.8424	0.5700	−0.2527	0.026*
C12	1.9766 (5)	0.64222 (16)	−0.2494 (4)	0.0234 (8)
H12	2.0286	0.6380	−0.3360	0.028*
C13	2.0104 (5)	0.68838 (16)	−0.1727 (4)	0.0252 (8)
H13	2.0856	0.7159	−0.2069	0.030*
C14	1.9355 (5)	0.69483 (16)	−0.0462 (4)	0.0272 (8)
H14	1.9600	0.7267	0.0059	0.033*
C15	1.8248 (5)	0.65500 (15)	0.0050 (4)	0.0242 (8)
H15	1.7731	0.6598	0.0916	0.029*
C16	1.4092 (5)	0.61491 (14)	−0.0616 (3)	0.0178 (7)
H16A	1.4751	0.6489	−0.0810	0.021*
H16B	1.2978	0.6255	−0.0197	0.021*
C17	1.3751 (4)	0.58415 (14)	−0.1933 (3)	0.0163 (6)
C18	1.4287 (4)	0.60578 (15)	−0.3151 (4)	0.0201 (7)
H18	1.4929	0.6390	−0.3166	0.024*
C19	1.3891 (5)	0.57905 (16)	−0.4367 (4)	0.0224 (7)
H19	1.4247	0.5944	−0.5207	0.027*
C20	1.2973 (5)	0.52985 (17)	−0.4347 (4)	0.0265 (8)
H20	1.2704	0.5115	−0.5171	0.032*
C21	1.2453 (5)	0.50774 (16)	−0.3114 (4)	0.0280 (8)
H21	1.1833	0.4741	−0.3098	0.034*
C22	1.2830 (5)	0.53436 (15)	−0.1908 (4)	0.0235 (8)
H22	1.2468	0.5191	−0.1068	0.028*
C23	0.5896 (4)	0.33461 (14)	−0.0012 (3)	0.0152 (6)
C24	0.5720 (5)	0.28392 (14)	−0.0668 (4)	0.0208 (7)
H24	0.6619	0.2574	−0.0607	0.025*
C25	0.4246 (5)	0.27233 (15)	−0.1403 (4)	0.0237 (8)
H25	0.4145	0.2383	−0.1869	0.028*
C26	0.2900 (5)	0.31064 (17)	−0.1465 (4)	0.0279 (9)
H26	0.1865	0.3019	−0.1938	0.033*
C27	0.3071 (5)	0.36096 (15)	−0.0840 (4)	0.0240 (8)
H27	0.2174	0.3875	−0.0911	0.029*
C28	0.4566 (4)	0.37286 (14)	−0.0104 (4)	0.0196 (7)
H28	0.4677	0.4074	0.0337	0.024*
C29	0.7538 (4)	0.34428 (14)	0.0742 (3)	0.0158 (6)
C30	0.9368 (4)	0.41485 (13)	0.1778 (3)	0.0153 (6)
C31	0.8927 (5)	0.35268 (14)	0.3720 (4)	0.0208 (7)
H31A	0.9526	0.3173	0.3878	0.025*
H31B	0.7812	0.3449	0.3265	0.025*
C32	0.8599 (5)	0.38108 (14)	0.5071 (3)	0.0182 (7)
C33	0.9196 (5)	0.35777 (15)	0.6274 (4)	0.0199 (7)
H33	0.9831	0.3244	0.6251	0.024*
C34	0.8866 (5)	0.38311 (16)	0.7499 (4)	0.0221 (7)
H34	0.9260	0.3668	0.8319	0.026*
C35	0.7964 (5)	0.43216 (16)	0.7538 (4)	0.0246 (8)
H35	0.7749	0.4497	0.8382	0.030*
C36	0.7367 (5)	0.45597 (15)	0.6329 (4)	0.0263 (8)
H36	0.6738	0.4895	0.6351	0.032*
C37	0.7702 (5)	0.43033 (16)	0.5101 (4)	0.0271 (8)
H37	0.7315	0.4466	0.4278	0.033*
C38	1.1725 (5)	0.40062 (15)	0.3372 (4)	0.0230 (8)
H38A	1.1607	0.4216	0.4227	0.028*
H38B	1.2339	0.4242	0.2712	0.028*
C39	1.2794 (5)	0.35003 (15)	0.3639 (4)	0.0212 (7)
C40	1.3815 (5)	0.34745 (16)	0.4800 (4)	0.0244 (8)
H40	1.3763	0.3760	0.5457	0.029*
C41	1.4926 (5)	0.30219 (17)	0.4997 (5)	0.0304 (9)
H41	1.5618	0.3001	0.5793	0.036*
C42	1.5013 (5)	0.26096 (16)	0.4041 (4)	0.0288 (9)
H42	1.5789	0.2311	0.4167	0.035*
C43	1.3972 (6)	0.26289 (17)	0.2894 (5)	0.0308 (9)
H43	1.4020	0.2341	0.2246	0.037*
C44	1.2852 (5)	0.30727 (16)	0.2692 (4)	0.0255 (8)
H44	1.2130	0.3084	0.1912	0.031*

	U11	U22	U33	U12	U13	U23
S1	0.0164 (4)	0.0154 (4)	0.0173 (4)	0.0015 (3)	−0.0008 (3)	0.0026 (3)
S2	0.0153 (4)	0.0147 (4)	0.0199 (4)	−0.0025 (3)	0.0031 (3)	0.0014 (3)
O1	0.0184 (12)	0.0191 (12)	0.0310 (15)	−0.0043 (10)	0.0077 (11)	−0.0040 (11)
O2	0.0204 (13)	0.0205 (12)	0.0309 (15)	0.0037 (10)	−0.0070 (11)	−0.0070 (11)
N1	0.0158 (14)	0.0158 (13)	0.0154 (14)	0.0053 (11)	0.0039 (11)	0.0037 (10)
N2	0.0145 (13)	0.0118 (12)	0.0157 (14)	−0.0011 (10)	0.0029 (11)	−0.0022 (10)
N3	0.0171 (14)	0.0161 (13)	0.0206 (15)	−0.0071 (11)	−0.0011 (12)	0.0006 (11)
N4	0.0141 (13)	0.0154 (13)	0.0191 (14)	−0.0001 (10)	0.0016 (11)	−0.0022 (11)
C1	0.0141 (15)	0.0159 (15)	0.0162 (16)	0.0013 (12)	−0.0003 (12)	−0.0014 (12)
C2	0.0191 (17)	0.0161 (16)	0.0259 (19)	−0.0012 (13)	0.0042 (14)	−0.0053 (13)
C3	0.0165 (17)	0.0258 (18)	0.030 (2)	−0.0058 (14)	0.0078 (15)	−0.0075 (15)
C4	0.0172 (17)	0.0254 (18)	0.029 (2)	0.0016 (14)	0.0050 (15)	−0.0027 (15)
C5	0.027 (2)	0.0170 (17)	0.027 (2)	0.0042 (14)	0.0069 (16)	−0.0024 (14)
C6	0.0264 (19)	0.0152 (16)	0.0209 (18)	−0.0008 (13)	0.0076 (14)	−0.0031 (13)
C7	0.0164 (16)	0.0163 (15)	0.0125 (15)	0.0004 (12)	−0.0008 (12)	0.0005 (12)
C8	0.0109 (14)	0.0167 (15)	0.0141 (15)	−0.0023 (12)	−0.0017 (12)	−0.0025 (12)
C9	0.0160 (16)	0.0184 (16)	0.0242 (18)	0.0031 (13)	0.0087 (14)	0.0039 (14)
C10	0.0139 (15)	0.0160 (15)	0.0228 (18)	−0.0004 (12)	0.0015 (13)	0.0021 (13)
C11	0.0162 (16)	0.0210 (17)	0.0271 (19)	−0.0009 (13)	0.0072 (14)	0.0023 (14)
C12	0.0160 (16)	0.0312 (19)	0.0231 (19)	0.0009 (14)	0.0057 (14)	0.0039 (15)
C13	0.0193 (18)	0.0255 (18)	0.031 (2)	−0.0004 (14)	0.0003 (15)	0.0101 (16)
C14	0.031 (2)	0.0213 (18)	0.029 (2)	−0.0020 (15)	−0.0030 (16)	0.0002 (15)
C15	0.030 (2)	0.0186 (17)	0.0242 (19)	−0.0007 (14)	0.0005 (15)	0.0011 (14)
C16	0.0190 (16)	0.0179 (15)	0.0163 (16)	0.0058 (12)	0.0048 (13)	0.0052 (13)
C17	0.0130 (15)	0.0192 (15)	0.0166 (16)	0.0035 (12)	0.0004 (12)	0.0034 (13)
C18	0.0195 (17)	0.0227 (17)	0.0180 (17)	−0.0022 (13)	−0.0012 (13)	0.0027 (14)
C19	0.0211 (18)	0.032 (2)	0.0141 (17)	−0.0012 (15)	0.0003 (14)	0.0044 (14)
C20	0.0238 (19)	0.031 (2)	0.0248 (19)	−0.0036 (15)	−0.0021 (15)	−0.0018 (16)
C21	0.031 (2)	0.0244 (19)	0.029 (2)	−0.0068 (15)	−0.0015 (16)	0.0006 (15)
C22	0.0289 (19)	0.0224 (17)	0.0192 (18)	−0.0051 (15)	0.0052 (15)	0.0039 (14)
C23	0.0145 (15)	0.0179 (15)	0.0132 (15)	−0.0013 (12)	0.0003 (12)	−0.0014 (12)
C24	0.0203 (18)	0.0170 (16)	0.0252 (19)	−0.0012 (13)	−0.0008 (15)	−0.0043 (14)
C25	0.0228 (18)	0.0198 (17)	0.028 (2)	−0.0004 (14)	−0.0053 (15)	−0.0087 (15)
C26	0.0183 (18)	0.0298 (19)	0.036 (2)	−0.0001 (15)	−0.0116 (16)	−0.0074 (17)
C27	0.0180 (18)	0.0263 (19)	0.028 (2)	0.0045 (14)	−0.0039 (15)	−0.0032 (15)
C28	0.0181 (17)	0.0207 (16)	0.0199 (17)	0.0000 (13)	−0.0019 (14)	−0.0019 (13)
C29	0.0175 (16)	0.0178 (15)	0.0121 (15)	0.0004 (12)	0.0002 (12)	0.0000 (12)
C30	0.0155 (15)	0.0130 (14)	0.0172 (16)	−0.0015 (12)	0.0033 (12)	−0.0041 (12)
C31	0.0266 (18)	0.0189 (16)	0.0170 (17)	−0.0093 (14)	0.0004 (14)	0.0010 (13)
C32	0.0219 (17)	0.0185 (16)	0.0142 (16)	−0.0085 (13)	0.0002 (13)	−0.0008 (13)
C33	0.0189 (17)	0.0204 (17)	0.0204 (18)	−0.0023 (13)	−0.0012 (13)	0.0030 (13)
C34	0.0172 (17)	0.0334 (19)	0.0156 (17)	0.0018 (14)	−0.0013 (13)	0.0018 (15)
C35	0.0258 (19)	0.029 (2)	0.0187 (18)	−0.0012 (15)	−0.0002 (15)	−0.0018 (15)
C36	0.027 (2)	0.0238 (19)	0.028 (2)	0.0093 (15)	−0.0025 (16)	−0.0043 (15)
C37	0.027 (2)	0.0275 (19)	0.027 (2)	−0.0015 (15)	−0.0071 (16)	0.0053 (16)
C38	0.0217 (17)	0.0205 (17)	0.027 (2)	−0.0067 (14)	−0.0072 (15)	−0.0003 (14)
C39	0.0210 (18)	0.0235 (17)	0.0190 (17)	−0.0059 (14)	−0.0022 (14)	0.0027 (14)
C40	0.0188 (18)	0.0309 (19)	0.0234 (19)	−0.0093 (15)	−0.0040 (14)	0.0052 (15)
C41	0.0180 (18)	0.036 (2)	0.037 (2)	−0.0102 (16)	−0.0069 (16)	0.0093 (17)
C42	0.0201 (18)	0.0238 (18)	0.043 (2)	−0.0037 (15)	0.0075 (17)	0.0078 (16)
C43	0.034 (2)	0.0236 (19)	0.035 (2)	0.0015 (17)	0.0039 (18)	−0.0001 (16)
C44	0.031 (2)	0.0240 (18)	0.0214 (19)	−0.0031 (15)	−0.0013 (15)	−0.0002 (15)

S1—C8	1.676 (3)	C18—H18	0.9500
S2—C30	1.678 (3)	C19—C20	1.393 (5)
O1—C7	1.214 (4)	C19—H19	0.9500
O2—C29	1.221 (4)	C20—C21	1.390 (6)
N1—C8	1.337 (4)	C20—H20	0.9500
N1—C16	1.480 (4)	C21—C22	1.385 (5)
N1—C9	1.484 (4)	C21—H21	0.9500
N2—C7	1.382 (4)	C22—H22	0.9500
N2—C8	1.396 (4)	C23—C28	1.390 (5)
N2—H2	0.8600	C23—C24	1.400 (5)
N3—C30	1.329 (4)	C23—C29	1.489 (5)
N3—C38	1.462 (4)	C24—C25	1.380 (5)
N3—C31	1.477 (4)	C24—H24	0.9500
N4—C29	1.386 (4)	C25—C26	1.399 (5)
N4—C30	1.410 (4)	C25—H25	0.9500
N4—H4	0.8600	C26—C27	1.378 (5)
C1—C2	1.393 (5)	C26—H26	0.9500
C1—C6	1.404 (5)	C27—C28	1.395 (5)
C1—C7	1.495 (5)	C27—H27	0.9500
C2—C3	1.386 (5)	C28—H28	0.9500
C2—H2A	0.9500	C31—C32	1.522 (5)
C3—C4	1.387 (5)	C31—H31A	0.9900
C3—H3	0.9500	C31—H31B	0.9900
C4—C5	1.384 (5)	C32—C37	1.386 (5)
C4—H4A	0.9500	C32—C33	1.393 (5)
C5—C6	1.384 (5)	C33—C34	1.381 (5)
C5—H5	0.9500	C33—H33	0.9500
C6—H6	0.9500	C34—C35	1.384 (5)
C9—C10	1.504 (5)	C34—H34	0.9500
C9—H9A	0.9900	C35—C36	1.403 (5)
C9—H9B	0.9900	C35—H35	0.9500
C10—C15	1.401 (5)	C36—C37	1.387 (6)
C10—C11	1.405 (5)	C36—H36	0.9500
C11—C12	1.394 (5)	C37—H37	0.9500
C11—H11	0.9500	C38—C39	1.507 (5)
C12—C13	1.379 (6)	C38—H38A	0.9900
C12—H12	0.9500	C38—H38B	0.9900
C13—C14	1.384 (6)	C39—C40	1.391 (5)
C13—H13	0.9500	C39—C44	1.399 (5)
C14—C15	1.389 (5)	C40—C41	1.411 (6)
C14—H14	0.9500	C40—H40	0.9500
C15—H15	0.9500	C41—C42	1.379 (6)
C16—C17	1.522 (5)	C41—H41	0.9500
C16—H16A	0.9900	C42—C43	1.388 (6)
C16—H16B	0.9900	C42—H42	0.9500
C17—C18	1.376 (5)	C43—C44	1.399 (6)
C17—C22	1.406 (5)	C43—H43	0.9500
C18—C19	1.398 (5)	C44—H44	0.9500
C8—N1—C16	123.3 (3)	C22—C21—C20	120.6 (3)
C8—N1—C9	119.3 (3)	C22—C21—H21	119.7
C16—N1—C9	115.5 (3)	C20—C21—H21	119.7
C7—N2—C8	124.4 (3)	C21—C22—C17	119.6 (3)
C7—N2—H2	117.8	C21—C22—H22	120.2
C8—N2—H2	117.8	C17—C22—H22	120.2
C30—N3—C38	121.0 (3)	C28—C23—C24	119.3 (3)
C30—N3—C31	122.8 (3)	C28—C23—C29	123.9 (3)
C38—N3—C31	115.3 (3)	C24—C23—C29	116.9 (3)
C29—N4—C30	122.3 (3)	C25—C24—C23	120.2 (3)
C29—N4—H4	118.8	C25—C24—H24	119.9
C30—N4—H4	118.8	C23—C24—H24	119.9
C2—C1—C6	118.9 (3)	C24—C25—C26	120.1 (3)
C2—C1—C7	124.1 (3)	C24—C25—H25	120.0
C6—C1—C7	117.0 (3)	C26—C25—H25	120.0
C3—C2—C1	120.5 (3)	C27—C26—C25	120.2 (3)
C3—C2—H2A	119.8	C27—C26—H26	119.9
C1—C2—H2A	119.8	C25—C26—H26	119.9
C2—C3—C4	119.9 (3)	C26—C27—C28	119.8 (3)
C2—C3—H3	120.0	C26—C27—H27	120.1
C4—C3—H3	120.0	C28—C27—H27	120.1
C5—C4—C3	120.3 (3)	C23—C28—C27	120.5 (3)
C5—C4—H4A	119.9	C23—C28—H28	119.7
C3—C4—H4A	119.9	C27—C28—H28	119.7
C6—C5—C4	120.0 (3)	O2—C29—N4	121.4 (3)
C6—C5—H5	120.0	O2—C29—C23	122.5 (3)
C4—C5—H5	120.0	N4—C29—C23	116.1 (3)
C5—C6—C1	120.3 (3)	N3—C30—N4	116.9 (3)
C5—C6—H6	119.8	N3—C30—S2	126.2 (2)
C1—C6—H6	119.8	N4—C30—S2	116.9 (3)
O1—C7—N2	121.7 (3)	N3—C31—C32	109.9 (3)
O1—C7—C1	122.9 (3)	N3—C31—H31A	109.7
N2—C7—C1	115.4 (3)	C32—C31—H31A	109.7
N1—C8—N2	117.1 (3)	N3—C31—H31B	109.7
N1—C8—S1	124.9 (3)	C32—C31—H31B	109.7
N2—C8—S1	117.9 (2)	H31A—C31—H31B	108.2
N1—C9—C10	113.8 (3)	C37—C32—C33	120.0 (3)
N1—C9—H9A	108.8	C37—C32—C31	119.7 (3)
C10—C9—H9A	108.8	C33—C32—C31	120.3 (3)
N1—C9—H9B	108.8	C34—C33—C32	120.1 (3)
C10—C9—H9B	108.8	C34—C33—H33	119.9
H9A—C9—H9B	107.7	C32—C33—H33	119.9
C15—C10—C11	119.3 (3)	C33—C34—C35	120.2 (3)
C15—C10—C9	120.9 (3)	C33—C34—H34	119.9
C11—C10—C9	119.7 (3)	C35—C34—H34	119.9
C12—C11—C10	120.1 (3)	C34—C35—C36	119.9 (3)
C12—C11—H11	120.0	C34—C35—H35	120.1
C10—C11—H11	120.0	C36—C35—H35	120.1
C13—C12—C11	120.0 (4)	C37—C36—C35	119.6 (3)
C13—C12—H12	120.0	C37—C36—H36	120.2
C11—C12—H12	120.0	C35—C36—H36	120.2
C12—C13—C14	120.4 (4)	C32—C37—C36	120.1 (4)
C12—C13—H13	119.8	C32—C37—H37	119.9
C14—C13—H13	119.8	C36—C37—H37	119.9
C13—C14—C15	120.5 (4)	N3—C38—C39	113.1 (3)
C13—C14—H14	119.8	N3—C38—H38A	109.0
C15—C14—H14	119.8	C39—C38—H38A	109.0
C14—C15—C10	119.8 (4)	N3—C38—H38B	109.0
C14—C15—H15	120.1	C39—C38—H38B	109.0
C10—C15—H15	120.1	H38A—C38—H38B	107.8
N1—C16—C17	110.5 (3)	C40—C39—C44	119.8 (4)
N1—C16—H16A	109.6	C40—C39—C38	119.4 (3)
C17—C16—H16A	109.6	C44—C39—C38	120.7 (3)
N1—C16—H16B	109.6	C39—C40—C41	119.6 (4)
C17—C16—H16B	109.6	C39—C40—H40	120.2
H16A—C16—H16B	108.1	C41—C40—H40	120.2
C18—C17—C22	119.9 (3)	C42—C41—C40	120.3 (4)
C18—C17—C16	120.3 (3)	C42—C41—H41	119.8
C22—C17—C16	119.7 (3)	C40—C41—H41	119.8
C17—C18—C19	120.3 (3)	C41—C42—C43	120.2 (4)
C17—C18—H18	119.8	C41—C42—H42	119.9
C19—C18—H18	119.8	C43—C42—H42	119.9
C20—C19—C18	119.9 (3)	C42—C43—C44	120.0 (4)
C20—C19—H19	120.0	C42—C43—H43	120.0
C18—C19—H19	120.0	C44—C43—H43	120.0
C21—C20—C19	119.6 (4)	C43—C44—C39	120.0 (4)
C21—C20—H20	120.2	C43—C44—H44	120.0
C19—C20—H20	120.2	C39—C44—H44	120.0
C6—C1—C2—C3	−0.2 (5)	C28—C23—C24—C25	0.3 (5)
C7—C1—C2—C3	−177.6 (3)	C29—C23—C24—C25	−179.0 (3)
C1—C2—C3—C4	−0.2 (6)	C23—C24—C25—C26	−1.8 (6)
C2—C3—C4—C5	0.5 (6)	C24—C25—C26—C27	2.8 (7)
C3—C4—C5—C6	−0.3 (6)	C25—C26—C27—C28	−2.3 (6)
C4—C5—C6—C1	−0.1 (6)	C24—C23—C28—C27	0.1 (5)
C2—C1—C6—C5	0.4 (5)	C29—C23—C28—C27	179.4 (3)
C7—C1—C6—C5	177.9 (3)	C26—C27—C28—C23	0.9 (6)
C8—N2—C7—O1	12.0 (5)	C30—N4—C29—O2	11.8 (5)
C8—N2—C7—C1	−168.0 (3)	C30—N4—C29—C23	−168.1 (3)
C2—C1—C7—O1	−178.0 (3)	C28—C23—C29—O2	174.3 (3)
C6—C1—C7—O1	4.6 (5)	C24—C23—C29—O2	−6.4 (5)
C2—C1—C7—N2	2.1 (5)	C28—C23—C29—N4	−5.8 (5)
C6—C1—C7—N2	−175.3 (3)	C24—C23—C29—N4	173.5 (3)
C16—N1—C8—N2	−19.0 (5)	C38—N3—C30—N4	174.2 (3)
C9—N1—C8—N2	177.2 (3)	C31—N3—C30—N4	−17.7 (5)
C16—N1—C8—S1	158.1 (3)	C38—N3—C30—S2	−7.3 (5)
C9—N1—C8—S1	−5.7 (5)	C31—N3—C30—S2	160.7 (3)
C7—N2—C8—N1	−61.4 (4)	C29—N4—C30—N3	−62.3 (4)
C7—N2—C8—S1	121.3 (3)	C29—N4—C30—S2	119.1 (3)
C8—N1—C9—C10	−146.6 (3)	C30—N3—C31—C32	−106.5 (4)
C16—N1—C9—C10	48.4 (4)	C38—N3—C31—C32	62.2 (4)
N1—C9—C10—C15	55.3 (5)	N3—C31—C32—C37	62.2 (4)
N1—C9—C10—C11	−128.9 (3)	N3—C31—C32—C33	−117.7 (3)
C15—C10—C11—C12	0.4 (5)	C37—C32—C33—C34	1.3 (5)
C9—C10—C11—C12	−175.5 (3)	C31—C32—C33—C34	−178.8 (3)
C10—C11—C12—C13	−0.2 (5)	C32—C33—C34—C35	−1.0 (5)
C11—C12—C13—C14	0.1 (6)	C33—C34—C35—C36	0.6 (6)
C12—C13—C14—C15	−0.2 (6)	C34—C35—C36—C37	−0.6 (6)
C13—C14—C15—C10	0.4 (6)	C33—C32—C37—C36	−1.3 (6)
C11—C10—C15—C14	−0.5 (5)	C31—C32—C37—C36	178.8 (4)
C9—C10—C15—C14	175.3 (3)	C35—C36—C37—C32	0.9 (6)
C8—N1—C16—C17	−103.7 (4)	C30—N3—C38—C39	−132.9 (3)
C9—N1—C16—C17	60.7 (4)	C31—N3—C38—C39	58.2 (4)
N1—C16—C17—C18	−123.1 (3)	N3—C38—C39—C40	−139.2 (3)
N1—C16—C17—C22	59.2 (4)	N3—C38—C39—C44	44.8 (5)
C22—C17—C18—C19	1.2 (5)	C44—C39—C40—C41	1.3 (5)
C16—C17—C18—C19	−176.5 (3)	C38—C39—C40—C41	−174.8 (3)
C17—C18—C19—C20	−1.0 (5)	C39—C40—C41—C42	0.5 (6)
C18—C19—C20—C21	0.2 (6)	C40—C41—C42—C43	−1.8 (6)
C19—C20—C21—C22	0.4 (6)	C41—C42—C43—C44	1.2 (6)
C20—C21—C22—C17	−0.2 (6)	C42—C43—C44—C39	0.7 (6)
C18—C17—C22—C21	−0.7 (5)	C40—C39—C44—C43	−1.9 (6)
C16—C17—C22—C21	177.1 (3)	C38—C39—C44—C43	174.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S2	0.86	2.54	3.334 (3)	154
N4—H4···S1i	0.86	2.54	3.334 (3)	154
C13—H13···O2ii	0.95	2.57	3.193 (5)	124
C14—H14···O2ii	0.95	2.60	3.207 (5)	122
C25—H25···O1iii	0.95	2.55	3.228 (4)	129

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯S2	0.86	2.54	3.334 (3)	154
N4—H4⋯S1i	0.86	2.54	3.334 (3)	154
C13—H13⋯O2ii	0.95	2.57	3.193 (5)	124
C14—H14⋯O2ii	0.95	2.60	3.207 (5)	122
C25—H25⋯O1iii	0.95	2.55	3.228 (4)	129

Symmetry codes: (i) ; (ii) ; (iii) .