N'-[(5-Methyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)(thio-phen-2-yl)methyl-idene]benzohydrazide.

In the title compound, C(22)H(18)N(4)O(2)S, the seven-membered ring generated by an intra-molecular N-H⋯O hydrogen bond adopts an envelope conformation in both of the two independent mol-ecules in the asymmetric unit. In the crystal, mol-ecules are linked into C(9) chains along [100] by N-H⋯O hydrogen bonds. The mol-ecules are also weakly linked by C-H⋯O and C-H⋯N inter-actions, forming dimers with edge-connected R(2) (2)(9) rings. The dimers are inter-linked by further weak C-H⋯N hydrogen bonds into chains along [010].

Related literature

For the biological activity of hydrazones, see: Mahalingam et al. (2009 ▶); Kocyigit-Kaymakcioglu et al. (2009 ▶); Zhang et al. (2007 ▶); Gemma et al. (2006 ▶). For uses of hydrazones, see: Gupta et al. (2007 ▶). For applications of pyrazolone derivatives, see: Li et al. (2000 ▶); Shi et al. (2005 ▶); Zhang et al. (2008 ▶). For related structures, see: Qiu (2009 ▶); Ren (2009 ▶).

Experimental

Crystal data

C22H18N4O2S

M = 402.46

Orthorhombic,

a = 13.562 (5) Å

b = 16.729 (6) Å

c = 17.258 (6) Å

V = 3916 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.19 mm−1

T = 113 K

0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn724 CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ▶) T min = 0.963, T max = 0.977

41426 measured reflections

9266 independent reflections

7812 reflections with I > 2σ(I)

R int = 0.082

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.103

S = 1.00

9266 reflections

541 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.53 e Å−3

Δρmin = −0.57 e Å−3

Absolute structure: Flack (1983 ▶), 4123 Friedel pairs

Flack parameter: −0.01 (6)

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear ; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014821/fj2536sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014821/fj2536Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812014821/fj2536Isup3.cml

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

C22H18N4O2S	F(000) = 1680
Mr = 402.46	Dx = 1.365 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 14107 reflections
a = 13.562 (5) Å	θ = 1.7–27.9°
b = 16.729 (6) Å	µ = 0.19 mm−1
c = 17.258 (6) Å	T = 113 K
V = 3916 (2) Å3	Prism, colourless
Z = 8	0.20 × 0.18 × 0.12 mm

Rigaku Saturn724 CCD diffractometer	9266 independent reflections
Radiation source: fine-focus sealed tube	7812 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
Detector resolution: 14.22 pixels mm-1	θmax = 27.9°, θmin = 1.7°
ω and φ scans	h = −17→17
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −22→22
Tmin = 0.963, Tmax = 0.977	l = −22→22
41426 measured reflections

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103	w = 1/[σ2(Fo2) + (0.0431P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
9266 reflections	Δρmax = 0.53 e Å−3
541 parameters	Δρmin = −0.57 e Å−3
7 restraints	Absolute structure: Flack (1983), 4123 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.01 (6)

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.

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 > σ(F2) is used only for calculating R-factors(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.

	x	y	z	Uiso*/Ueq
S1	−0.03830 (5)	0.71956 (4)	1.11387 (4)	0.02597 (15)
O1	0.32273 (11)	0.58102 (9)	0.99164 (10)	0.0192 (4)
O2	0.00489 (12)	0.62704 (10)	0.85706 (10)	0.0225 (4)
N1	0.41739 (14)	0.68241 (10)	1.04849 (11)	0.0162 (4)
N2	0.39591 (14)	0.75401 (11)	1.08442 (12)	0.0179 (4)
N3	0.09446 (14)	0.65442 (11)	0.99061 (11)	0.0175 (4)
N4	0.14777 (14)	0.63005 (11)	0.92562 (11)	0.0167 (4)
C1	0.51201 (16)	0.64760 (13)	1.05797 (13)	0.0162 (5)
C2	0.53891 (17)	0.58191 (13)	1.01313 (14)	0.0208 (5)
H2	0.4952	0.5606	0.9754	0.025*
C3	0.63134 (17)	0.54841 (14)	1.02498 (15)	0.0235 (5)
H3	0.6501	0.5028	0.9957	0.028*
C4	0.69714 (18)	0.57982 (15)	1.07857 (16)	0.0259 (6)
H4	0.7604	0.5564	1.0851	0.031*
C5	0.67008 (18)	0.64501 (15)	1.12212 (15)	0.0262 (6)
H5	0.7150	0.6671	1.1585	0.031*
C6	0.57672 (17)	0.67876 (13)	1.11298 (15)	0.0210 (5)
H6	0.5573	0.7228	1.1442	0.025*
C7	0.32789 (16)	0.64663 (13)	1.02580 (13)	0.0147 (5)
C8	0.25253 (16)	0.70038 (13)	1.05077 (13)	0.0153 (5)
C9	0.29774 (16)	0.76560 (13)	1.08431 (13)	0.0160 (5)
C11	0.14507 (17)	0.68506 (13)	1.04734 (13)	0.0152 (5)
C12	0.08755 (17)	0.70277 (13)	1.11724 (14)	0.0182 (5)
C13	0.12018 (18)	0.70293 (14)	1.19226 (14)	0.0214 (5)
H13	0.1870	0.6940	1.2063	0.026*
C14	0.04498 (19)	0.71769 (15)	1.24670 (14)	0.0257 (6)
H14	0.0558	0.7200	1.3010	0.031*
C15	−0.0450 (2)	0.72826 (15)	1.21298 (15)	0.0268 (6)
H15	−0.1040	0.7391	1.2408	0.032*
C16	0.09352 (17)	0.61021 (13)	0.86222 (13)	0.0165 (5)
C17	0.14549 (18)	0.56975 (13)	0.79726 (13)	0.0174 (5)
C18	0.24761 (19)	0.57110 (17)	0.78695 (15)	0.0288 (6)
H18	0.2883	0.5976	0.8237	0.035*
C19	0.28974 (19)	0.53406 (18)	0.72339 (17)	0.0339 (7)
H19	0.3592	0.5360	0.7165	0.041*
C20	0.23189 (19)	0.49425 (16)	0.66971 (15)	0.0268 (6)
H20	0.2611	0.4686	0.6263	0.032*
C21	0.1307 (2)	0.49244 (16)	0.68048 (16)	0.0310 (6)
H21	0.0902	0.4651	0.6442	0.037*
C22	0.08813 (19)	0.52985 (15)	0.74315 (16)	0.0274 (6)
H22	0.0186	0.5283	0.7494	0.033*
S2	−0.09874 (5)	0.34519 (4)	0.00961 (4)	0.03026 (16)
O3	0.24984 (11)	0.24796 (9)	0.17686 (9)	0.0199 (4)
O4	−0.02713 (12)	0.08734 (9)	0.08119 (10)	0.0208 (4)
N5	0.35661 (14)	0.31492 (11)	0.09300 (11)	0.0186 (4)
N6	0.34621 (14)	0.35697 (11)	0.02458 (12)	0.0182 (4)
N7	0.04294 (14)	0.23573 (11)	0.07448 (11)	0.0181 (4)
N8	0.10040 (14)	0.17233 (11)	0.10211 (12)	0.0170 (4)
C10	0.25968 (17)	0.84234 (14)	1.11489 (15)	0.0212 (5)
H10A	0.2638	0.8422	1.1716	0.032*
H10B	0.1908	0.8491	1.0990	0.032*
H10C	0.2992	0.8865	1.0943	0.032*
C23	0.45209 (16)	0.30388 (13)	0.12491 (13)	0.0179 (5)
C24	0.46974 (18)	0.24164 (14)	0.17687 (15)	0.0227 (5)
H24	0.4177	0.2074	0.1929	0.027*
C25	0.56520 (18)	0.23076 (15)	0.20470 (15)	0.0255 (6)
H25	0.5777	0.1892	0.2409	0.031*
C26	0.64183 (19)	0.27877 (17)	0.18090 (16)	0.0295 (6)
H26	0.7068	0.2698	0.1995	0.035*
C27	0.62270 (18)	0.34085 (17)	0.12900 (16)	0.0305 (6)
H27	0.6751	0.3740	0.1117	0.037*
C28	0.52799 (18)	0.35436 (15)	0.10266 (15)	0.0243 (5)
H28	0.5149	0.3983	0.0693	0.029*
C29	0.26401 (16)	0.28772 (13)	0.11669 (13)	0.0157 (5)
C30	0.19616 (16)	0.31593 (12)	0.05886 (13)	0.0159 (5)
C31	0.25075 (16)	0.35685 (13)	0.00345 (14)	0.0177 (5)
C32	0.22506 (18)	0.39519 (15)	−0.07270 (14)	0.0233 (5)
H32A	0.2275	0.4535	−0.0673	0.035*
H32B	0.1585	0.3789	−0.0882	0.035*
H32C	0.2724	0.3782	−0.1123	0.035*
C33	0.08897 (16)	0.30131 (13)	0.05762 (13)	0.0154 (5)
C34	0.02208 (17)	0.36645 (14)	0.03500 (14)	0.0193 (5)
C35	0.04202 (17)	0.45161 (14)	0.03426 (14)	0.0204 (5)
H35	0.1023	0.4764	0.0488	0.025*
C36	−0.04525 (18)	0.49200 (14)	0.00765 (16)	0.0265 (6)
H36	−0.0479	0.5483	0.0006	0.032*
C37	−0.12364 (18)	0.44355 (15)	−0.00669 (17)	0.0288 (6)
H37	−0.1859	0.4626	−0.0240	0.035*
C38	0.05203 (17)	0.10249 (13)	0.11298 (14)	0.0174 (5)
C39	0.09756 (17)	0.04402 (13)	0.16751 (14)	0.0180 (5)
C40	0.19398 (18)	0.04933 (14)	0.19578 (15)	0.0222 (5)
H40	0.2371	0.0898	0.1772	0.027*
C41	0.22648 (19)	−0.00513 (16)	0.25131 (16)	0.0270 (6)
H41	0.2924	−0.0025	0.2699	0.032*
C42	0.1631 (2)	−0.06279 (15)	0.27940 (15)	0.0278 (6)
H42	0.1849	−0.0985	0.3186	0.033*
C43	0.06866 (19)	−0.06888 (15)	0.25105 (16)	0.0274 (6)
H43	0.0257	−0.1090	0.2705	0.033*
C44	0.03588 (19)	−0.01664 (14)	0.19422 (15)	0.0241 (5)
H44	−0.0286	−0.0222	0.1735	0.029*
H2A	0.4390 (14)	0.7935 (11)	1.0964 (15)	0.025 (7)*
H4A	0.2090 (9)	0.6092 (13)	0.9308 (14)	0.016 (6)*
H6A	0.3952 (14)	0.3734 (15)	−0.0057 (13)	0.034 (8)*
H8A	0.1528 (13)	0.1844 (15)	0.1327 (13)	0.033 (8)*

	U11	U22	U33	U12	U13	U23
S1	0.0178 (3)	0.0374 (4)	0.0227 (3)	0.0044 (3)	0.0035 (3)	0.0032 (3)
O1	0.0183 (9)	0.0169 (8)	0.0223 (9)	0.0009 (6)	−0.0017 (7)	−0.0046 (7)
O2	0.0187 (9)	0.0254 (9)	0.0235 (9)	0.0047 (7)	−0.0045 (7)	−0.0060 (8)
N1	0.0163 (10)	0.0123 (8)	0.0199 (10)	0.0008 (8)	0.0008 (8)	−0.0044 (8)
N2	0.0185 (11)	0.0148 (9)	0.0203 (10)	−0.0024 (8)	0.0002 (9)	−0.0049 (8)
N3	0.0179 (10)	0.0175 (9)	0.0170 (10)	0.0030 (8)	−0.0001 (9)	−0.0010 (8)
N4	0.0147 (11)	0.0190 (10)	0.0163 (10)	0.0014 (8)	−0.0006 (9)	−0.0033 (8)
C1	0.0124 (12)	0.0166 (11)	0.0198 (11)	−0.0010 (9)	0.0032 (9)	0.0032 (10)
C2	0.0197 (13)	0.0227 (12)	0.0199 (12)	−0.0014 (10)	0.0041 (11)	−0.0022 (10)
C3	0.0204 (13)	0.0234 (12)	0.0267 (13)	0.0013 (10)	0.0043 (11)	−0.0017 (11)
C4	0.0186 (13)	0.0299 (13)	0.0291 (14)	0.0069 (11)	−0.0022 (11)	0.0032 (12)
C5	0.0221 (14)	0.0294 (13)	0.0272 (14)	−0.0005 (11)	−0.0046 (11)	0.0003 (12)
C6	0.0235 (13)	0.0187 (11)	0.0207 (12)	0.0003 (10)	0.0000 (11)	0.0009 (10)
C7	0.0163 (12)	0.0151 (10)	0.0126 (10)	−0.0019 (9)	−0.0014 (9)	0.0019 (9)
C8	0.0135 (11)	0.0172 (11)	0.0152 (11)	−0.0008 (9)	0.0011 (9)	0.0008 (9)
C9	0.0156 (12)	0.0168 (11)	0.0157 (11)	0.0013 (9)	−0.0006 (9)	0.0009 (9)
C11	0.0182 (12)	0.0138 (10)	0.0137 (11)	0.0019 (9)	0.0004 (10)	0.0006 (9)
C12	0.0170 (12)	0.0181 (11)	0.0194 (12)	0.0004 (10)	0.0009 (10)	−0.0032 (10)
C13	0.0202 (13)	0.0234 (12)	0.0208 (12)	−0.0058 (10)	0.0013 (10)	0.0006 (10)
C14	0.0313 (15)	0.0274 (13)	0.0183 (12)	−0.0060 (12)	0.0039 (12)	−0.0003 (11)
C15	0.0261 (14)	0.0308 (14)	0.0234 (13)	0.0014 (12)	0.0087 (12)	0.0033 (11)
C16	0.0176 (13)	0.0130 (10)	0.0188 (12)	−0.0009 (10)	−0.0035 (10)	−0.0007 (9)
C17	0.0234 (13)	0.0138 (10)	0.0149 (11)	0.0021 (10)	−0.0025 (10)	−0.0005 (9)
C18	0.0211 (14)	0.0414 (16)	0.0237 (13)	−0.0044 (12)	−0.0027 (11)	−0.0102 (12)
C19	0.0189 (14)	0.0537 (18)	0.0292 (15)	0.0023 (13)	0.0019 (12)	−0.0114 (14)
C20	0.0335 (16)	0.0269 (13)	0.0198 (12)	0.0041 (12)	0.0040 (12)	−0.0064 (11)
C21	0.0347 (16)	0.0319 (14)	0.0264 (14)	−0.0033 (12)	−0.0041 (12)	−0.0153 (12)
C22	0.0196 (13)	0.0320 (14)	0.0307 (14)	−0.0008 (11)	−0.0020 (12)	−0.0090 (12)
S2	0.0233 (3)	0.0276 (3)	0.0399 (4)	0.0031 (3)	−0.0033 (3)	−0.0053 (3)
O3	0.0203 (9)	0.0225 (8)	0.0168 (8)	−0.0038 (7)	−0.0004 (7)	0.0045 (7)
O4	0.0210 (9)	0.0189 (8)	0.0225 (9)	−0.0014 (7)	−0.0076 (8)	0.0038 (7)
N5	0.0202 (11)	0.0189 (9)	0.0167 (10)	−0.0020 (8)	−0.0001 (8)	0.0041 (8)
N6	0.0176 (11)	0.0201 (10)	0.0169 (10)	−0.0022 (9)	0.0010 (9)	0.0053 (8)
N7	0.0186 (10)	0.0165 (9)	0.0192 (10)	0.0018 (8)	−0.0001 (9)	0.0019 (8)
N8	0.0126 (10)	0.0172 (9)	0.0212 (11)	−0.0002 (8)	−0.0031 (9)	0.0035 (8)
C10	0.0185 (12)	0.0201 (11)	0.0249 (12)	0.0003 (10)	0.0010 (11)	−0.0033 (11)
C23	0.0139 (12)	0.0217 (11)	0.0182 (12)	−0.0012 (9)	−0.0004 (10)	−0.0033 (10)
C24	0.0213 (13)	0.0241 (12)	0.0226 (12)	−0.0017 (10)	0.0007 (11)	0.0024 (11)
C25	0.0263 (14)	0.0270 (13)	0.0233 (13)	0.0031 (11)	−0.0037 (11)	0.0013 (11)
C26	0.0165 (13)	0.0416 (15)	0.0304 (15)	0.0012 (12)	−0.0085 (12)	−0.0003 (13)
C27	0.0222 (14)	0.0385 (15)	0.0307 (15)	−0.0127 (12)	−0.0042 (11)	0.0062 (13)
C28	0.0232 (13)	0.0266 (13)	0.0230 (12)	−0.0040 (11)	−0.0049 (11)	0.0036 (11)
C29	0.0142 (12)	0.0161 (10)	0.0167 (11)	−0.0007 (9)	0.0030 (10)	−0.0009 (10)
C30	0.0172 (12)	0.0141 (10)	0.0162 (11)	0.0005 (9)	0.0012 (10)	0.0022 (9)
C31	0.0164 (12)	0.0158 (10)	0.0209 (12)	0.0009 (9)	−0.0002 (10)	0.0002 (10)
C32	0.0222 (13)	0.0273 (13)	0.0204 (13)	0.0001 (11)	−0.0005 (11)	0.0072 (11)
C33	0.0143 (12)	0.0175 (11)	0.0145 (11)	−0.0010 (9)	0.0019 (10)	−0.0001 (9)
C34	0.0186 (9)	0.0220 (10)	0.0173 (11)	0.0011 (9)	0.0032 (9)	−0.0003 (10)
C35	0.0136 (11)	0.0227 (10)	0.0250 (12)	0.0090 (9)	0.0097 (10)	0.0138 (10)
C36	0.0225 (12)	0.0204 (12)	0.0368 (15)	0.0061 (10)	−0.0032 (12)	0.0042 (12)
C37	0.0252 (14)	0.0256 (13)	0.0355 (16)	0.0087 (11)	−0.0043 (12)	−0.0011 (12)
C38	0.0157 (12)	0.0181 (11)	0.0184 (11)	0.0018 (9)	0.0006 (10)	0.0002 (10)
C39	0.0199 (12)	0.0175 (11)	0.0166 (11)	0.0020 (10)	−0.0022 (10)	0.0006 (9)
C40	0.0221 (13)	0.0198 (12)	0.0248 (13)	0.0043 (10)	−0.0035 (11)	−0.0014 (10)
C41	0.0271 (15)	0.0270 (13)	0.0270 (14)	0.0078 (12)	−0.0116 (12)	−0.0071 (12)
C42	0.0383 (16)	0.0216 (12)	0.0235 (13)	0.0111 (12)	−0.0032 (12)	0.0022 (11)
C43	0.0300 (15)	0.0218 (12)	0.0305 (15)	0.0063 (11)	0.0045 (12)	0.0092 (11)
C44	0.0250 (14)	0.0220 (12)	0.0252 (13)	0.0041 (11)	−0.0011 (12)	0.0039 (11)

S1—C15	1.719 (3)	O4—C38	1.232 (3)
S1—C12	1.731 (2)	N5—N6	1.382 (3)
O1—C7	1.248 (3)	N5—C29	1.397 (3)
O2—C16	1.238 (3)	N5—C23	1.419 (3)
N1—N2	1.380 (2)	N6—C31	1.345 (3)
N1—C7	1.409 (3)	N6—H6A	0.889 (10)
N1—C1	1.419 (3)	N7—C33	1.295 (3)
N2—C9	1.346 (3)	N7—N8	1.400 (3)
N2—H2A	0.906 (10)	N8—C38	1.353 (3)
N3—C11	1.301 (3)	N8—H8A	0.908 (10)
N3—N4	1.395 (3)	C10—H10A	0.9800
N4—C16	1.360 (3)	C10—H10B	0.9800
N4—H4A	0.905 (10)	C10—H10C	0.9800
C1—C2	1.393 (3)	C23—C28	1.386 (3)
C1—C6	1.394 (3)	C23—C24	1.395 (3)
C2—C3	1.388 (3)	C24—C25	1.393 (3)
C2—H2	0.9500	C24—H24	0.9500
C3—C4	1.389 (4)	C25—C26	1.376 (4)
C3—H3	0.9500	C25—H25	0.9500
C4—C5	1.374 (4)	C26—C27	1.396 (4)
C4—H4	0.9500	C26—H26	0.9500
C5—C6	1.395 (3)	C27—C28	1.381 (3)
C5—H5	0.9500	C27—H27	0.9500
C6—H6	0.9500	C28—H28	0.9500
C7—C8	1.428 (3)	C29—C30	1.437 (3)
C8—C9	1.379 (3)	C30—C31	1.390 (3)
C8—C11	1.481 (3)	C30—C33	1.474 (3)
C9—C10	1.481 (3)	C31—C32	1.503 (3)
C11—C12	1.467 (3)	C32—H32A	0.9800
C12—C13	1.368 (3)	C32—H32B	0.9800
C13—C14	1.409 (3)	C32—H32C	0.9800
C13—H13	0.9500	C33—C34	1.471 (3)
C14—C15	1.363 (4)	C34—C35	1.450 (3)
C14—H14	0.9500	C35—C36	1.438 (3)
C15—H15	0.9500	C35—H35	0.9500
C16—C17	1.487 (3)	C36—C37	1.360 (4)
C17—C22	1.387 (3)	C36—H36	0.9500
C17—C18	1.397 (3)	C37—H37	0.9500
C18—C19	1.383 (4)	C38—C39	1.491 (3)
C18—H18	0.9500	C39—C44	1.394 (3)
C19—C20	1.385 (4)	C39—C40	1.399 (3)
C19—H19	0.9500	C40—C41	1.394 (3)
C20—C21	1.385 (4)	C40—H40	0.9500
C20—H20	0.9500	C41—C42	1.380 (4)
C21—C22	1.377 (4)	C41—H41	0.9500
C21—H21	0.9500	C42—C43	1.375 (4)
C22—H22	0.9500	C42—H42	0.9500
S2—C37	1.703 (3)	C43—C44	1.387 (3)
S2—C34	1.733 (3)	C43—H43	0.9500
O3—C29	1.248 (3)	C44—H44	0.9500
C15—S1—C12	91.84 (13)	N5—N6—H6A	125.7 (18)
N2—N1—C7	108.16 (18)	C33—N7—N8	116.74 (19)
N2—N1—C1	119.69 (19)	C38—N8—N7	115.57 (18)
C7—N1—C1	129.57 (18)	C38—N8—H8A	119.4 (16)
C9—N2—N1	109.47 (18)	N7—N8—H8A	117.7 (16)
C9—N2—H2A	122.2 (15)	C9—C10—H10A	109.5
N1—N2—H2A	126.8 (16)	C9—C10—H10B	109.5
C11—N3—N4	116.53 (19)	H10A—C10—H10B	109.5
C16—N4—N3	115.96 (19)	C9—C10—H10C	109.5
C16—N4—H4A	118.8 (15)	H10A—C10—H10C	109.5
N3—N4—H4A	120.6 (16)	H10B—C10—H10C	109.5
C2—C1—C6	120.6 (2)	C28—C23—C24	120.4 (2)
C2—C1—N1	119.8 (2)	C28—C23—N5	119.4 (2)
C6—C1—N1	119.6 (2)	C24—C23—N5	120.2 (2)
C3—C2—C1	118.2 (2)	C25—C24—C23	118.6 (2)
C3—C2—H2	120.9	C25—C24—H24	120.7
C1—C2—H2	120.9	C23—C24—H24	120.7
C4—C3—C2	121.7 (2)	C26—C25—C24	121.5 (2)
C4—C3—H3	119.1	C26—C25—H25	119.2
C2—C3—H3	119.1	C24—C25—H25	119.2
C5—C4—C3	119.5 (2)	C25—C26—C27	119.0 (2)
C5—C4—H4	120.2	C25—C26—H26	120.5
C3—C4—H4	120.2	C27—C26—H26	120.5
C4—C5—C6	120.1 (2)	C28—C27—C26	120.4 (2)
C4—C5—H5	119.9	C28—C27—H27	119.8
C6—C5—H5	119.9	C26—C27—H27	119.8
C1—C6—C5	119.8 (2)	C27—C28—C23	120.0 (2)
C1—C6—H6	120.1	C27—C28—H28	120.0
C5—C6—H6	120.1	C23—C28—H28	120.0
O1—C7—N1	123.6 (2)	O3—C29—N5	123.7 (2)
O1—C7—C8	131.0 (2)	O3—C29—C30	130.9 (2)
N1—C7—C8	105.38 (18)	N5—C29—C30	105.40 (19)
C9—C8—C7	107.87 (19)	C31—C30—C29	107.4 (2)
C9—C8—C11	126.2 (2)	C31—C30—C33	126.7 (2)
C7—C8—C11	125.7 (2)	C29—C30—C33	125.9 (2)
N2—C9—C8	109.06 (19)	N6—C31—C30	109.1 (2)
N2—C9—C10	118.0 (2)	N6—C31—C32	117.4 (2)
C8—C9—C10	132.9 (2)	C30—C31—C32	133.5 (2)
N3—C11—C12	114.7 (2)	C31—C32—H32A	109.5
N3—C11—C8	128.1 (2)	C31—C32—H32B	109.5
C12—C11—C8	117.09 (19)	H32A—C32—H32B	109.5
C13—C12—C11	127.3 (2)	C31—C32—H32C	109.5
C13—C12—S1	110.52 (18)	H32A—C32—H32C	109.5
C11—C12—S1	121.98 (18)	H32B—C32—H32C	109.5
C12—C13—C14	113.4 (2)	N7—C33—C34	112.9 (2)
C12—C13—H13	123.3	N7—C33—C30	127.8 (2)
C14—C13—H13	123.3	C34—C33—C30	119.29 (19)
C15—C14—C13	112.7 (2)	C35—C34—C33	128.0 (2)
C15—C14—H14	123.6	C35—C34—S2	112.07 (17)
C13—C14—H14	123.6	C33—C34—S2	119.88 (17)
C14—C15—S1	111.5 (2)	C36—C35—C34	108.1 (2)
C14—C15—H15	124.2	C36—C35—H35	125.9
S1—C15—H15	124.2	C34—C35—H35	125.9
O2—C16—N4	121.9 (2)	C37—C36—C35	114.9 (2)
O2—C16—C17	120.6 (2)	C37—C36—H36	122.5
N4—C16—C17	117.5 (2)	C35—C36—H36	122.5
C22—C17—C18	118.6 (2)	C36—C37—S2	113.01 (19)
C22—C17—C16	117.4 (2)	C36—C37—H37	123.5
C18—C17—C16	124.0 (2)	S2—C37—H37	123.5
C19—C18—C17	120.2 (2)	O4—C38—N8	122.6 (2)
C19—C18—H18	119.9	O4—C38—C39	120.5 (2)
C17—C18—H18	119.9	N8—C38—C39	117.0 (2)
C18—C19—C20	120.8 (2)	C44—C39—C40	119.5 (2)
C18—C19—H19	119.6	C44—C39—C38	116.0 (2)
C20—C19—H19	119.6	C40—C39—C38	124.4 (2)
C19—C20—C21	118.8 (2)	C41—C40—C39	119.6 (2)
C19—C20—H20	120.6	C41—C40—H40	120.2
C21—C20—H20	120.6	C39—C40—H40	120.2
C22—C21—C20	120.7 (2)	C42—C41—C40	120.1 (2)
C22—C21—H21	119.6	C42—C41—H41	119.9
C20—C21—H21	119.6	C40—C41—H41	119.9
C21—C22—C17	120.8 (2)	C43—C42—C41	120.5 (2)
C21—C22—H22	119.6	C43—C42—H42	119.8
C17—C22—H22	119.6	C41—C42—H42	119.8
C37—S2—C34	91.78 (12)	C42—C43—C44	120.2 (2)
N6—N5—C29	108.91 (18)	C42—C43—H43	119.9
N6—N5—C23	119.41 (18)	C44—C43—H43	119.9
C29—N5—C23	131.63 (19)	C43—C44—C39	120.0 (2)
C31—N6—N5	109.22 (19)	C43—C44—H44	120.0
C31—N6—H6A	124.1 (18)	C39—C44—H44	120.0
C7—N1—N2—C9	−1.0 (2)	C29—N5—N6—C31	−0.6 (2)
C1—N1—N2—C9	−164.5 (2)	C23—N5—N6—C31	177.2 (2)
C11—N3—N4—C16	−169.83 (19)	C33—N7—N8—C38	−174.6 (2)
N2—N1—C1—C2	−170.6 (2)	N6—N5—C23—C28	20.2 (3)
C7—N1—C1—C2	29.8 (3)	C29—N5—C23—C28	−162.6 (2)
N2—N1—C1—C6	10.3 (3)	N6—N5—C23—C24	−158.4 (2)
C7—N1—C1—C6	−149.2 (2)	C29—N5—C23—C24	18.8 (4)
C6—C1—C2—C3	0.2 (3)	C28—C23—C24—C25	−1.0 (4)
N1—C1—C2—C3	−178.8 (2)	N5—C23—C24—C25	177.6 (2)
C1—C2—C3—C4	−1.5 (4)	C23—C24—C25—C26	−1.3 (4)
C2—C3—C4—C5	1.0 (4)	C24—C25—C26—C27	1.5 (4)
C3—C4—C5—C6	0.7 (4)	C25—C26—C27—C28	0.7 (4)
C2—C1—C6—C5	1.4 (3)	C26—C27—C28—C23	−3.0 (4)
N1—C1—C6—C5	−179.6 (2)	C24—C23—C28—C27	3.2 (4)
C4—C5—C6—C1	−1.9 (4)	N5—C23—C28—C27	−175.4 (2)
N2—N1—C7—O1	179.9 (2)	N6—N5—C29—O3	−179.8 (2)
C1—N1—C7—O1	−18.7 (4)	C23—N5—C29—O3	2.8 (4)
N2—N1—C7—C8	−0.5 (2)	N6—N5—C29—C30	−0.2 (2)
C1—N1—C7—C8	160.9 (2)	C23—N5—C29—C30	−177.7 (2)
O1—C7—C8—C9	−178.7 (2)	O3—C29—C30—C31	−179.5 (2)
N1—C7—C8—C9	1.8 (2)	N5—C29—C30—C31	1.0 (2)
O1—C7—C8—C11	6.2 (4)	O3—C29—C30—C33	−1.5 (4)
N1—C7—C8—C11	−173.3 (2)	N5—C29—C30—C33	179.0 (2)
N1—N2—C9—C8	2.2 (3)	N5—N6—C31—C30	1.3 (3)
N1—N2—C9—C10	−175.35 (19)	N5—N6—C31—C32	−176.10 (19)
C7—C8—C9—N2	−2.5 (3)	C29—C30—C31—N6	−1.4 (3)
C11—C8—C9—N2	172.6 (2)	C33—C30—C31—N6	−179.4 (2)
C7—C8—C9—C10	174.5 (2)	C29—C30—C31—C32	175.4 (2)
C11—C8—C9—C10	−10.4 (4)	C33—C30—C31—C32	−2.6 (4)
N4—N3—C11—C12	−174.44 (18)	N8—N7—C33—C34	−175.45 (19)
N4—N3—C11—C8	2.5 (3)	N8—N7—C33—C30	4.6 (3)
C9—C8—C11—N3	141.6 (3)	C31—C30—C33—N7	136.9 (3)
C7—C8—C11—N3	−44.2 (4)	C29—C30—C33—N7	−40.7 (4)
C9—C8—C11—C12	−41.5 (3)	C31—C30—C33—C34	−43.1 (3)
C7—C8—C11—C12	132.7 (2)	C29—C30—C33—C34	139.3 (2)
N3—C11—C12—C13	150.7 (2)	N7—C33—C34—C35	160.4 (2)
C8—C11—C12—C13	−26.6 (3)	C30—C33—C34—C35	−19.6 (4)
N3—C11—C12—S1	−24.2 (3)	N7—C33—C34—S2	−16.1 (3)
C8—C11—C12—S1	158.49 (16)	C30—C33—C34—S2	163.83 (17)
C15—S1—C12—C13	1.0 (2)	C37—S2—C34—C35	2.7 (2)
C15—S1—C12—C11	176.6 (2)	C37—S2—C34—C33	179.8 (2)
C11—C12—C13—C14	−176.3 (2)	C33—C34—C35—C36	179.8 (2)
S1—C12—C13—C14	−1.0 (3)	S2—C34—C35—C36	−3.4 (3)
C12—C13—C14—C15	0.4 (3)	C34—C35—C36—C37	2.6 (3)
C13—C14—C15—S1	0.4 (3)	C35—C36—C37—S2	−0.7 (3)
C12—S1—C15—C14	−0.8 (2)	C34—S2—C37—C36	−1.2 (2)
N3—N4—C16—O2	13.4 (3)	N7—N8—C38—O4	20.2 (3)
N3—N4—C16—C17	−168.81 (18)	N7—N8—C38—C39	−158.3 (2)
O2—C16—C17—C22	−19.8 (3)	O4—C38—C39—C44	−15.3 (3)
N4—C16—C17—C22	162.4 (2)	N8—C38—C39—C44	163.2 (2)
O2—C16—C17—C18	158.8 (2)	O4—C38—C39—C40	168.5 (2)
N4—C16—C17—C18	−19.0 (3)	N8—C38—C39—C40	−13.0 (4)
C22—C17—C18—C19	0.8 (4)	C44—C39—C40—C41	−1.2 (4)
C16—C17—C18—C19	−177.8 (3)	C38—C39—C40—C41	174.9 (2)
C17—C18—C19—C20	−0.9 (4)	C39—C40—C41—C42	−1.4 (4)
C18—C19—C20—C21	0.3 (4)	C40—C41—C42—C43	2.3 (4)
C19—C20—C21—C22	0.3 (4)	C41—C42—C43—C44	−0.4 (4)
C20—C21—C22—C17	−0.4 (4)	C42—C43—C44—C39	−2.2 (4)
C18—C17—C22—C21	−0.1 (4)	C40—C39—C44—C43	3.0 (4)
C16—C17—C22—C21	178.6 (2)	C38—C39—C44—C43	−173.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2i	0.91 (1)	1.79 (1)	2.677 (3)	165 (2)
C15—H15···O3ii	0.95	2.44	3.383 (3)	171
N6—H6A···O4iii	0.89 (1)	1.80 (1)	2.674 (3)	167 (3)
C36—H36···N3iv	0.95	2.63	3.326 (3)	131
C14—H14···N7ii	0.95	2.55	3.322 (3)	139
N4—H4A···O1	0.91 (1)	1.93 (2)	2.757 (3)	152 (2)
N8—H8A···O3	0.91 (1)	1.86 (1)	2.715 (3)	157 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2i	0.91 (1)	1.79 (1)	2.677 (3)	165 (2)
C15—H15⋯O3ii	0.95	2.44	3.383 (3)	171
N6—H6A⋯O4iii	0.89 (1)	1.80 (1)	2.674 (3)	167 (3)
C36—H36⋯N3iv	0.95	2.63	3.326 (3)	131
C14—H14⋯N7ii	0.95	2.55	3.322 (3)	139
N4—H4A⋯O1	0.91 (1)	1.93 (2)	2.757 (3)	152 (2)
N8—H8A⋯O3	0.91 (1)	1.86 (1)	2.715 (3)	157 (2)

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