A monoclinic polymorph of N-eth-oxy-carbonyl-N'-(3-phenyl-1H-1,2,4-triazol-5-yl)thio-urea.

The title compound, C(12)H(13)N(5)O(2)S {systematic name: ethyl N-[N-(3-phenyl-1H-1,2,4-triazol-5-yl)carbamothio-yl]carbamate}, is a monoclinic polymorph (space group P2(1)/c) which crystallizes with three similar independent mol-ecules in the asymmetric unit. The triazole ring makes dihedral angles of 6.6 (2), 8.4 (2) and 10.6 (2)° with the phenyl ring in the three independent molecules. The structure was previously reported [Dolzhenko et al. (2010a ▶). Acta Cryst., E46, o425] as a triclinic polymorph crystallizing in space group P. Mol-ecules in both polymorphs possess two S(6) rings generated by intra-molecular N-H⋯S and N-H⋯O hydrogen bonds, resulting in similar mol-ecular geometries. However, the two polymorphs differ in the crystal packing. In contrast to the dimers of the triclinic polymorph, mol-ecules of the monoclinic polymorph are connected by inter-molecular N-H⋯S and N-H⋯N hydrogen bonds, forming pseudosymmetric trimers arranged in sheets parallel to (302).

Related literature

For the synthesis, tautomerism and crystal structure studies of related 1,2,4-triazoles, see: Dolzhenko et al. (2007 ▶, 2009 ▶). For the crystal structure of the triclinic polymorph, see: Dolzhenko et al. (2010a ▶). For the crystal structure of N-carbeth­oxy-N′-(3-aryl-1H-1,2,4-triazol-5-yl)thio­urea, see: Dol­zhenko et al. (2010b ▶). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C12H13N5O2S

M = 291.33

Monoclinic,

a = 13.4743 (6) Å

b = 20.4817 (9) Å

c = 15.0266 (7) Å

β = 104.040 (1)°

V = 4023.1 (3) Å3

Z = 12

Mo Kα radiation

μ = 0.25 mm−1

T = 223 K

0.56 × 0.24 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.872, T max = 0.971

28189 measured reflections

9216 independent reflections

5772 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.164

S = 1.03

9216 reflections

598 parameters

86 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.85 e Å−3

Δρmin = −0.52 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810026164/ci5124sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810026164/ci5124Isup2.hkl

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

C12H13N5O2S	F(000) = 1824
Mr = 291.33	Dx = 1.443 Mg m−3
Monoclinic, P21/c	Melting point: 454 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.4743 (6) Å	Cell parameters from 3587 reflections
b = 20.4817 (9) Å	θ = 2.4–21.7°
c = 15.0266 (7) Å	µ = 0.25 mm−1
β = 104.040 (1)°	T = 223 K
V = 4023.1 (3) Å3	Rod, colourless
Z = 12	0.56 × 0.24 × 0.12 mm

Bruker SMART APEX CCD diffractometer	9216 independent reflections
Radiation source: fine-focus sealed tube	5772 reflections with I > 2σ(I)
graphite	Rint = 0.055
φ and ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −17→17
Tmin = 0.872, Tmax = 0.971	k = −25→26
28189 measured reflections	l = −11→19

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0784P)2 + 0.4202P] where P = (Fo2 + 2Fc2)/3
9216 reflections	(Δ/σ)max = 0.001
598 parameters	Δρmax = 0.85 e Å−3
86 restraints	Δρmin = −0.52 e Å−3

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	Occ. (<1)
S1	0.20531 (6)	0.64994 (3)	−0.06103 (6)	0.0441 (2)
S2	0.17227 (7)	0.48747 (3)	0.97238 (6)	0.0513 (2)
S3	0.31718 (9)	0.53635 (4)	0.83353 (7)	0.0713 (3)
O1	0.23376 (15)	0.88193 (8)	−0.06109 (14)	0.0410 (5)
O2	0.17439 (15)	0.85011 (9)	0.06024 (14)	0.0404 (5)
O3	0.04408 (16)	0.38003 (9)	1.20243 (14)	0.0455 (5)
O4	0.06816 (16)	0.30621 (9)	1.09867 (14)	0.0445 (5)
O6	0.4656 (2)	0.50555 (10)	0.59819 (18)	0.0682 (7)
N1	0.07377 (17)	0.68052 (10)	0.18244 (15)	0.0328 (5)
N2	0.07758 (18)	0.57196 (10)	0.15331 (16)	0.0369 (5)
N3	0.11842 (18)	0.60701 (10)	0.09369 (16)	0.0347 (5)
H3N	0.1465 (19)	0.5860 (12)	0.0535 (15)	0.042*
N4	0.15156 (17)	0.72134 (10)	0.06799 (16)	0.0327 (5)
H4N	0.144 (2)	0.7611 (7)	0.0893 (18)	0.039*
N5	0.21787 (18)	0.77628 (10)	−0.03862 (16)	0.0354 (5)
H5N	0.244 (2)	0.7715 (14)	−0.0874 (13)	0.043*
N6	0.21916 (17)	0.28401 (10)	0.88026 (16)	0.0339 (5)
N7	0.28571 (17)	0.35600 (10)	0.79634 (16)	0.0372 (5)
N8	0.24310 (17)	0.38767 (10)	0.85782 (16)	0.0353 (5)
H8N	0.243 (2)	0.4314 (5)	0.860 (2)	0.042*
N9	0.15402 (17)	0.35768 (10)	0.97396 (16)	0.0340 (5)
H9N	0.1309 (19)	0.3232 (9)	0.9998 (18)	0.041*
N10	0.09302 (18)	0.41605 (10)	1.08206 (16)	0.0361 (5)
H10N	0.087 (2)	0.4548 (8)	1.1074 (18)	0.043*
N11	0.40967 (17)	0.69867 (10)	0.67246 (16)	0.0361 (5)
N12	0.34161 (18)	0.74325 (10)	0.78232 (18)	0.0418 (6)
N13	0.34239 (19)	0.67680 (10)	0.78753 (17)	0.0391 (6)
H13N	0.318 (2)	0.6556 (13)	0.8300 (15)	0.047*
N14	0.39497 (18)	0.58664 (10)	0.70279 (16)	0.0349 (5)
H14N	0.421 (2)	0.5794 (14)	0.6543 (13)	0.042*
N15	0.37852 (18)	0.47458 (10)	0.70418 (17)	0.0373 (6)
H15N	0.353 (2)	0.4418 (10)	0.7300 (18)	0.045*
C1	−0.0235 (2)	0.65393 (13)	0.3321 (2)	0.0389 (7)
H1	−0.0021	0.6967	0.3239	0.047*
C2	−0.0761 (2)	0.64147 (14)	0.3989 (2)	0.0455 (7)
H2	−0.0906	0.6756	0.4355	0.055*
C3	−0.1069 (2)	0.57897 (14)	0.4112 (2)	0.0483 (8)
H3	−0.1420	0.5705	0.4569	0.058*
C4	−0.0870 (2)	0.52842 (14)	0.3573 (2)	0.0462 (8)
H4	−0.1090	0.4858	0.3659	0.055*
C5	−0.0343 (2)	0.54099 (13)	0.2905 (2)	0.0409 (7)
H5	−0.0203	0.5067	0.2538	0.049*
C6	−0.0022 (2)	0.60396 (12)	0.27731 (19)	0.0328 (6)
C7	0.0510 (2)	0.61851 (12)	0.20477 (19)	0.0316 (6)
C8	0.11565 (19)	0.67033 (12)	0.11294 (18)	0.0303 (6)
C9	0.1901 (2)	0.71755 (12)	−0.00656 (19)	0.0317 (6)
C10	0.2060 (2)	0.83789 (12)	−0.0065 (2)	0.0336 (6)
C11	0.2122 (2)	0.94956 (12)	−0.0410 (2)	0.0422 (7)
H11A	0.2514	0.9618	0.0205	0.051*
H11B	0.1392	0.9551	−0.0441	0.051*
C12	0.2431 (2)	0.99114 (13)	−0.1123 (2)	0.0506 (8)
H12A	0.3157	0.9858	−0.1076	0.061*
H12B	0.2286	1.0366	−0.1024	0.061*
H12C	0.2049	0.9778	−0.1729	0.061*
C13	0.2936 (2)	0.17599 (13)	0.7891 (2)	0.0432 (7)
H13	0.2675	0.1673	0.8404	0.052*
C14	0.3236 (3)	0.12477 (14)	0.7417 (2)	0.0517 (8)
H14	0.3181	0.0817	0.7614	0.062*
C15	0.3612 (2)	0.13640 (14)	0.6660 (2)	0.0491 (8)
H15	0.3809	0.1015	0.6334	0.059*
C16	0.3697 (3)	0.20008 (15)	0.6385 (2)	0.0531 (8)
H16	0.3960	0.2086	0.5872	0.064*
C17	0.3401 (2)	0.25111 (14)	0.6854 (2)	0.0460 (7)
H17	0.3459	0.2942	0.6656	0.055*
C18	0.3016 (2)	0.23983 (12)	0.7617 (2)	0.0348 (6)
C19	0.2690 (2)	0.29402 (12)	0.81255 (19)	0.0333 (6)
C20	0.2040 (2)	0.34429 (12)	0.90587 (19)	0.0317 (6)
C21	0.1390 (2)	0.41679 (12)	1.00938 (19)	0.0329 (6)
C22	0.0671 (2)	0.36185 (13)	1.1259 (2)	0.0366 (6)
C23	0.0197 (3)	0.32624 (14)	1.2587 (2)	0.0491 (8)
H23A	0.0681	0.2902	1.2611	0.059*
H23B	−0.0495	0.3099	1.2323	0.059*
C24	0.0270 (3)	0.35195 (17)	1.3519 (3)	0.0707 (11)
H24A	0.0939	0.3714	1.3754	0.085*
H24B	0.0174	0.3166	1.3919	0.085*
H24C	−0.0255	0.3847	1.3496	0.085*
C25	0.4554 (2)	0.82809 (14)	0.6144 (2)	0.0499 (8)
H25	0.4852	0.7915	0.5933	0.060*
C26	0.4684 (3)	0.88965 (16)	0.5801 (3)	0.0598 (9)
H26	0.5072	0.8948	0.5364	0.072*
C27	0.4241 (3)	0.94289 (15)	0.6103 (3)	0.0633 (10)
H27	0.4321	0.9846	0.5869	0.076*
C28	0.3683 (3)	0.93515 (15)	0.6747 (3)	0.0591 (10)
H28	0.3381	0.9718	0.6951	0.071*
C29	0.3559 (2)	0.87429 (13)	0.7100 (2)	0.0485 (8)
H29	0.3181	0.8697	0.7546	0.058*
C30	0.3992 (2)	0.82008 (13)	0.6793 (2)	0.0403 (7)
C31	0.3835 (2)	0.75410 (12)	0.7126 (2)	0.0357 (6)
C32	0.3826 (2)	0.65233 (12)	0.72182 (19)	0.0327 (6)
C33	0.3652 (2)	0.53406 (12)	0.7427 (2)	0.0353 (6)
C34	0.4265 (3)	0.46419 (14)	0.6349 (2)	0.0472 (8)
O5	0.4364 (4)	0.4001 (3)	0.6227 (3)	0.0402 (13)	0.634 (7)
C35	0.4867 (5)	0.3865 (3)	0.5460 (5)	0.0637 (17)	0.634 (7)
H35A	0.4571	0.4146	0.4935	0.076*	0.634 (7)
H35B	0.5600	0.3959	0.5660	0.076*	0.634 (7)
C36	0.4716 (6)	0.3202 (3)	0.5201 (5)	0.0745 (18)	0.634 (7)
H36A	0.5042	0.3111	0.4705	0.089*	0.634 (7)
H36B	0.3989	0.3112	0.4998	0.089*	0.634 (7)
H36C	0.5015	0.2926	0.5722	0.089*	0.634 (7)
O5A	0.3960 (7)	0.4021 (5)	0.5995 (6)	0.041 (2)	0.366 (7)
C35A	0.4221 (8)	0.3748 (5)	0.5141 (6)	0.076 (3)	0.366 (7)
H35C	0.3752	0.3392	0.4884	0.091*	0.366 (7)
H35D	0.4166	0.4089	0.4675	0.091*	0.366 (7)
C36A	0.5241 (7)	0.3513 (7)	0.5415 (9)	0.088 (3)	0.366 (7)
H36D	0.5445	0.3340	0.4886	0.106*	0.366 (7)
H36E	0.5281	0.3171	0.5869	0.106*	0.366 (7)
H36F	0.5694	0.3868	0.5679	0.106*	0.366 (7)

	U11	U22	U33	U12	U13	U23
S1	0.0679 (5)	0.0275 (3)	0.0481 (5)	0.0027 (3)	0.0359 (4)	−0.0004 (3)
S2	0.0890 (6)	0.0220 (3)	0.0586 (5)	−0.0087 (3)	0.0485 (5)	−0.0055 (3)
S3	0.1328 (9)	0.0264 (4)	0.0852 (7)	−0.0089 (4)	0.0859 (7)	−0.0078 (4)
O1	0.0559 (12)	0.0216 (9)	0.0544 (13)	−0.0001 (8)	0.0309 (10)	0.0031 (9)
O2	0.0540 (12)	0.0286 (9)	0.0454 (12)	−0.0025 (8)	0.0254 (10)	−0.0023 (9)
O3	0.0715 (14)	0.0304 (10)	0.0441 (12)	−0.0072 (9)	0.0322 (11)	0.0013 (9)
O4	0.0625 (13)	0.0262 (10)	0.0512 (13)	−0.0044 (9)	0.0263 (11)	0.0021 (9)
O6	0.121 (2)	0.0318 (11)	0.0786 (17)	0.0009 (12)	0.0760 (16)	0.0008 (12)
N1	0.0418 (13)	0.0264 (11)	0.0341 (13)	0.0006 (9)	0.0166 (10)	−0.0002 (10)
N2	0.0496 (14)	0.0283 (11)	0.0377 (13)	−0.0019 (10)	0.0198 (11)	0.0033 (10)
N3	0.0477 (14)	0.0252 (11)	0.0378 (13)	0.0000 (10)	0.0229 (11)	−0.0001 (10)
N4	0.0452 (13)	0.0216 (10)	0.0368 (13)	0.0009 (9)	0.0207 (11)	0.0000 (10)
N5	0.0494 (14)	0.0254 (11)	0.0393 (14)	0.0012 (10)	0.0261 (11)	0.0027 (10)
N6	0.0449 (13)	0.0208 (10)	0.0377 (13)	0.0008 (9)	0.0135 (11)	−0.0021 (10)
N7	0.0485 (14)	0.0272 (11)	0.0408 (14)	−0.0003 (10)	0.0204 (11)	−0.0054 (11)
N8	0.0501 (14)	0.0213 (10)	0.0411 (14)	−0.0016 (10)	0.0235 (11)	−0.0023 (10)
N9	0.0490 (14)	0.0192 (10)	0.0383 (13)	−0.0029 (9)	0.0198 (11)	0.0004 (10)
N10	0.0510 (14)	0.0240 (11)	0.0402 (14)	0.0000 (10)	0.0242 (11)	−0.0002 (10)
N11	0.0446 (14)	0.0246 (11)	0.0413 (14)	−0.0028 (9)	0.0146 (11)	0.0024 (10)
N12	0.0541 (15)	0.0229 (11)	0.0496 (16)	−0.0003 (10)	0.0148 (13)	−0.0021 (11)
N13	0.0577 (16)	0.0243 (11)	0.0412 (15)	−0.0009 (10)	0.0235 (12)	−0.0014 (11)
N14	0.0503 (14)	0.0232 (10)	0.0381 (14)	−0.0002 (10)	0.0244 (11)	−0.0007 (10)
N15	0.0537 (15)	0.0208 (11)	0.0461 (15)	−0.0024 (10)	0.0287 (12)	−0.0028 (10)
C1	0.0518 (18)	0.0317 (14)	0.0360 (16)	−0.0018 (12)	0.0163 (13)	0.0029 (13)
C2	0.066 (2)	0.0379 (16)	0.0387 (17)	0.0036 (14)	0.0235 (15)	0.0006 (14)
C3	0.071 (2)	0.0423 (17)	0.0416 (17)	0.0021 (15)	0.0328 (16)	0.0105 (15)
C4	0.063 (2)	0.0311 (14)	0.0522 (19)	−0.0042 (13)	0.0298 (16)	0.0100 (14)
C5	0.0547 (18)	0.0312 (14)	0.0425 (17)	−0.0002 (12)	0.0232 (14)	0.0013 (13)
C6	0.0382 (15)	0.0285 (13)	0.0336 (15)	−0.0001 (11)	0.0127 (12)	0.0050 (12)
C7	0.0368 (15)	0.0268 (13)	0.0335 (15)	0.0009 (11)	0.0129 (12)	0.0015 (12)
C8	0.0344 (14)	0.0258 (12)	0.0327 (15)	0.0015 (10)	0.0118 (12)	0.0001 (12)
C9	0.0354 (14)	0.0254 (12)	0.0378 (15)	−0.0005 (10)	0.0155 (12)	0.0045 (12)
C10	0.0333 (15)	0.0265 (13)	0.0437 (17)	−0.0017 (10)	0.0146 (13)	0.0004 (12)
C11	0.0544 (18)	0.0239 (13)	0.0523 (19)	0.0022 (12)	0.0210 (15)	0.0014 (13)
C12	0.062 (2)	0.0268 (14)	0.071 (2)	0.0003 (13)	0.0310 (18)	0.0062 (15)
C13	0.0514 (18)	0.0285 (14)	0.0544 (19)	0.0027 (12)	0.0219 (15)	−0.0029 (14)
C14	0.068 (2)	0.0262 (14)	0.066 (2)	0.0040 (14)	0.0261 (18)	−0.0050 (15)
C15	0.056 (2)	0.0363 (16)	0.056 (2)	0.0050 (14)	0.0173 (16)	−0.0157 (15)
C16	0.069 (2)	0.0500 (19)	0.048 (2)	−0.0010 (16)	0.0298 (17)	−0.0092 (16)
C17	0.065 (2)	0.0281 (14)	0.0504 (19)	−0.0030 (13)	0.0243 (16)	−0.0037 (14)
C18	0.0348 (15)	0.0277 (13)	0.0422 (17)	−0.0012 (11)	0.0099 (12)	−0.0042 (12)
C19	0.0367 (15)	0.0278 (13)	0.0353 (16)	−0.0022 (11)	0.0085 (12)	−0.0011 (12)
C20	0.0347 (15)	0.0257 (12)	0.0340 (15)	−0.0011 (10)	0.0068 (12)	−0.0009 (12)
C21	0.0406 (15)	0.0252 (12)	0.0350 (15)	0.0001 (11)	0.0133 (12)	−0.0004 (12)
C22	0.0437 (16)	0.0321 (15)	0.0377 (16)	−0.0013 (12)	0.0169 (13)	0.0031 (13)
C23	0.066 (2)	0.0380 (16)	0.0505 (19)	−0.0121 (14)	0.0289 (17)	0.0066 (15)
C24	0.116 (3)	0.052 (2)	0.062 (2)	−0.011 (2)	0.059 (2)	0.0019 (19)
C25	0.0508 (19)	0.0303 (15)	0.069 (2)	−0.0012 (13)	0.0158 (17)	0.0057 (15)
C26	0.062 (2)	0.0415 (18)	0.076 (3)	−0.0066 (15)	0.0177 (19)	0.0157 (18)
C27	0.070 (2)	0.0277 (16)	0.084 (3)	−0.0066 (15)	0.004 (2)	0.0120 (18)
C28	0.073 (2)	0.0249 (15)	0.073 (3)	0.0055 (15)	0.005 (2)	−0.0047 (16)
C29	0.057 (2)	0.0295 (15)	0.056 (2)	0.0001 (13)	0.0076 (16)	−0.0052 (14)
C30	0.0403 (16)	0.0268 (13)	0.0480 (18)	−0.0036 (12)	−0.0004 (14)	0.0009 (13)
C31	0.0388 (16)	0.0237 (13)	0.0425 (17)	−0.0014 (11)	0.0055 (13)	−0.0012 (12)
C32	0.0366 (15)	0.0248 (12)	0.0374 (15)	−0.0012 (11)	0.0101 (12)	−0.0020 (12)
C33	0.0439 (16)	0.0266 (13)	0.0418 (16)	−0.0023 (11)	0.0227 (13)	−0.0036 (12)
C34	0.069 (2)	0.0275 (14)	0.054 (2)	0.0017 (14)	0.0334 (17)	−0.0047 (14)
O5	0.047 (3)	0.0255 (19)	0.053 (3)	0.002 (2)	0.021 (2)	−0.010 (2)
C35	0.067 (4)	0.050 (3)	0.092 (4)	−0.011 (3)	0.056 (3)	−0.030 (3)
C36	0.089 (4)	0.064 (3)	0.086 (4)	−0.012 (3)	0.051 (3)	−0.016 (3)
O5A	0.060 (6)	0.032 (3)	0.026 (3)	0.022 (4)	0.001 (4)	−0.001 (3)
C35A	0.077 (5)	0.058 (4)	0.096 (5)	−0.006 (4)	0.028 (4)	0.024 (4)
C36A	0.083 (5)	0.080 (6)	0.107 (5)	−0.016 (5)	0.034 (5)	0.001 (5)

S1—C9	1.647 (3)	C5—C6	1.390 (4)
S2—C21	1.651 (3)	C5—H5	0.94
S3—C33	1.647 (3)	C6—C7	1.473 (4)
O1—C10	1.332 (3)	C11—C12	1.503 (4)
O1—C11	1.462 (3)	C11—H11A	0.98
O2—C10	1.208 (3)	C11—H11B	0.98
O3—C22	1.316 (3)	C12—H12A	0.97
O3—C23	1.474 (3)	C12—H12B	0.97
O4—C22	1.212 (3)	C12—H12C	0.97
O6—C34	1.200 (3)	C13—C14	1.382 (4)
N1—C8	1.318 (3)	C13—C18	1.383 (4)
N1—C7	1.367 (3)	C13—H13	0.94
N2—C7	1.330 (3)	C14—C15	1.374 (4)
N2—N3	1.364 (3)	C14—H14	0.94
N3—C8	1.331 (3)	C15—C16	1.381 (4)
N3—H3N	0.897 (10)	C15—H15	0.94
N4—C9	1.346 (3)	C16—C17	1.373 (4)
N4—C8	1.393 (3)	C16—H16	0.94
N4—H4N	0.889 (10)	C17—C18	1.387 (4)
N5—C10	1.374 (3)	C17—H17	0.94
N5—C9	1.381 (3)	C18—C19	1.473 (4)
N5—H5N	0.890 (10)	C23—C24	1.476 (5)
N6—C20	1.324 (3)	C23—H23A	0.98
N6—C19	1.364 (3)	C23—H23B	0.98
N7—C19	1.322 (3)	C24—H24A	0.97
N7—N8	1.364 (3)	C24—H24B	0.97
N8—C20	1.331 (3)	C24—H24C	0.97
N8—H8N	0.897 (10)	C25—C30	1.382 (4)
N9—C21	1.357 (3)	C25—C26	1.389 (4)
N9—C20	1.382 (3)	C25—H25	0.94
N9—H9N	0.896 (10)	C26—C27	1.372 (5)
N10—C22	1.378 (3)	C26—H26	0.94
N10—C21	1.380 (3)	C27—C28	1.371 (5)
N10—H10N	0.892 (10)	C27—H27	0.94
N11—C32	1.310 (3)	C28—C29	1.381 (4)
N11—C31	1.371 (3)	C28—H28	0.94
N12—C31	1.324 (4)	C29—C30	1.384 (4)
N12—N13	1.363 (3)	C29—H29	0.94
N13—C32	1.334 (3)	C30—C31	1.474 (4)
N13—H13N	0.896 (10)	C34—O5	1.337 (6)
N14—C33	1.341 (3)	C34—O5A	1.401 (12)
N14—C32	1.394 (3)	O5—C35	1.499 (6)
N14—H14N	0.891 (10)	C35—C36	1.414 (6)
N15—C34	1.369 (4)	C35—H35A	0.98
N15—C33	1.379 (3)	C35—H35B	0.98
N15—H15N	0.883 (10)	C36—H36A	0.97
C1—C2	1.384 (4)	C36—H36B	0.97
C1—C6	1.387 (4)	C36—H36C	0.97
C1—H1	0.94	O5A—C35A	1.517 (7)
C2—C3	1.372 (4)	C35A—C36A	1.420 (7)
C2—H2	0.94	C35A—H35C	0.98
C3—C4	1.380 (4)	C35A—H35D	0.98
C3—H3	0.94	C36A—H36D	0.97
C4—C5	1.388 (4)	C36A—H36E	0.97
C4—H4	0.94	C36A—H36F	0.97
C10—O1—C11	114.5 (2)	C16—C17—C18	120.7 (3)
C22—O3—C23	115.0 (2)	C16—C17—H17	119.6
C8—N1—C7	102.2 (2)	C18—C17—H17	119.6
C7—N2—N3	102.3 (2)	C13—C18—C17	118.4 (3)
C8—N3—N2	109.5 (2)	C13—C18—C19	120.2 (3)
C8—N3—H3N	130.7 (18)	C17—C18—C19	121.4 (2)
N2—N3—H3N	119.6 (18)	N7—C19—N6	114.7 (2)
C9—N4—C8	127.6 (2)	N7—C19—C18	122.9 (2)
C9—N4—H4N	116.9 (19)	N6—C19—C18	122.4 (2)
C8—N4—H4N	115.4 (19)	N6—C20—N8	110.8 (2)
C10—N5—C9	127.8 (2)	N6—C20—N9	122.5 (2)
C10—N5—H5N	119.5 (19)	N8—C20—N9	126.7 (2)
C9—N5—H5N	112.6 (19)	N9—C21—N10	116.0 (2)
C20—N6—C19	102.4 (2)	N9—C21—S2	124.9 (2)
C19—N7—N8	102.3 (2)	N10—C21—S2	119.12 (19)
C20—N8—N7	109.7 (2)	O4—C22—O3	125.9 (3)
C20—N8—H8N	130 (2)	O4—C22—N10	124.8 (3)
N7—N8—H8N	121 (2)	O3—C22—N10	109.3 (2)
C21—N9—C20	127.8 (2)	O3—C23—C24	107.8 (2)
C21—N9—H9N	115.6 (18)	O3—C23—H23A	110.2
C20—N9—H9N	116.5 (18)	C24—C23—H23A	110.2
C22—N10—C21	127.0 (2)	O3—C23—H23B	110.2
C22—N10—H10N	116.9 (19)	C24—C23—H23B	110.2
C21—N10—H10N	115.7 (19)	H23A—C23—H23B	108.5
C32—N11—C31	102.4 (2)	C23—C24—H24A	109.5
C31—N12—N13	102.4 (2)	C23—C24—H24B	109.5
C32—N13—N12	109.4 (2)	H24A—C24—H24B	109.5
C32—N13—H13N	128.9 (19)	C23—C24—H24C	109.5
N12—N13—H13N	121.8 (19)	H24A—C24—H24C	109.5
C33—N14—C32	128.3 (2)	H24B—C24—H24C	109.5
C33—N14—H14N	116.7 (19)	C30—C25—C26	120.7 (3)
C32—N14—H14N	114.7 (19)	C30—C25—H25	119.7
C34—N15—C33	126.2 (2)	C26—C25—H25	119.7
C34—N15—H15N	121.2 (19)	C27—C26—C25	119.6 (4)
C33—N15—H15N	112.7 (19)	C27—C26—H26	120.2
C2—C1—C6	120.7 (3)	C25—C26—H26	120.2
C2—C1—H1	119.7	C28—C27—C26	119.9 (3)
C6—C1—H1	119.7	C28—C27—H27	120.0
C3—C2—C1	119.7 (3)	C26—C27—H27	120.0
C3—C2—H2	120.2	C27—C28—C29	120.9 (3)
C1—C2—H2	120.2	C27—C28—H28	119.5
C2—C3—C4	120.8 (3)	C29—C28—H28	119.5
C2—C3—H3	119.6	C28—C29—C30	119.7 (3)
C4—C3—H3	119.6	C28—C29—H29	120.1
C3—C4—C5	119.5 (3)	C30—C29—H29	120.1
C3—C4—H4	120.3	C25—C30—C29	119.1 (3)
C5—C4—H4	120.3	C25—C30—C31	119.8 (3)
C4—C5—C6	120.5 (3)	C29—C30—C31	121.0 (3)
C4—C5—H5	119.8	N12—C31—N11	114.4 (2)
C6—C5—H5	119.8	N12—C31—C30	123.1 (3)
C1—C6—C5	118.9 (3)	N11—C31—C30	122.5 (3)
C1—C6—C7	119.9 (2)	N11—C32—N13	111.5 (2)
C5—C6—C7	121.2 (2)	N11—C32—N14	121.3 (2)
N2—C7—N1	114.5 (2)	N13—C32—N14	127.2 (2)
N2—C7—C6	122.2 (2)	N14—C33—N15	116.0 (2)
N1—C7—C6	123.2 (2)	N14—C33—S3	124.6 (2)
N1—C8—N3	111.5 (2)	N15—C33—S3	119.4 (2)
N1—C8—N4	122.1 (2)	O6—C34—O5	124.1 (3)
N3—C8—N4	126.4 (2)	O6—C34—N15	125.5 (3)
N4—C9—N5	115.6 (2)	O5—C34—N15	109.7 (3)
N4—C9—S1	125.57 (19)	O6—C34—O5A	125.9 (5)
N5—C9—S1	118.8 (2)	N15—C34—O5A	106.3 (4)
O2—C10—O1	125.4 (2)	C34—O5—C35	111.5 (5)
O2—C10—N5	125.2 (2)	C36—C35—O5	109.2 (5)
O1—C10—N5	109.4 (2)	C36—C35—H35A	109.8
O1—C11—C12	106.7 (2)	O5—C35—H35A	109.8
O1—C11—H11A	110.4	C36—C35—H35B	109.8
C12—C11—H11A	110.4	O5—C35—H35B	109.8
O1—C11—H11B	110.4	H35A—C35—H35B	108.3
C12—C11—H11B	110.4	C35—C36—H36A	109.5
H11A—C11—H11B	108.6	C35—C36—H36B	109.5
C11—C12—H12A	109.5	H36A—C36—H36B	109.5
C11—C12—H12B	109.5	C35—C36—H36C	109.5
H12A—C12—H12B	109.5	H36A—C36—H36C	109.5
C11—C12—H12C	109.5	H36B—C36—H36C	109.5
H12A—C12—H12C	109.5	C34—O5A—C35A	123.3 (9)
H12B—C12—H12C	109.5	C36A—C35A—O5A	106.6 (6)
C14—C13—C18	120.7 (3)	C36A—C35A—H35C	110.4
C14—C13—H13	119.6	O5A—C35A—H35C	110.4
C18—C13—H13	119.6	C36A—C35A—H35D	110.4
C15—C14—C13	120.5 (3)	O5A—C35A—H35D	110.4
C15—C14—H14	119.7	H35C—C35A—H35D	108.6
C13—C14—H14	119.7	C35A—C36A—H36D	109.5
C14—C15—C16	119.0 (3)	C35A—C36A—H36E	109.5
C14—C15—H15	120.5	H36D—C36A—H36E	109.5
C16—C15—H15	120.5	C35A—C36A—H36F	109.5
C17—C16—C15	120.7 (3)	H36D—C36A—H36F	109.5
C17—C16—H16	119.7	H36E—C36A—H36F	109.5
C15—C16—H16	119.7
C7—N2—N3—C8	0.9 (3)	C19—N6—C20—N9	179.4 (2)
C19—N7—N8—C20	−0.2 (3)	N7—N8—C20—N6	0.6 (3)
C31—N12—N13—C32	−0.6 (3)	N7—N8—C20—N9	−179.5 (2)
C6—C1—C2—C3	0.3 (5)	C21—N9—C20—N6	176.1 (3)
C1—C2—C3—C4	−0.6 (5)	C21—N9—C20—N8	−3.8 (5)
C2—C3—C4—C5	0.6 (5)	C20—N9—C21—N10	−175.3 (3)
C3—C4—C5—C6	−0.3 (5)	C20—N9—C21—S2	4.2 (4)
C2—C1—C6—C5	0.0 (4)	C22—N10—C21—N9	4.6 (4)
C2—C1—C6—C7	178.1 (3)	C22—N10—C21—S2	−175.0 (2)
C4—C5—C6—C1	0.0 (4)	C23—O3—C22—O4	1.2 (4)
C4—C5—C6—C7	−178.1 (3)	C23—O3—C22—N10	−177.1 (2)
N3—N2—C7—N1	−0.9 (3)	C21—N10—C22—O4	−10.9 (5)
N3—N2—C7—C6	176.8 (2)	C21—N10—C22—O3	167.5 (3)
C8—N1—C7—N2	0.6 (3)	C22—O3—C23—C24	163.0 (3)
C8—N1—C7—C6	−177.2 (2)	C30—C25—C26—C27	−0.6 (5)
C1—C6—C7—N2	176.7 (3)	C25—C26—C27—C28	0.6 (5)
C5—C6—C7—N2	−5.2 (4)	C26—C27—C28—C29	0.1 (5)
C1—C6—C7—N1	−5.7 (4)	C27—C28—C29—C30	−0.8 (5)
C5—C6—C7—N1	172.4 (3)	C26—C25—C30—C29	0.0 (5)
C7—N1—C8—N3	0.1 (3)	C26—C25—C30—C31	177.9 (3)
C7—N1—C8—N4	−179.7 (2)	C28—C29—C30—C25	0.7 (5)
N2—N3—C8—N1	−0.7 (3)	C28—C29—C30—C31	−177.2 (3)
N2—N3—C8—N4	179.1 (2)	N13—N12—C31—N11	0.7 (3)
C9—N4—C8—N1	−175.8 (3)	N13—N12—C31—C30	179.7 (2)
C9—N4—C8—N3	4.4 (4)	C32—N11—C31—N12	−0.6 (3)
C8—N4—C9—N5	178.4 (2)	C32—N11—C31—C30	−179.6 (2)
C8—N4—C9—S1	−1.1 (4)	C25—C30—C31—N12	171.4 (3)
C10—N5—C9—N4	−3.7 (4)	C29—C30—C31—N12	−10.6 (4)
C10—N5—C9—S1	175.9 (2)	C25—C30—C31—N11	−9.6 (4)
C11—O1—C10—O2	−6.9 (4)	C29—C30—C31—N11	168.3 (3)
C11—O1—C10—N5	172.5 (2)	C31—N11—C32—N13	0.1 (3)
C9—N5—C10—O2	5.1 (5)	C31—N11—C32—N14	179.1 (2)
C9—N5—C10—O1	−174.3 (2)	N12—N13—C32—N11	0.3 (3)
C10—O1—C11—C12	−176.9 (2)	N12—N13—C32—N14	−178.6 (3)
C18—C13—C14—C15	−0.5 (5)	C33—N14—C32—N11	−175.2 (3)
C13—C14—C15—C16	0.7 (5)	C33—N14—C32—N13	3.6 (5)
C14—C15—C16—C17	−0.6 (5)	C32—N14—C33—N15	173.9 (3)
C15—C16—C17—C18	0.4 (5)	C32—N14—C33—S3	−7.3 (4)
C14—C13—C18—C17	0.3 (4)	C34—N15—C33—N14	5.8 (4)
C14—C13—C18—C19	179.8 (3)	C34—N15—C33—S3	−173.0 (3)
C16—C17—C18—C13	−0.2 (5)	C33—N15—C34—O6	1.1 (6)
C16—C17—C18—C19	−179.7 (3)	C33—N15—C34—O5	172.4 (3)
N8—N7—C19—N6	−0.2 (3)	C33—N15—C34—O5A	−162.6 (4)
N8—N7—C19—C18	179.8 (2)	O6—C34—O5—C35	−9.8 (7)
C20—N6—C19—N7	0.6 (3)	N15—C34—O5—C35	178.8 (4)
C20—N6—C19—C18	−179.4 (2)	O5A—C34—O5—C35	93.0 (14)
C13—C18—C19—N7	172.0 (3)	C34—O5—C35—C36	−164.9 (7)
C17—C18—C19—N7	−8.6 (4)	O6—C34—O5A—C35A	8.9 (10)
C13—C18—C19—N6	−8.0 (4)	O5—C34—O5A—C35A	−85.4 (14)
C17—C18—C19—N6	171.4 (3)	N15—C34—O5A—C35A	172.6 (6)
C19—N6—C20—N8	−0.7 (3)	C34—O5A—C35A—C36A	80.4 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···S1	0.90 (1)	2.44 (3)	2.978 (2)	119 (2)
N8—H8N···S2	0.90 (1)	2.42 (3)	2.975 (2)	121 (2)
N13—H13N···S3	0.90 (1)	2.44 (3)	2.997 (2)	120 (2)
N8—H8N···S3	0.90 (1)	2.44 (2)	3.253 (2)	150 (2)
N3—H3N···S2i	0.90 (2)	2.43 (2)	3.238 (2)	151 (2)
N13—H13N···S1ii	0.90 (2)	2.49 (3)	3.306 (3)	151 (2)
N4—H4N···O2	0.89 (1)	1.94 (2)	2.661 (3)	137 (2)
N9—H9N···O4	0.90 (1)	1.91 (2)	2.648 (3)	138 (2)
N14—H14N···O6	0.89 (1)	1.90 (2)	2.619 (3)	136 (2)
N10—H10N···N2ii	0.89 (2)	2.51 (2)	3.390 (3)	170 (2)
N15—H15N···N7	0.89 (2)	2.31 (2)	3.197 (3)	180 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯S1	0.90 (1)	2.44 (3)	2.978 (2)	119 (2)
N8—H8N⋯S2	0.90 (1)	2.42 (3)	2.975 (2)	121 (2)
N13—H13N⋯S3	0.90 (1)	2.44 (3)	2.997 (2)	120 (2)
N8—H8N⋯S3	0.90 (1)	2.44 (2)	3.253 (2)	150 (2)
N3—H3N⋯S2i	0.90 (2)	2.43 (2)	3.238 (2)	151 (2)
N13—H13N⋯S1ii	0.90 (2)	2.49 (3)	3.306 (3)	151 (2)
N4—H4N⋯O2	0.89 (1)	1.94 (2)	2.661 (3)	137 (2)
N9—H9N⋯O4	0.90 (1)	1.91 (2)	2.648 (3)	138 (2)
N14—H14N⋯O6	0.89 (1)	1.90 (2)	2.619 (3)	136 (2)
N10—H10N⋯N2ii	0.89 (2)	2.51 (2)	3.390 (3)	170 (2)
N15—H15N⋯N7	0.89 (2)	2.31 (2)	3.197 (3)	180 (3)

Symmetry codes: (i) ; (ii) .