2-[(5,6,7-Trimeth­yl[1,2,4]triazolo[1,5-a]pyrimidin-2-ylsulfan­yl)meth­yl]benzoic acid

He, Y.-Z.

doi:10.1107/S1600536807019538

2-[(5,6,7-Trimethyl[1,2,4]triazolo[1,5-a]pyrimidin-2-ylsulfanyl)methyl]benzoic acid

In the crystal structure of the title compound, C₁₆H₁₆N₄O₂S, there are two independent molecules with different conformations in the asymmetric unit; these are linked into chains by O—H

N hydrogen bonds. Further stability may be provided by offset π–π stacking interactions involving inversion-related pyrimidine rings [centroid–centroid distance = 3.84 (1) Å] and benzene rings [centroid–centroid distance = 3.45 (1) Å].

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807019538/hb2373sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807019538/hb2373Isup2.hkl Contains datablock I

CCDC reference: 647690

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Key indicators

Single-crystal X-ray study
T = 299 K
Mean (C-C) = 0.004 Å
R factor = 0.058
wR factor = 0.154
Data-to-parameter ratio = 16.6

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No syntax errors found



Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            golden
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000)         100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          3

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

Triazolopyrimidine derivatives have broad biological properties: in particular triazolopyrimidine sulfonamide is a highly effective herbicide with acetohydroxyacid synthase (AHAS) as target (Kleschich et al., 1990). We herein report the crystal structure of one such triazolopyrimidine derivative, the title compound, (I).

The crystal structure of the the title compound contains two independent molecules (A and B) in the asymmetric unit (Fig. 1) with bond lengths and angles are within normal ranges (Allen et al., 1987). In molecule A, the triazolopyrimidine fused rings (N1—N4/C9—C13) are close to planarity with a maximum deviation of 0.028 (2)Å for C13. The dihedral angle between triazolopyrimidine and benzene rings is 70.56 (3)°.

In molecule B, the triazolopyrimidine fused rings (N5—N8/C25—C29) are almost planar with a maximum deviation of 0.031 (2)Å for C25. The dihedral angle between triazolopyrimidine and benzene rings is 54.83 (3)°.

In the crystal of (I), intermolecular O—H···N hydrogen bonds (Table 2) lead to chains of molecules (Fig. 2). Further stability is provided by offset π-π stacking interactions (Janiak, 2000). The adjacent pyrimidine rings (N6/N8/C26—C29) have a centroid-centroid distance of 3.84 (1) %A [symmetry code: - x, 1 - y, 1 - z], while the adjacent benzene rings (C1—C6) have a centroid-centroid distance of 3.45 (1) %A [symmetry

code: 1 - x, 2 - y, - z].

Related literature top

For related structures, see: Chen, Li et al. (2005); Chen, Wu et al. (2005); Teng et al. (2005).

For related literature, see: Allen et al. (1987); Janiak (2000); Kleschich et al. (1990).

Experimental top

Sodium hydroxide (0.08 g, 2 mmol) was dissolved in ethanol (5 ml), and then 5-amino-1H-1,2,4-triazole-3-thiol (0.23 g, 2 mmol) was added. Then, methyl 2-(chloromethyl)benzoate (0.37 g, 2 mmol) was added dropwise until the solid dissolved completely. After stirring for 2 h at room temperature, the precipitate was filtered off, washed with water and dried to give methyl 2-((5-amino-1H-1,2,4-triazol-3-ylthio)methyl)benzoate (0.38 g, yield 72%). This ester (1.06 g, 4 mmol) in 4 ml glacial acetic acid with 3-methylpentane-2,4-dione (0.46 g, 4 mmol) was refluxed for 6 h. The solution was poured into 50 ml ice and water and stirred overnight. The solid which separated from water was dried to obtain methyl 2-((5,6,7-trimethyl-[1,2,4]triazolo[1,5-a]pyrimidin-2-ylthio)methyl) benzoate (1.24 g, yield 91%). Then it (0.6 g, 1.75 mmol) was added into the solution of NaOH (0.14 g, 3.5 mmol) in ethanol (5 ml) and water (5 ml) and the mixture was refluxed for 30 minutes. The solution was quenched with 20 ml water and then treated with diluted hydrochloric acid until pH = 1 was reached. The precipitate was collected by filtration and recrystallized from ethanol to obtain golden yellow crystals of the title compound (0.40 g, yield 67%). Crystals of (I) suitable for X-ray analysis were grown from acetone at 277 K.

Structure description top

code: 1 - x, 2 - y, - z].

For related structures, see: Chen, Li et al. (2005); Chen, Wu et al. (2005); Teng et al. (2005).

For related literature, see: Allen et al. (1987); Janiak (2000); Kleschich et al. (1990).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines.

2-[(5,6,7-Trimethyl[1,2,4]triazolo[1,5-a]pyrimidin-2-ylsulfanyl)methyl]benzoic acid top

Crystal data top

C₁₆H₁₆N₄O₂S	Z = 4
M_r = 328.39	F(000) = 688
Triclinic, P1	D_x = 1.393 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9704 (5) Å	Cell parameters from 2157 reflections
b = 13.3058 (8) Å	θ = 2.2–24.5°
c = 15.9084 (9) Å	µ = 0.22 mm⁻¹
α = 110.257 (1)°	T = 299 K
β = 96.446 (1)°	Block, golden yellow
γ = 92.620 (1)°	0.30 × 0.20 × 0.10 mm
V = 1566.28 (16) Å³

Data collection top

Bruker SMART 4K CCD diffractometer	7079 independent reflections
Radiation source: fine-focus sealed tube	5206 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.936, T_max = 0.978	k = −17→17
17990 measured reflections	l = −20→20

Refinement top

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0843P)² + 0.1225P] where P = (F_o² + 2F_c²)/3
7079 reflections	(Δ/σ)_max = 0.001
427 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₆H₁₆N₄O₂S	γ = 92.620 (1)°
M_r = 328.39	V = 1566.28 (16) Å³
Triclinic, P1	Z = 4
a = 7.9704 (5) Å	Mo Kα radiation
b = 13.3058 (8) Å	µ = 0.22 mm⁻¹
c = 15.9084 (9) Å	T = 299 K
α = 110.257 (1)°	0.30 × 0.20 × 0.10 mm
β = 96.446 (1)°

Data collection top

Bruker SMART 4K CCD diffractometer	7079 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5206 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.978	R_int = 0.031
17990 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.36 e Å⁻³
7079 reflections	Δρ_min = −0.25 e Å⁻³
427 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.0916 (3)	0.66968 (18)	0.02579 (15)	0.0404 (5)
C2	0.1370 (3)	0.5831 (2)	−0.04390 (17)	0.0525 (6)
H2	0.0930	0.5724	−0.1033	0.063*
C3	0.2454 (3)	0.5129 (2)	−0.0268 (2)	0.0621 (7)
H3	0.2743	0.4554	−0.0744	0.075*
C4	0.3110 (3)	0.5280 (2)	0.0610 (2)	0.0585 (7)
H4	0.3861	0.4816	0.0729	0.070*
C5	0.2649 (3)	0.6122 (2)	0.13099 (18)	0.0498 (6)
H5	0.3078	0.6210	0.1902	0.060*
C6	0.1559 (3)	0.68464 (17)	0.11557 (15)	0.0378 (5)
C7	−0.0240 (3)	0.7404 (2)	−0.00253 (16)	0.0468 (6)
C8	0.1109 (3)	0.77229 (18)	0.19690 (15)	0.0422 (5)
H8A	0.1385	0.8410	0.1908	0.051*
H8B	0.1818	0.7709	0.2501	0.051*
C9	−0.1156 (3)	0.66328 (17)	0.26135 (13)	0.0378 (5)
C10	−0.2154 (3)	0.55875 (18)	0.32078 (14)	0.0423 (5)
C11	−0.2305 (4)	0.4334 (2)	0.38613 (17)	0.0561 (7)
C12	−0.0607 (4)	0.4109 (2)	0.37478 (17)	0.0553 (7)
C13	0.0312 (3)	0.46493 (19)	0.33293 (16)	0.0504 (6)
C14	−0.3379 (5)	0.3743 (3)	0.4296 (2)	0.0879 (10)
H14A	−0.4440	0.4054	0.4374	0.132*
H14B	−0.2796	0.3801	0.4875	0.132*
H14C	−0.3584	0.2999	0.3916	0.132*
C15	0.0175 (5)	0.3289 (3)	0.4084 (2)	0.0859 (10)
H15A	0.1310	0.3218	0.3937	0.129*
H15B	−0.0486	0.2608	0.3801	0.129*
H15C	0.0200	0.3517	0.4728	0.129*
C16	0.2060 (4)	0.4496 (3)	0.3089 (2)	0.0736 (9)
H16A	0.2021	0.4268	0.2444	0.110*
H16B	0.2525	0.3959	0.3299	0.110*
H16C	0.2759	0.5163	0.3369	0.110*
C17	0.6049 (2)	1.14480 (16)	0.50037 (13)	0.0326 (4)
C18	0.7736 (3)	1.17560 (18)	0.53904 (15)	0.0389 (5)
H18	0.7989	1.2305	0.5951	0.047*
C19	0.9034 (3)	1.1257 (2)	0.49523 (17)	0.0497 (6)
H19	1.0156	1.1475	0.5212	0.060*
C20	0.8663 (3)	1.0437 (2)	0.41324 (18)	0.0547 (7)
H20	0.9534	1.0095	0.3836	0.066*
C21	0.7000 (3)	1.01192 (19)	0.37471 (16)	0.0465 (6)
H21	0.6766	0.9555	0.3194	0.056*
C22	0.5665 (3)	1.06159 (17)	0.41607 (13)	0.0349 (5)
C23	0.4685 (3)	1.20209 (17)	0.54894 (14)	0.0374 (5)
C24	0.3889 (3)	1.02269 (18)	0.36945 (15)	0.0415 (5)
H24A	0.3184	1.0156	0.4133	0.050*
H24B	0.3894	0.9520	0.3238	0.050*
C25	0.3128 (3)	1.04492 (17)	0.20231 (14)	0.0373 (5)
C26	0.2631 (3)	1.01239 (17)	0.06348 (14)	0.0361 (5)
C27	0.2523 (3)	0.9258 (2)	−0.08829 (15)	0.0443 (5)
C28	0.3533 (3)	0.8463 (2)	−0.07553 (16)	0.0464 (6)
C29	0.4127 (3)	0.85393 (18)	0.01195 (16)	0.0404 (5)
C30	0.1838 (4)	0.9204 (3)	−0.18193 (17)	0.0663 (8)
H30A	0.0950	0.8629	−0.2076	0.099*
H30B	0.2732	0.9075	−0.2191	0.099*
H30C	0.1394	0.9873	−0.1789	0.099*
C31	0.3967 (4)	0.7532 (2)	−0.15416 (19)	0.0719 (8)
H31A	0.4912	0.7211	−0.1340	0.108*
H31B	0.4259	0.7788	−0.2006	0.108*
H31C	0.3007	0.7006	−0.1778	0.108*
C32	0.5236 (3)	0.7820 (2)	0.04002 (18)	0.0527 (6)
H32A	0.5969	0.8230	0.0946	0.079*
H32B	0.5908	0.7488	−0.0069	0.079*
H32C	0.4553	0.7274	0.0506	0.079*
N1	−0.2602 (2)	0.63664 (15)	0.28941 (12)	0.0436 (5)
N2	−0.0514 (2)	0.54084 (14)	0.30882 (12)	0.0411 (4)
N3	0.0152 (2)	0.60808 (15)	0.26981 (12)	0.0417 (4)
N4	−0.3095 (3)	0.50543 (17)	0.35896 (14)	0.0550 (5)
N5	0.2299 (2)	1.08180 (14)	0.14094 (12)	0.0407 (4)
N6	0.3622 (2)	0.93763 (14)	0.07882 (11)	0.0353 (4)
N7	0.3971 (2)	0.95893 (14)	0.17080 (12)	0.0380 (4)
N8	0.2086 (2)	1.00780 (15)	−0.02147 (12)	0.0421 (4)
O1	−0.0147 (2)	0.83985 (14)	0.05479 (11)	0.0506 (4)
H1	−0.084 (4)	0.889 (2)	0.0340 (19)	0.076*
O2	−0.1170 (3)	0.70967 (18)	−0.07322 (14)	0.0903 (7)
O3	0.3282 (2)	1.20440 (16)	0.51303 (11)	0.0607 (5)
O4	0.5167 (2)	1.25087 (15)	0.63675 (11)	0.0541 (5)
H4A	0.444 (4)	1.287 (2)	0.661 (2)	0.081*
S1	−0.10910 (8)	0.76491 (5)	0.21583 (4)	0.04530 (17)
S2	0.29647 (8)	1.11214 (5)	0.31609 (4)	0.04801 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0380 (11)	0.0426 (12)	0.0398 (12)	−0.0046 (9)	0.0061 (9)	0.0142 (10)
C2	0.0513 (14)	0.0559 (15)	0.0410 (13)	−0.0019 (12)	0.0086 (11)	0.0058 (11)
C3	0.0586 (16)	0.0462 (15)	0.0687 (19)	0.0025 (12)	0.0208 (14)	0.0008 (13)
C4	0.0485 (14)	0.0522 (15)	0.080 (2)	0.0142 (12)	0.0184 (14)	0.0263 (14)
C5	0.0419 (13)	0.0565 (15)	0.0550 (15)	0.0050 (11)	0.0063 (11)	0.0248 (12)
C6	0.0336 (11)	0.0398 (12)	0.0402 (12)	−0.0020 (9)	0.0062 (9)	0.0150 (10)
C7	0.0468 (13)	0.0542 (15)	0.0403 (13)	−0.0032 (11)	0.0007 (10)	0.0206 (11)
C8	0.0469 (13)	0.0416 (12)	0.0363 (12)	−0.0042 (10)	−0.0002 (9)	0.0145 (10)
C9	0.0453 (12)	0.0382 (11)	0.0278 (10)	0.0086 (10)	0.0076 (9)	0.0079 (9)
C10	0.0473 (13)	0.0428 (13)	0.0349 (12)	0.0071 (10)	0.0073 (10)	0.0105 (10)
C11	0.0758 (18)	0.0456 (14)	0.0461 (14)	−0.0007 (13)	0.0053 (13)	0.0171 (12)
C12	0.0789 (19)	0.0411 (13)	0.0440 (14)	0.0094 (13)	0.0019 (13)	0.0142 (11)
C13	0.0621 (16)	0.0446 (13)	0.0428 (13)	0.0136 (12)	0.0016 (11)	0.0139 (11)
C14	0.108 (3)	0.082 (2)	0.091 (2)	−0.0063 (19)	0.019 (2)	0.053 (2)
C15	0.118 (3)	0.065 (2)	0.086 (2)	0.0262 (19)	0.008 (2)	0.0412 (18)
C16	0.0677 (19)	0.084 (2)	0.080 (2)	0.0341 (16)	0.0126 (16)	0.0382 (18)
C17	0.0325 (10)	0.0382 (11)	0.0320 (10)	0.0051 (8)	0.0059 (8)	0.0179 (9)
C18	0.0348 (11)	0.0474 (13)	0.0371 (12)	0.0000 (9)	0.0019 (9)	0.0197 (10)
C19	0.0316 (11)	0.0684 (17)	0.0593 (16)	0.0095 (11)	0.0064 (11)	0.0345 (14)
C20	0.0483 (14)	0.0714 (18)	0.0568 (16)	0.0264 (13)	0.0229 (12)	0.0309 (14)
C21	0.0581 (15)	0.0474 (13)	0.0377 (12)	0.0158 (11)	0.0124 (11)	0.0164 (10)
C22	0.0411 (11)	0.0382 (11)	0.0307 (11)	0.0050 (9)	0.0052 (9)	0.0185 (9)
C23	0.0337 (11)	0.0444 (12)	0.0334 (11)	0.0036 (9)	0.0037 (9)	0.0132 (9)
C24	0.0466 (13)	0.0418 (12)	0.0356 (12)	−0.0024 (10)	−0.0024 (9)	0.0161 (10)
C25	0.0341 (11)	0.0393 (12)	0.0372 (11)	−0.0017 (9)	−0.0036 (9)	0.0152 (9)
C26	0.0332 (10)	0.0383 (11)	0.0394 (12)	−0.0022 (9)	−0.0003 (9)	0.0193 (10)
C27	0.0378 (12)	0.0587 (15)	0.0366 (12)	−0.0080 (11)	0.0030 (9)	0.0194 (11)
C28	0.0412 (12)	0.0529 (14)	0.0401 (13)	−0.0066 (11)	0.0091 (10)	0.0103 (11)
C29	0.0314 (11)	0.0416 (12)	0.0489 (13)	−0.0026 (9)	0.0090 (9)	0.0164 (10)
C30	0.0600 (16)	0.098 (2)	0.0409 (15)	0.0016 (15)	0.0020 (12)	0.0274 (15)
C31	0.079 (2)	0.0725 (19)	0.0550 (17)	0.0015 (16)	0.0204 (15)	0.0087 (14)
C32	0.0441 (13)	0.0485 (14)	0.0663 (17)	0.0083 (11)	0.0126 (12)	0.0194 (13)
N1	0.0460 (11)	0.0474 (11)	0.0413 (11)	0.0119 (9)	0.0140 (8)	0.0171 (9)
N2	0.0477 (11)	0.0398 (10)	0.0360 (10)	0.0096 (8)	0.0061 (8)	0.0128 (8)
N3	0.0432 (10)	0.0424 (10)	0.0417 (10)	0.0077 (8)	0.0069 (8)	0.0170 (8)
N4	0.0614 (13)	0.0547 (13)	0.0538 (13)	0.0023 (10)	0.0146 (10)	0.0237 (11)
N5	0.0425 (10)	0.0419 (10)	0.0389 (10)	0.0046 (8)	−0.0014 (8)	0.0178 (8)
N6	0.0319 (9)	0.0394 (10)	0.0348 (9)	−0.0007 (7)	0.0016 (7)	0.0149 (8)
N7	0.0374 (9)	0.0414 (10)	0.0342 (10)	0.0010 (8)	−0.0019 (7)	0.0145 (8)
N8	0.0410 (10)	0.0507 (11)	0.0380 (10)	−0.0021 (8)	0.0003 (8)	0.0225 (9)
O1	0.0548 (10)	0.0472 (10)	0.0511 (10)	0.0056 (8)	−0.0034 (8)	0.0222 (8)
O2	0.1126 (18)	0.0799 (15)	0.0601 (13)	0.0129 (13)	−0.0336 (12)	0.0152 (11)
O3	0.0384 (9)	0.0916 (14)	0.0435 (10)	0.0207 (9)	0.0016 (7)	0.0124 (9)
O4	0.0445 (9)	0.0730 (12)	0.0340 (9)	0.0208 (8)	0.0044 (7)	0.0037 (8)
S1	0.0544 (4)	0.0425 (3)	0.0446 (3)	0.0164 (3)	0.0148 (3)	0.0185 (3)
S2	0.0550 (4)	0.0494 (4)	0.0350 (3)	0.0131 (3)	−0.0044 (3)	0.0113 (3)

Geometric parameters (Å, º) top

C1—C2	1.389 (3)	C17—C23	1.489 (3)
C1—C6	1.404 (3)	C18—C19	1.379 (3)
C1—C7	1.489 (3)	C18—H18	0.9300
C2—C3	1.375 (4)	C19—C20	1.370 (4)
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.377 (4)	C20—C21	1.378 (3)
C3—H3	0.9300	C20—H20	0.9300
C4—C5	1.377 (3)	C21—C22	1.386 (3)
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.391 (3)	C22—C24	1.501 (3)
C5—H5	0.9300	C23—O3	1.204 (2)
C6—C8	1.503 (3)	C23—O4	1.322 (3)
C7—O2	1.203 (3)	C24—S2	1.822 (2)
C7—O1	1.315 (3)	C24—H24A	0.9700
C8—S1	1.816 (2)	C24—H24B	0.9700
C8—H8A	0.9700	C25—N7	1.327 (3)
C8—H8B	0.9700	C25—N5	1.359 (3)
C9—N3	1.323 (3)	C25—S2	1.742 (2)
C9—N1	1.357 (3)	C26—N5	1.322 (3)
C9—S1	1.742 (2)	C26—N8	1.352 (3)
C10—N4	1.337 (3)	C26—N6	1.368 (3)
C10—N1	1.343 (3)	C27—N8	1.325 (3)
C10—N2	1.362 (3)	C27—C28	1.414 (3)
C11—N4	1.335 (3)	C27—C30	1.504 (3)
C11—C12	1.417 (4)	C28—C29	1.386 (3)
C11—C14	1.509 (4)	C28—C31	1.511 (4)
C12—C13	1.374 (4)	C29—N6	1.360 (3)
C12—C15	1.502 (4)	C29—C32	1.477 (3)
C13—N2	1.369 (3)	C30—H30A	0.9600
C13—C16	1.490 (4)	C30—H30B	0.9600
C14—H14A	0.9600	C30—H30C	0.9600
C14—H14B	0.9600	C31—H31A	0.9600
C14—H14C	0.9600	C31—H31B	0.9600
C15—H15A	0.9600	C31—H31C	0.9600
C15—H15B	0.9600	C32—H32A	0.9600
C15—H15C	0.9600	C32—H32B	0.9600
C16—H16A	0.9600	C32—H32C	0.9600
C16—H16B	0.9600	N2—N3	1.372 (3)
C16—H16C	0.9600	N6—N7	1.383 (2)
C17—C18	1.394 (3)	O1—H1	0.99 (3)
C17—C22	1.402 (3)	O4—H4A	0.82 (3)

C2—C1—C6	119.2 (2)	C18—C19—H19	120.2
C2—C1—C7	115.7 (2)	C19—C20—C21	120.0 (2)
C6—C1—C7	125.1 (2)	C19—C20—H20	120.0
C3—C2—C1	121.4 (2)	C21—C20—H20	120.0
C3—C2—H2	119.3	C20—C21—C22	121.9 (2)
C1—C2—H2	119.3	C20—C21—H21	119.1
C2—C3—C4	119.8 (2)	C22—C21—H21	119.1
C2—C3—H3	120.1	C21—C22—C17	118.0 (2)
C4—C3—H3	120.1	C21—C22—C24	118.6 (2)
C5—C4—C3	119.6 (2)	C17—C22—C24	123.40 (19)
C5—C4—H4	120.2	O3—C23—O4	122.8 (2)
C3—C4—H4	120.2	O3—C23—C17	124.2 (2)
C4—C5—C6	121.8 (2)	O4—C23—C17	113.04 (17)
C4—C5—H5	119.1	C22—C24—S2	113.11 (15)
C6—C5—H5	119.1	C22—C24—H24A	109.0
C5—C6—C1	118.2 (2)	S2—C24—H24A	109.0
C5—C6—C8	117.4 (2)	C22—C24—H24B	109.0
C1—C6—C8	124.3 (2)	S2—C24—H24B	109.0
O2—C7—O1	122.3 (2)	H24A—C24—H24B	107.8
O2—C7—C1	122.7 (2)	N7—C25—N5	117.43 (19)
O1—C7—C1	114.94 (19)	N7—C25—S2	124.95 (16)
C6—C8—S1	115.71 (15)	N5—C25—S2	117.61 (16)
C6—C8—H8A	108.4	N5—C26—N8	128.4 (2)
S1—C8—H8A	108.4	N5—C26—N6	110.32 (18)
C6—C8—H8B	108.4	N8—C26—N6	121.2 (2)
S1—C8—H8B	108.4	N8—C27—C28	124.1 (2)
H8A—C8—H8B	107.4	N8—C27—C30	115.2 (2)
N3—C9—N1	116.7 (2)	C28—C27—C30	120.6 (2)
N3—C9—S1	123.20 (17)	C29—C28—C27	118.7 (2)
N1—C9—S1	120.07 (16)	C29—C28—C31	119.3 (2)
N4—C10—N1	128.0 (2)	C27—C28—C31	122.0 (2)
N4—C10—N2	123.1 (2)	N6—C29—C28	115.6 (2)
N1—C10—N2	108.87 (19)	N6—C29—C32	117.1 (2)
N4—C11—C12	124.1 (2)	C28—C29—C32	127.4 (2)
N4—C11—C14	114.6 (3)	C27—C30—H30A	109.5
C12—C11—C14	121.3 (3)	C27—C30—H30B	109.5
C13—C12—C11	119.3 (2)	H30A—C30—H30B	109.5
C13—C12—C15	120.6 (3)	C27—C30—H30C	109.5
C11—C12—C15	120.1 (3)	H30A—C30—H30C	109.5
N2—C13—C12	115.1 (2)	H30B—C30—H30C	109.5
N2—C13—C16	116.4 (2)	C28—C31—H31A	109.5
C12—C13—C16	128.4 (2)	C28—C31—H31B	109.5
C11—C14—H14A	109.5	H31A—C31—H31B	109.5
C11—C14—H14B	109.5	C28—C31—H31C	109.5
H14A—C14—H14B	109.5	H31A—C31—H31C	109.5
C11—C14—H14C	109.5	H31B—C31—H31C	109.5
H14A—C14—H14C	109.5	C29—C32—H32A	109.5
H14B—C14—H14C	109.5	C29—C32—H32B	109.5
C12—C15—H15A	109.5	H32A—C32—H32B	109.5
C12—C15—H15B	109.5	C29—C32—H32C	109.5
H15A—C15—H15B	109.5	H32A—C32—H32C	109.5
C12—C15—H15C	109.5	H32B—C32—H32C	109.5
H15A—C15—H15C	109.5	C10—N1—C9	102.63 (18)
H15B—C15—H15C	109.5	C10—N2—C13	123.1 (2)
C13—C16—H16A	109.5	C10—N2—N3	110.72 (17)
C13—C16—H16B	109.5	C13—N2—N3	126.16 (19)
H16A—C16—H16B	109.5	C9—N3—N2	101.02 (17)
C13—C16—H16C	109.5	C11—N4—C10	115.2 (2)
H16A—C16—H16C	109.5	C26—N5—C25	102.08 (18)
H16B—C16—H16C	109.5	C29—N6—C26	123.83 (18)
C18—C17—C22	119.63 (19)	C29—N6—N7	126.37 (18)
C18—C17—C23	119.25 (19)	C26—N6—N7	109.76 (17)
C22—C17—C23	121.12 (18)	C25—N7—N6	100.40 (16)
C19—C18—C17	120.9 (2)	C27—N8—C26	116.5 (2)
C19—C18—H18	119.6	C7—O1—H1	115.3 (16)
C17—C18—H18	119.6	C23—O4—H4A	112 (2)
C20—C19—C18	119.7 (2)	C9—S1—C8	101.72 (11)
C20—C19—H19	120.2	C25—S2—C24	102.45 (10)

C6—C1—C2—C3	−1.0 (3)	C27—C28—C29—C32	−177.9 (2)
C7—C1—C2—C3	178.9 (2)	C31—C28—C29—C32	2.6 (3)
C1—C2—C3—C4	0.0 (4)	N4—C10—N1—C9	178.1 (2)
C2—C3—C4—C5	1.2 (4)	N2—C10—N1—C9	−1.2 (2)
C3—C4—C5—C6	−1.4 (4)	N3—C9—N1—C10	1.6 (2)
C4—C5—C6—C1	0.4 (3)	S1—C9—N1—C10	−178.97 (15)
C4—C5—C6—C8	178.8 (2)	N4—C10—N2—C13	1.5 (3)
C2—C1—C6—C5	0.8 (3)	N1—C10—N2—C13	−179.1 (2)
C7—C1—C6—C5	−179.1 (2)	N4—C10—N2—N3	−178.8 (2)
C2—C1—C6—C8	−177.4 (2)	N1—C10—N2—N3	0.6 (2)
C7—C1—C6—C8	2.7 (3)	C12—C13—N2—C10	−3.2 (3)
C2—C1—C7—O2	24.1 (3)	C16—C13—N2—C10	175.5 (2)
C6—C1—C7—O2	−156.0 (3)	C12—C13—N2—N3	177.1 (2)
C2—C1—C7—O1	−154.6 (2)	C16—C13—N2—N3	−4.2 (3)
C6—C1—C7—O1	25.3 (3)	N1—C9—N3—N2	−1.2 (2)
C5—C6—C8—S1	−113.2 (2)	S1—C9—N3—N2	179.36 (15)
C1—C6—C8—S1	65.0 (2)	C10—N2—N3—C9	0.4 (2)
N4—C11—C12—C13	−0.4 (4)	C13—N2—N3—C9	−179.9 (2)
C14—C11—C12—C13	178.5 (3)	C12—C11—N4—C10	−1.4 (4)
N4—C11—C12—C15	179.5 (3)	C14—C11—N4—C10	179.6 (2)
C14—C11—C12—C15	−1.6 (4)	N1—C10—N4—C11	−178.4 (2)
C11—C12—C13—N2	2.6 (3)	N2—C10—N4—C11	0.9 (3)
C15—C12—C13—N2	−177.3 (2)	N8—C26—N5—C25	178.0 (2)
C11—C12—C13—C16	−175.9 (3)	N6—C26—N5—C25	−0.2 (2)
C15—C12—C13—C16	4.2 (4)	N7—C25—N5—C26	0.7 (2)
C22—C17—C18—C19	0.3 (3)	S2—C25—N5—C26	−177.89 (15)
C23—C17—C18—C19	−178.8 (2)	C28—C29—N6—C26	−1.6 (3)
C17—C18—C19—C20	−0.9 (3)	C32—C29—N6—C26	178.36 (19)
C18—C19—C20—C21	0.3 (4)	C28—C29—N6—N7	176.33 (18)
C19—C20—C21—C22	0.8 (4)	C32—C29—N6—N7	−3.7 (3)
C20—C21—C22—C17	−1.4 (3)	N5—C26—N6—C29	177.89 (18)
C20—C21—C22—C24	179.6 (2)	N8—C26—N6—C29	−0.4 (3)
C18—C17—C22—C21	0.8 (3)	N5—C26—N6—N7	−0.3 (2)
C23—C17—C22—C21	179.92 (19)	N8—C26—N6—N7	−178.66 (17)
C18—C17—C22—C24	179.73 (19)	N5—C25—N7—N6	−0.8 (2)
C23—C17—C22—C24	−1.1 (3)	S2—C25—N7—N6	177.61 (15)
C18—C17—C23—O3	158.2 (2)	C29—N6—N7—C25	−177.50 (19)
C22—C17—C23—O3	−21.0 (3)	C26—N6—N7—C25	0.7 (2)
C18—C17—C23—O4	−22.0 (3)	C28—C27—N8—C26	−1.4 (3)
C22—C17—C23—O4	158.90 (19)	C30—C27—N8—C26	177.56 (19)
C21—C22—C24—S2	−104.0 (2)	N5—C26—N8—C27	−176.1 (2)
C17—C22—C24—S2	77.1 (2)	N6—C26—N8—C27	1.9 (3)
N8—C27—C28—C29	−0.6 (3)	N3—C9—S1—C8	−3.9 (2)
C30—C27—C28—C29	−179.5 (2)	N1—C9—S1—C8	176.71 (16)
N8—C27—C28—C31	178.9 (2)	C6—C8—S1—C9	76.95 (18)
C30—C27—C28—C31	0.0 (3)	N7—C25—S2—C24	−8.8 (2)
C27—C28—C29—N6	2.0 (3)	N5—C25—S2—C24	169.62 (16)
C31—C28—C29—N6	−177.5 (2)	C22—C24—S2—C25	102.64 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···N1ⁱ	0.82 (3)	1.90 (3)	2.721 (2)	175 (3)
O1—H1···N8ⁱⁱ	0.99 (3)	1.79 (3)	2.762 (2)	168 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₆H₁₆N₄O₂S
M_r	328.39
Crystal system, space group	Triclinic, P1
Temperature (K)	299
a, b, c (Å)	7.9704 (5), 13.3058 (8), 15.9084 (9)
α, β, γ (°)	110.257 (1), 96.446 (1), 92.620 (1)
V (Å³)	1566.28 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART 4K CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.936, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	17990, 7079, 5206
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.154, 1.04
No. of reflections	7079
No. of parameters	427
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.25

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXTL (Bruker, 2001).