1-Acetonyl-4-(2,5-dimethyl-4H-1,2,4-triazol-4-yl)-3-(2-thienylmeth­yl)-1H-1,2,4-triazol-5(4H)-one

Ustabaş, R.; Çoruh, U.; Sancak, K.; Demirkan, E.

doi:10.1107/S160053680703231X

1-Acetonyl-4-(2,5-dimethyl-4H-1,2,4-triazol-4-yl)-3-(2-thienylmethyl)-1H-1,2,4-triazol-5(4H)-one

R. Ustabaş, U. Çoruh, K. Sancak and E. Demirkan

The thiophene ring of the title compound, C₁₄H₁₆N₆O₂S, is disordered over two positions, with a site-occupancy ratio of approximately 5:4, corresponding to rotation of approximately 180° about the single C—C bond. Intermolecular C—H

N and C—H

O interactions stabilize the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703231X/is2184sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680703231X/is2184Isup2.hkl Contains datablock I

CCDC reference: 657722

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
Disorder in main residue
R factor = 0.033
wR factor = 0.097
Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.65 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C52
PLAT301_ALERT_3_C Main Residue  Disorder .........................      18.00 Perc.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C53
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C14 H16 N6 O2 S

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.12
           From the CIF: _reflns_number_total               3357
           Count of symmetry unique reflns         1793
           Completeness (_total/calc)            187.23%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1564
           Fraction of Friedel pairs measured     0.872
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......        179

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

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

Comment top

In a continuing search for pharmacologically active, 1,2,4-triazol and 1,2,4-triazol-5-one compounds, it has been found that most azole fungicides have been developed for diseases of cereal crops; examples include fluconazole (Ichikawa et al., 2001), ravuconazole (Ueda, 2003) and posaconazole (Kim et al., 2003). Moreover, 1,2,4-triazole derivatives have broad-spectrum biological effects, such as insecticidal (Tsuda et al., 2004), herbicidal (Chai et al., 2003), anticonvulsant (Er-Rahimini & Mornet, 1992), antitumor (Nakib et al., 1994) and plant growth regulatory activities (Jenkins et al., 1989).

The title compound, (I), consists of a triazole ring with an acetonyl group substituted at atom N5, a thienylmethyl group substituted at C4, a 1,2,4-triazole ring substituted at N4 atom and an oxo O atom at C3 (Fig. 1). The C1═N2 bond length, 1.298 (3) Å, is a little longer than some values reported in the literature [1.288 (3) Å in C₁₆H₂₈N₆O₂ Çoruh et al., 2003) and 1.267 (2) Å in 4-(4-hydroxybenzylidenamino)-4H-1,2,4-triazole hemihydrate (Zhu et al., 2000)]. In the central 1,2,4-triazole ring, atoms N2 and N3 have no substituents and the N2—N3 bond length, 1.398 (3) Å, is essentially identical to that [1.403 (8) Å] reported for a similar compound (Sancak et al., 2005). Atom C4 has a trigonal configuration, the sums of the three bond angles around them being 359.99 (13)°.

The thiophene ring is disordered over two positions, corresponding to rotation of approximately 180° about the single C41—C42 bond, with a major-minor ratio of 55.9 (3):44.1 (3). The crystal structure of (I) is stabilized by two C—H···N and five C—H···O intermolecular hydrogen bonds (Table 1).

Related literature top

For related literature, see: Chai et al. (2003); Er-Rahimini & Mornet (1992); Ichikawa et al. (2001); Jenkins et al. (1989); Kim et al. (2003); Nakib et al. (1994); Sancak et al. (2005); Tsuda et al. (2004); Ueda (2003); Zhu et al. (2000); Çoruh et al. (2003).

Experimental top

4-(3,5-Dimethyl-4H-1,2,4-triazol-4-yl)-3-(2-thienyl methyl)-1H-1,2,4-triazol-5(4H)-one (0.001 mol) was refluxed with sodium metal (0.001 mol) in absolute ethanol (50 ml) for 1 h. Chloroacetone (0.001 mol) was added and the solution refluxed for 8 h. The resulting solution was filtered and then evaporated under reduced pressure. The solid residue was crystallized from absolute ethanol-diethylether (1:4) (yield 67%; m.p. 493–494 K).

Structure description top

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. An ORTEP drawing of (I), with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Both disorder components are shown.

1-acetonyl-4-(2,5-dimethyl-4H-\1,2,4-triazol-4-yl)-3-(2-thienylmethyl)-1H-1,2,4-triazol-5(4H)-one top

Crystal data top

C₁₄H₁₆N₆O₂S	F(000) = 696
M_r = 332.39	D_x = 1.364 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 3185 reflections
a = 21.1928 (16) Å	θ = 2.4–27.1°
b = 9.6058 (6) Å	µ = 0.22 mm⁻¹
c = 8.3020 (7) Å	T = 293 K
β = 106.696 (6)°	Prism, colourless
V = 1618.8 (2) Å³	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3185 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.039
Graphite monochromator	θ_max = 27.1°, θ_min = 2.4°
φ and ω scans	h = −27→27
9238 measured reflections	k = −12→12
3357 independent reflections	l = −10→10

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0678P)² + 0.126P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.15 e Å⁻³
3357 reflections	Δρ_min = −0.18 e Å⁻³
246 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
179 restraints	Extinction coefficient: 0.015 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1644 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.02 (8)

Crystal data top

C₁₄H₁₆N₆O₂S	V = 1618.8 (2) Å³
M_r = 332.39	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 21.1928 (16) Å	µ = 0.22 mm⁻¹
b = 9.6058 (6) Å	T = 293 K
c = 8.3020 (7) Å	0.30 × 0.20 × 0.15 mm
β = 106.696 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3185 reflections with I > 2σ(I)
9238 measured reflections	R_int = 0.039
3357 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.097	Δρ_max = 0.15 e Å⁻³
S = 1.06	Δρ_min = −0.18 e Å⁻³
3357 reflections	Absolute structure: Flack (1983), 1644 Friedel pairs
246 parameters	Absolute structure parameter: −0.02 (8)
179 restraints

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	Occ. (<1)
O1	0.03169 (6)	0.79946 (12)	−0.49156 (15)	0.0472 (3)
N1	0.13400 (7)	0.64873 (13)	−0.25347 (17)	0.0422 (3)
N6	0.11847 (7)	0.99970 (13)	−0.14966 (18)	0.0393 (3)
N5	0.07161 (7)	0.98340 (12)	−0.30460 (17)	0.0398 (3)
C41	0.19981 (8)	0.84790 (17)	0.0412 (2)	0.0438 (3)
H41A	0.1928	0.7556	0.0803	0.053*
H41B	0.1976	0.9139	0.1278	0.053*
C42	0.26718 (8)	0.85404 (16)	0.0173 (2)	0.0445 (3)	0.559 (3)
S1	0.32023 (8)	0.71922 (19)	0.0776 (3)	0.0634 (5)	0.559 (3)
C43	0.3784 (4)	0.8126 (10)	0.0046 (16)	0.0627 (17)	0.559 (3)
H43	0.4199	0.7770	0.0110	0.075*	0.559 (3)
C44	0.3585 (4)	0.9386 (11)	−0.0606 (16)	0.0633 (15)	0.559 (3)
H44	0.3831	1.0013	−0.1033	0.076*	0.559 (3)
C45	0.2952 (5)	0.9576 (8)	−0.0527 (14)	0.0614 (16)	0.559 (3)
H45	0.2720	1.0385	−0.0938	0.074*	0.559 (3)
C42'	0.26718 (8)	0.85404 (16)	0.0173 (2)	0.0445 (3)	0.441 (3)
S1'	0.29405 (13)	0.9970 (2)	−0.0653 (4)	0.0565 (5)	0.441 (3)
C43'	0.3687 (5)	0.9102 (13)	−0.047 (2)	0.0600 (18)	0.441 (3)
H43'	0.4027	0.9515	−0.0798	0.072*	0.441 (3)
C44'	0.3743 (7)	0.7795 (13)	0.018 (2)	0.068 (2)	0.441 (3)
H44'	0.4096	0.7185	0.0342	0.082*	0.441 (3)
C45'	0.3165 (5)	0.7580 (9)	0.0556 (15)	0.0654 (19)	0.441 (3)
H45'	0.3105	0.6757	0.1085	0.078*	0.441 (3)
C3	0.06799 (7)	0.85162 (14)	−0.36608 (19)	0.0381 (3)
C52	−0.03960 (8)	1.0779 (2)	−0.3428 (2)	0.0517 (4)
O2	−0.05226 (8)	0.97759 (18)	−0.2716 (2)	0.0688 (4)
N4	0.11834 (6)	0.78629 (12)	−0.24189 (17)	0.0396 (3)
C4	0.14634 (7)	0.87926 (14)	−0.11427 (19)	0.0372 (3)
C1	0.09964 (10)	0.53665 (16)	−0.2186 (2)	0.0487 (4)
N3	0.17852 (10)	0.46323 (18)	−0.3180 (3)	0.0668 (5)
N2	0.12657 (10)	0.42417 (16)	−0.2552 (2)	0.0648 (5)
C51	0.02666 (8)	1.09491 (16)	−0.3740 (2)	0.0442 (3)
H51A	0.0205	1.0996	−0.4943	0.053*
H51B	0.0460	1.1823	−0.3252	0.053*
C2	0.18161 (9)	0.59797 (19)	−0.3193 (2)	0.0506 (4)
C11	0.04103 (12)	0.5476 (2)	−0.1593 (3)	0.0646 (5)
H11A	0.0328	0.6437	−0.1408	0.097*
H11B	0.0482	0.4970	−0.0559	0.097*
H11C	0.0038	0.5093	−0.2423	0.097*
C53	−0.08696 (15)	1.1932 (4)	−0.4126 (5)	0.0988 (10)
H53A	−0.1278	1.1756	−0.3880	0.148*
H53B	−0.0946	1.1981	−0.5322	0.148*
H53C	−0.0688	1.2798	−0.3625	0.148*
C22	0.22523 (12)	0.6864 (3)	−0.3854 (3)	0.0695 (6)
H22A	0.2169	0.7825	−0.3674	0.104*
H22B	0.2169	0.6695	−0.5037	0.104*
H22C	0.2703	0.6647	−0.3283	0.104*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0443 (6)	0.0462 (6)	0.0463 (7)	−0.0034 (4)	0.0053 (5)	−0.0036 (4)
N1	0.0450 (6)	0.0316 (6)	0.0473 (7)	0.0032 (5)	0.0089 (5)	−0.0028 (5)
N6	0.0380 (6)	0.0364 (6)	0.0433 (7)	0.0000 (4)	0.0115 (5)	−0.0026 (5)
N5	0.0375 (5)	0.0363 (6)	0.0430 (7)	0.0038 (4)	0.0074 (5)	−0.0014 (5)
C41	0.0437 (7)	0.0436 (7)	0.0413 (9)	−0.0009 (6)	0.0078 (6)	−0.0003 (6)
C42	0.0420 (7)	0.0429 (7)	0.0433 (8)	0.0031 (6)	0.0038 (6)	−0.0019 (6)
S1	0.0519 (5)	0.0596 (9)	0.0741 (9)	0.0193 (6)	0.0109 (5)	0.0121 (6)
C43	0.0359 (17)	0.068 (4)	0.079 (3)	0.007 (2)	0.0082 (18)	−0.002 (3)
C44	0.049 (3)	0.064 (4)	0.074 (3)	0.005 (2)	0.013 (2)	0.002 (3)
C45	0.054 (2)	0.057 (3)	0.067 (3)	0.009 (3)	0.0088 (18)	0.003 (3)
C42'	0.0420 (7)	0.0429 (7)	0.0433 (8)	0.0031 (6)	0.0038 (6)	−0.0019 (6)
S1'	0.0475 (7)	0.0541 (11)	0.0683 (9)	−0.0008 (8)	0.0174 (6)	0.0090 (9)
C43'	0.043 (3)	0.060 (5)	0.078 (4)	0.010 (2)	0.018 (3)	0.008 (3)
C44'	0.053 (3)	0.062 (4)	0.084 (3)	0.013 (3)	0.010 (3)	0.012 (3)
C45'	0.062 (3)	0.053 (4)	0.072 (4)	0.013 (3)	0.004 (2)	0.011 (3)
C3	0.0361 (6)	0.0366 (6)	0.0416 (8)	−0.0014 (5)	0.0111 (5)	−0.0003 (6)
C52	0.0412 (8)	0.0618 (10)	0.0495 (10)	0.0039 (7)	0.0091 (7)	−0.0066 (8)
O2	0.0551 (7)	0.0827 (10)	0.0708 (11)	−0.0165 (7)	0.0218 (7)	−0.0037 (7)
N4	0.0405 (6)	0.0312 (5)	0.0443 (8)	0.0022 (4)	0.0074 (5)	−0.0042 (4)
C4	0.0357 (6)	0.0355 (7)	0.0413 (8)	−0.0022 (5)	0.0127 (5)	−0.0026 (5)
C1	0.0615 (10)	0.0363 (7)	0.0411 (9)	−0.0047 (6)	0.0031 (7)	0.0001 (6)
N3	0.0782 (11)	0.0488 (8)	0.0673 (11)	0.0169 (8)	0.0111 (9)	−0.0156 (7)
N2	0.0870 (12)	0.0369 (7)	0.0619 (11)	0.0018 (7)	0.0078 (9)	−0.0044 (6)
C51	0.0442 (7)	0.0380 (7)	0.0484 (9)	0.0064 (6)	0.0102 (6)	0.0020 (6)
C2	0.0495 (8)	0.0488 (8)	0.0485 (9)	0.0093 (7)	0.0062 (7)	−0.0115 (7)
C11	0.0683 (12)	0.0631 (11)	0.0615 (12)	−0.0164 (10)	0.0171 (10)	0.0037 (9)
C53	0.0668 (14)	0.112 (2)	0.116 (2)	0.0472 (15)	0.0246 (15)	0.0128 (17)
C22	0.0564 (10)	0.0831 (14)	0.0750 (15)	−0.0073 (9)	0.0284 (10)	−0.0232 (11)

Geometric parameters (Å, º) top

O1—C3	1.2114 (19)	C44'—H44'	0.9300
N1—C2	1.368 (2)	C45'—H45'	0.9300
N1—N4	1.3726 (17)	C3—N4	1.4011 (19)
N1—C1	1.376 (2)	C52—O2	1.201 (3)
N6—C4	1.2939 (19)	C52—C53	1.495 (3)
N6—N5	1.3897 (19)	C52—C51	1.508 (2)
N5—C3	1.3587 (18)	N4—C4	1.3824 (19)
N5—C51	1.4392 (19)	C1—N2	1.298 (3)
C41—C4	1.483 (2)	C1—C11	1.465 (3)
C41—C42	1.498 (2)	N3—C2	1.296 (3)
C41—H41A	0.9700	N3—N2	1.398 (3)
C41—H41B	0.9700	C51—H51A	0.9700
C42—C45	1.371 (9)	C51—H51B	0.9700
C42—S1	1.694 (2)	C2—C22	1.473 (3)
S1—C43	1.766 (8)	C11—H11A	0.9600
C43—C44	1.343 (8)	C11—H11B	0.9600
C43—H43	0.9300	C11—H11C	0.9600
C44—C45	1.375 (13)	C53—H53A	0.9600
C44—H44	0.9300	C53—H53B	0.9600
C45—H45	0.9300	C53—H53C	0.9600
S1'—C43'	1.756 (10)	C22—H22A	0.9600
C43'—C44'	1.358 (10)	C22—H22B	0.9600
C43'—H43'	0.9300	C22—H22C	0.9600
C44'—C45'	1.362 (16)

C2—N1—N4	126.30 (14)	N1—N4—C4	128.05 (12)
C2—N1—C1	107.52 (14)	N1—N4—C3	121.87 (12)
N4—N1—C1	125.81 (14)	C4—N4—C3	110.07 (12)
C4—N6—N5	105.52 (12)	N6—C4—N4	109.64 (13)
C3—N5—N6	113.63 (12)	N6—C4—C41	124.33 (14)
C3—N5—C51	125.70 (14)	N4—C4—C41	126.02 (13)
N6—N5—C51	120.09 (13)	N2—C1—N1	107.86 (18)
C4—C41—C42	113.30 (12)	N2—C1—C11	127.64 (18)
C4—C41—H41A	108.9	N1—C1—C11	124.42 (15)
C42—C41—H41A	108.9	C2—N3—N2	108.53 (15)
C4—C41—H41B	108.9	C1—N2—N3	108.08 (16)
C42—C41—H41B	108.9	N5—C51—C52	113.11 (14)
H41A—C41—H41B	107.7	N5—C51—H51A	109.0
C45—C42—C41	129.1 (4)	C52—C51—H51A	109.0
C45—C42—S1	110.4 (4)	N5—C51—H51B	109.0
C41—C42—S1	120.51 (14)	C52—C51—H51B	109.0
C42—S1—C43	88.8 (4)	H51A—C51—H51B	107.8
C44—C43—S1	115.3 (9)	N3—C2—N1	107.94 (18)
C44—C43—H43	122.3	N3—C2—C22	128.11 (17)
S1—C43—H43	122.3	N1—C2—C22	123.88 (17)
C43—C44—C45	107.3 (10)	C1—C11—H11A	109.5
C43—C44—H44	126.4	C1—C11—H11B	109.5
C45—C44—H44	126.4	H11A—C11—H11B	109.5
C42—C45—C44	118.2 (8)	C1—C11—H11C	109.5
C42—C45—H45	120.9	H11A—C11—H11C	109.5
C44—C45—H45	120.9	H11B—C11—H11C	109.5
C44'—C43'—S1'	116.6 (12)	C52—C53—H53A	109.5
C44'—C43'—H43'	121.7	C52—C53—H53B	109.5
S1'—C43'—H43'	121.7	H53A—C53—H53B	109.5
C43'—C44'—C45'	104.4 (13)	C52—C53—H53C	109.5
C43'—C44'—H44'	127.8	H53A—C53—H53C	109.5
C45'—C44'—H44'	127.8	H53B—C53—H53C	109.5
C44'—C45'—H45'	119.2	C2—C22—H22A	109.5
O1—C3—N5	131.43 (14)	C2—C22—H22B	109.5
O1—C3—N4	127.49 (13)	H22A—C22—H22B	109.5
N5—C3—N4	101.07 (12)	C2—C22—H22C	109.5
O2—C52—C53	124.4 (2)	H22A—C22—H22C	109.5
O2—C52—C51	121.49 (16)	H22B—C22—H22C	109.5
C53—C52—C51	114.1 (2)

C4—N6—N5—C3	1.96 (16)	N5—N6—C4—C41	−179.87 (13)
C4—N6—N5—C51	173.77 (13)	N1—N4—C4—N6	179.59 (14)
C4—C41—C42—C45	50.9 (6)	C3—N4—C4—N6	−1.31 (16)
C4—C41—C42—S1	−128.07 (16)	N1—N4—C4—C41	−0.9 (2)
C45—C42—S1—C43	0.3 (7)	C3—N4—C4—C41	178.23 (13)
C41—C42—S1—C43	179.5 (4)	C42—C41—C4—N6	−97.73 (17)
C42—S1—C43—C44	0.3 (9)	C42—C41—C4—N4	82.80 (18)
S1—C43—C44—C45	−0.8 (13)	C2—N1—C1—N2	2.27 (19)
C41—C42—C45—C44	−180.0 (8)	N4—N1—C1—N2	175.59 (15)
S1—C42—C45—C44	−0.9 (12)	C2—N1—C1—C11	−174.74 (19)
C43—C44—C45—C42	1.1 (15)	N4—N1—C1—C11	−1.4 (3)
S1'—C43'—C44'—C45'	−1.8 (18)	N1—C1—N2—N3	−1.1 (2)
N6—N5—C3—O1	176.56 (14)	C11—C1—N2—N3	175.8 (2)
C51—N5—C3—O1	5.3 (3)	C2—N3—N2—C1	−0.5 (2)
N6—N5—C3—N4	−2.60 (16)	C3—N5—C51—C52	72.9 (2)
C51—N5—C3—N4	−173.87 (13)	N6—N5—C51—C52	−97.89 (16)
C2—N1—N4—C4	−87.1 (2)	O2—C52—C51—N5	−2.3 (2)
C1—N1—N4—C4	100.82 (19)	C53—C52—C51—N5	179.6 (2)
C2—N1—N4—C3	93.89 (19)	N2—N3—C2—N1	1.9 (2)
C1—N1—N4—C3	−78.2 (2)	N2—N3—C2—C22	−175.4 (2)
O1—C3—N4—N1	2.3 (2)	N4—N1—C2—N3	−175.84 (15)
N5—C3—N4—N1	−178.52 (13)	C1—N1—C2—N3	−2.57 (19)
O1—C3—N4—C4	−176.90 (14)	N4—N1—C2—C22	1.6 (3)
N5—C3—N4—C4	2.31 (15)	C1—N1—C2—C22	174.83 (19)
N5—N6—C4—N4	−0.33 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22B···N2ⁱ	0.96	2.56	3.352 (3)	140
C41—H41A···N3ⁱⁱ	0.97	2.32	3.287 (3)	178
C43—H43···O1ⁱⁱⁱ	0.93	2.49	3.414 (10)	174
C44′—H44′···O2ⁱⁱⁱ	0.93	2.46	3.162 (14)	132
C51—H51A···O2^iv	0.97	2.49	3.318 (2)	143

Symmetry codes: (i) x, −y+1, z−1/2; (ii) x, −y+1, z+1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) x, −y+2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₆O₂S
M_r	332.39
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	21.1928 (16), 9.6058 (6), 8.3020 (7)
β (°)	106.696 (6)
V (Å³)	1618.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.30 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9238, 3357, 3185
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.097, 1.06
No. of reflections	3357
No. of parameters	246
No. of restraints	179
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.18
Absolute structure	Flack (1983), 1644 Friedel pairs
Absolute structure parameter	−0.02 (8)

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).