Ethyl 2-benzyl­sulfanyl-7-(2-chloro­phen­yl)-5-methyl-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxyl­ate

Song, D.-D.; Chen, Q.

doi:10.1107/S1600536807062174

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o44

https://doi.org/10.1107/S1600536807062174

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Ethyl 2-benzylsulfanyl-7-(2-chlorophenyl)-5-methyl-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylate

Dan-Dan Song ^a and Qiong Chen ^b ^*

^aCollege of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China, and ^bKey Laboratory of Pesticides and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: qchen@mail.ccnu.edu.cn

(Received 22 November 2007; accepted 22 November 2007; online 6 December 2007)

In the title compound, C₂₂H₂₁ClN₄O₂S, the bicyclic triazolopyrimidine ring system is nearly planar, and oriented at dihedral angles of 89.45 (3)° with respect to the chlorobenzene ring and 87.03 (3)° with respect to the terminal phenyl ring. In the crystal structure, molecules are linked by π–π stacking interactions between the triazolopyrimidine rings [centroid–centroid distances of 3.88 (1) and 3.63 (1) Å].

Related literature

For general background, see: Fedorova et al. (2003 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₂H₂₁ClN₄O₂S
M_r = 440.94
Triclinic, $[P \overline 1]$
a = 7.5884 (9) Å
b = 10.7303 (12) Å
c = 14.8825 (16) Å
α = 70.655 (2)°
β = 86.097 (2)°
γ = 70.032 (2)°
V = 1073.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 292 (2) K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer
Absorption correction: none
7183 measured reflections
4374 independent reflections
3305 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.143
S = 1.07
4374 reflections
277 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062174/hk2397sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062174/hk2397Isup2.hkl

checkCIF report

Comment top

In recent years, growing attention has been paid to analogues of purines and nucleosides, including azolopyrimidines containing the bridge head nitrogen atom and their dihydro derivatives, among which promising biologically active compounds were found (Fedorova et al., 2003). We synthesized a novel class of ethyl 7-alkylthio-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine-6- carboxylate derivatives by three component condensation of 3-amino-5-alkyl- thio-1,2,4-triazoles with aromatic aldehydes and β-keto ester. We report herein the crystal structure of one such analogue, a triazolopyrimidine derivative, the title compound, (I).

In the molecule of (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A (C1—C6), B (N1—N3/C8/C9), C (N3/N4/C9/C10/C12/C13) and D (C14—C19) are, of course, planar. The bicyclic triazolopyrimidine ring system (N1—N4/C8—C10/C12/C13) is nearly planar with a maximum deviation of 0.034 (2) Å (for atom C8), and it is oriented with respect to rings A and D at dihedral angles of 87.03 (3)° and 89.45 (3)°, respectively.

In the crystal structure (Fig. 2), molecules are linked by π···π stacking interactions involving B and C rings of the adjacent molecules with a centroid-centroid distance of 3.88 (1) Å (symmetry code: 1 - x, -y, 1 - z). The adjacent B rings have a centroid-centroid distance of 3.63 (1) %A (symmetry code: 1 - x, -y, 1 - z).

Related literature top

For general background, see: Fedorova et al. (2003). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, a mixture of acetylacetic ester (1 mmol), 2-chloro benzaldehyde (1 mmol) and 3-amino-5-benzyllthio-1,2,4 -triazole (1 mmol) in EtOH (3 ml) was added into a microwave tube. The sealed tube was placed in a Smith synthesizer and irradiated at 323 K for 30 min. The reaction mixture was cooled to room temperature, and the precipitate was filtered and recrystallized from ethanol to give the title compound, (I). Single crystals of (I), suitable for X-ray analysis were grown from an acetone solution at 293 K. ¹H NMR (CDCl3, 400 MHz): σ 10.89(s, 1 H), 7.14–7.41(m, 9 H), 6.84(s, 1H), 4.25(d, 1H), 4.11(d, 1H), 4.02(q,2 H), 2.59(s, 3H),1.08(t, 3H).

Structure description top

For general background, see: Fedorova et al. (2003). For bond-length data, see: Allen et al. (1987).

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 of (I).

Ethyl 2-benzylsulfanyl-7-(2-chlorophenyl)-5-methyl-4,7-dihydro-1,2,4-τriazolo[1,5-a]pyrimidine-6-carboxylate top

Crystal data top

C₂₂H₂₁ClN₄O₂S	Z = 2
M_r = 440.94	F(000) = 460
Triclinic, P1	D_x = 1.364 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5884 (9) Å	Cell parameters from 2807 reflections
b = 10.7303 (12) Å	θ = 2.9–27.5°
c = 14.8825 (16) Å	µ = 0.30 mm⁻¹
α = 70.655 (2)°	T = 292 K
β = 86.097 (2)°	Block, colorless
γ = 70.032 (2)°	0.30 × 0.20 × 0.20 mm
V = 1073.3 (2) Å³

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	3305 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 26.5°, θ_min = 2.1°
φ and ω scans	h = −9→9
7183 measured reflections	k = −13→9
4374 independent reflections	l = −18→15

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0766P)² + 0.0197P] where P = (F_o² + 2F_c²)/3
4374 reflections	(Δ/σ)_max = 0.004
277 parameters	Δρ_max = 0.27 e Å⁻³
1 restraint	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₂H₂₁ClN₄O₂S	γ = 70.032 (2)°
M_r = 440.94	V = 1073.3 (2) Å³
Triclinic, P1	Z = 2
a = 7.5884 (9) Å	Mo Kα radiation
b = 10.7303 (12) Å	µ = 0.30 mm⁻¹
c = 14.8825 (16) Å	T = 292 K
α = 70.655 (2)°	0.30 × 0.20 × 0.20 mm
β = 86.097 (2)°

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	3305 reflections with I > 2σ(I)
7183 measured reflections	R_int = 0.042
4374 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	1 restraint
wR(F²) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.27 e Å⁻³
4374 reflections	Δρ_min = −0.25 e Å⁻³
277 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
Cl1	0.00615 (8)	0.74321 (8)	0.62526 (6)	0.0777 (3)
S1	0.56904 (7)	0.74334 (6)	0.26984 (4)	0.04454 (19)
O1	0.3353 (2)	0.58296 (17)	0.80362 (10)	0.0535 (4)
O2	0.6149 (3)	0.4999 (3)	0.87766 (13)	0.1116 (10)
N1	0.4468 (2)	0.69605 (17)	0.45014 (11)	0.0355 (4)
N2	0.7612 (2)	0.59780 (17)	0.43894 (11)	0.0348 (4)
N3	0.5383 (2)	0.62604 (17)	0.53959 (11)	0.0341 (4)
N4	0.8411 (2)	0.4984 (2)	0.60747 (12)	0.0427 (5)
H4A	0.9574 (16)	0.473 (2)	0.5949 (17)	0.060 (7)*
C1	0.3133 (4)	1.0947 (3)	0.1521 (2)	0.0676 (7)
H1	0.3380	1.1077	0.2081	0.081*
C2	0.2929 (4)	1.2023 (3)	0.0662 (2)	0.0850 (10)
H2	0.3046	1.2865	0.0646	0.102*
C3	0.2559 (4)	1.1840 (4)	−0.0153 (2)	0.0835 (10)
H3	0.2431	1.2559	−0.0732	0.100*
C4	0.2374 (4)	1.0625 (4)	−0.0136 (2)	0.0831 (10)
H4	0.2119	1.0507	−0.0699	0.100*
C5	0.2567 (4)	0.9554 (3)	0.07242 (19)	0.0660 (7)
H5	0.2417	0.8723	0.0737	0.079*
C6	0.2977 (3)	0.9705 (3)	0.15594 (15)	0.0495 (6)
C7	0.3236 (3)	0.8548 (3)	0.24988 (18)	0.0621 (7)
H7A	0.2458	0.7996	0.2495	0.075*
H7B	0.2859	0.8944	0.3009	0.075*
C8	0.5887 (3)	0.6745 (2)	0.39400 (13)	0.0341 (4)
C9	0.7215 (2)	0.5707 (2)	0.52975 (13)	0.0317 (4)
C10	0.7745 (3)	0.4899 (2)	0.69732 (14)	0.0383 (5)
C11	0.9306 (3)	0.4099 (3)	0.77410 (16)	0.0550 (6)
H11A	0.9949	0.4710	0.7783	0.082*
H11B	1.0175	0.3318	0.7585	0.082*
H11C	0.8785	0.3762	0.8342	0.082*
C12	0.5919 (3)	0.5486 (2)	0.70996 (14)	0.0386 (5)
C13	0.4428 (3)	0.6291 (2)	0.62811 (13)	0.0319 (4)
H13	0.3501	0.5818	0.6358	0.038*
C14	0.3429 (3)	0.7812 (2)	0.62213 (13)	0.0350 (4)
C15	0.4487 (3)	0.8657 (2)	0.61846 (16)	0.0492 (6)
H15	0.5789	0.8280	0.6198	0.059*
C16	0.3652 (5)	1.0036 (3)	0.6129 (2)	0.0687 (8)
H16	0.4385	1.0584	0.6110	0.082*
C17	0.1726 (5)	1.0605 (3)	0.6103 (2)	0.0786 (9)
H17	0.1158	1.1537	0.6070	0.094*
C18	0.0637 (4)	0.9802 (3)	0.61266 (19)	0.0689 (8)
H18	−0.0665	1.0193	0.6098	0.083*
C19	0.1489 (3)	0.8412 (2)	0.61929 (16)	0.0466 (5)
C20	0.5222 (3)	0.5380 (3)	0.80635 (16)	0.0561 (7)
C21	0.2431 (4)	0.6005 (3)	0.88953 (18)	0.0694 (8)
H21A	0.3170	0.5283	0.9451	0.083*
H21B	0.1207	0.5906	0.8897	0.083*
C22	0.2210 (4)	0.7414 (4)	0.8942 (2)	0.0875 (10)
H22A	0.3425	0.7480	0.8998	0.131*
H22B	0.1514	0.7547	0.9486	0.131*
H22C	0.1547	0.8126	0.8372	0.131*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0371 (3)	0.0746 (5)	0.1093 (6)	−0.0209 (3)	−0.0024 (3)	−0.0116 (4)
S1	0.0428 (3)	0.0496 (4)	0.0296 (3)	−0.0035 (2)	−0.0003 (2)	−0.0104 (2)
O1	0.0514 (9)	0.0655 (11)	0.0360 (8)	−0.0116 (8)	0.0119 (7)	−0.0175 (8)
O2	0.0598 (12)	0.191 (3)	0.0364 (11)	0.0100 (14)	−0.0070 (9)	−0.0289 (13)
N1	0.0338 (8)	0.0388 (10)	0.0301 (8)	−0.0072 (7)	−0.0019 (6)	−0.0111 (7)
N2	0.0324 (8)	0.0383 (10)	0.0319 (9)	−0.0079 (7)	−0.0003 (6)	−0.0129 (7)
N3	0.0326 (8)	0.0373 (9)	0.0279 (8)	−0.0050 (7)	−0.0007 (6)	−0.0115 (7)
N4	0.0304 (9)	0.0548 (12)	0.0321 (9)	−0.0044 (8)	0.0003 (7)	−0.0108 (8)
C1	0.0695 (17)	0.0662 (18)	0.0560 (16)	−0.0130 (14)	−0.0143 (13)	−0.0132 (14)
C2	0.081 (2)	0.066 (2)	0.081 (2)	−0.0156 (17)	−0.0161 (17)	0.0031 (17)
C3	0.0563 (17)	0.096 (3)	0.0545 (18)	−0.0082 (17)	−0.0071 (13)	0.0148 (18)
C4	0.0726 (19)	0.110 (3)	0.0423 (16)	−0.0028 (19)	−0.0116 (13)	−0.0199 (17)
C5	0.0603 (16)	0.0753 (19)	0.0547 (16)	−0.0098 (14)	−0.0082 (12)	−0.0232 (14)
C6	0.0347 (11)	0.0571 (15)	0.0402 (12)	−0.0010 (10)	−0.0045 (9)	−0.0087 (11)
C7	0.0415 (12)	0.0680 (17)	0.0490 (14)	−0.0026 (12)	−0.0010 (10)	0.0002 (12)
C8	0.0394 (10)	0.0297 (10)	0.0310 (10)	−0.0069 (8)	−0.0003 (8)	−0.0118 (8)
C9	0.0294 (9)	0.0324 (10)	0.0337 (10)	−0.0097 (8)	0.0005 (8)	−0.0120 (8)
C10	0.0410 (11)	0.0388 (12)	0.0308 (10)	−0.0102 (9)	−0.0009 (8)	−0.0087 (9)
C11	0.0398 (12)	0.0708 (17)	0.0410 (13)	−0.0093 (11)	−0.0071 (9)	−0.0094 (12)
C12	0.0404 (11)	0.0395 (12)	0.0312 (10)	−0.0084 (9)	−0.0010 (8)	−0.0104 (9)
C13	0.0311 (9)	0.0358 (11)	0.0295 (10)	−0.0119 (8)	0.0045 (7)	−0.0118 (8)
C14	0.0390 (10)	0.0359 (11)	0.0291 (10)	−0.0116 (9)	0.0036 (8)	−0.0111 (8)
C15	0.0508 (13)	0.0477 (14)	0.0553 (14)	−0.0207 (11)	0.0022 (11)	−0.0205 (11)
C16	0.097 (2)	0.0515 (16)	0.0724 (19)	−0.0353 (16)	0.0013 (16)	−0.0280 (14)
C17	0.114 (3)	0.0395 (15)	0.0695 (19)	−0.0033 (17)	0.0066 (17)	−0.0253 (14)
C18	0.0657 (17)	0.0520 (16)	0.0658 (17)	0.0071 (13)	0.0101 (13)	−0.0194 (14)
C19	0.0425 (12)	0.0437 (13)	0.0452 (12)	−0.0071 (10)	0.0046 (9)	−0.0123 (10)
C20	0.0497 (13)	0.0652 (16)	0.0344 (12)	−0.0010 (11)	0.0008 (10)	−0.0109 (11)
C21	0.0662 (17)	0.090 (2)	0.0438 (14)	−0.0183 (15)	0.0244 (12)	−0.0237 (14)
C22	0.080 (2)	0.109 (3)	0.082 (2)	−0.0193 (19)	0.0220 (17)	−0.058 (2)

Geometric parameters (Å, º) top

Cl1—C19	1.729 (2)	C10—C11	1.512 (3)
N1—C8	1.322 (2)	C11—H11A	0.9600
N1—N3	1.387 (2)	C11—H11B	0.9600
N2—C9	1.321 (2)	C11—H11C	0.9600
N2—C8	1.362 (2)	C12—C20	1.477 (3)
N3—C9	1.332 (2)	C12—C13	1.528 (3)
N3—C13	1.464 (2)	C13—C14	1.521 (3)
N4—C9	1.353 (2)	C13—H13	0.9800
N4—C10	1.382 (2)	C14—C19	1.388 (3)
N4—H4A	0.857 (10)	C14—C15	1.388 (3)
C1—C6	1.360 (4)	C15—C16	1.373 (3)
C1—C2	1.385 (4)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.376 (4)
C2—C3	1.354 (4)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.374 (4)
C3—C4	1.350 (4)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.381 (3)
C4—C5	1.384 (4)	C18—H18	0.9300
C4—H4	0.9300	C20—O2	1.186 (3)
C5—C6	1.375 (3)	C20—O1	1.331 (3)
C5—H5	0.9300	C21—O1	1.452 (3)
C6—C7	1.502 (3)	C21—C22	1.488 (4)
C7—S1	1.818 (2)	C21—H21A	0.9700
C7—H7A	0.9700	C21—H21B	0.9700
C7—H7B	0.9700	C22—H22A	0.9600
C8—S1	1.744 (2)	C22—H22B	0.9600
C10—C12	1.341 (3)	C22—H22C	0.9600

C8—N1—N3	101.27 (15)	H11B—C11—H11C	109.5
C9—N2—C8	102.11 (15)	C10—C12—C20	121.06 (19)
C9—N3—N1	109.35 (15)	C10—C12—C13	123.50 (18)
C9—N3—C13	127.46 (15)	C20—C12—C13	115.45 (17)
N1—N3—C13	122.90 (14)	N3—C13—C14	108.91 (15)
C9—N4—C10	119.78 (17)	N3—C13—C12	107.18 (15)
C9—N4—H4A	114.4 (16)	C14—C13—C12	113.01 (16)
C10—N4—H4A	125.0 (16)	N3—C13—H13	109.2
C6—C1—C2	121.1 (3)	C14—C13—H13	109.2
C6—C1—H1	119.4	C12—C13—H13	109.2
C2—C1—H1	119.4	C19—C14—C15	117.7 (2)
C3—C2—C1	119.5 (3)	C19—C14—C13	123.08 (19)
C3—C2—H2	120.2	C15—C14—C13	119.19 (18)
C1—C2—H2	120.2	C16—C15—C14	121.4 (2)
C4—C3—C2	120.6 (3)	C16—C15—H15	119.3
C4—C3—H3	119.7	C14—C15—H15	119.3
C2—C3—H3	119.7	C15—C16—C17	119.7 (3)
C3—C4—C5	119.8 (3)	C15—C16—H16	120.2
C3—C4—H4	120.1	C17—C16—H16	120.2
C5—C4—H4	120.1	C18—C17—C16	120.4 (2)
C6—C5—C4	120.6 (3)	C18—C17—H17	119.8
C6—C5—H5	119.7	C16—C17—H17	119.8
C4—C5—H5	119.7	C17—C18—C19	119.5 (3)
C1—C6—C5	118.3 (2)	C17—C18—H18	120.2
C1—C6—C7	120.0 (2)	C19—C18—H18	120.2
C5—C6—C7	121.7 (3)	C18—C19—C14	121.2 (2)
C6—C7—S1	109.29 (16)	C18—C19—Cl1	117.8 (2)
C6—C7—H7A	109.8	C14—C19—Cl1	120.93 (17)
S1—C7—H7A	109.8	O2—C20—O1	122.7 (2)
C6—C7—H7B	109.8	O2—C20—C12	126.4 (2)
S1—C7—H7B	109.8	O1—C20—C12	110.83 (19)
H7A—C7—H7B	108.3	O1—C21—C22	110.2 (2)
N1—C8—N2	115.88 (17)	O1—C21—H21A	109.6
N1—C8—S1	124.52 (15)	C22—C21—H21A	109.6
N2—C8—S1	119.54 (14)	O1—C21—H21B	109.6
N2—C9—N3	111.39 (16)	C22—C21—H21B	109.6
N2—C9—N4	128.22 (17)	H21A—C21—H21B	108.1
N3—C9—N4	120.38 (17)	C21—C22—H22A	109.5
C12—C10—N4	121.53 (18)	C21—C22—H22B	109.5
C12—C10—C11	126.76 (19)	H22A—C22—H22B	109.5
N4—C10—C11	111.71 (18)	C21—C22—H22C	109.5
C10—C11—H11A	109.5	H22A—C22—H22C	109.5
C10—C11—H11B	109.5	H22B—C22—H22C	109.5
H11A—C11—H11B	109.5	C20—O1—C21	117.94 (19)
C10—C11—H11C	109.5	C8—S1—C7	101.13 (10)
H11A—C11—H11C	109.5

C8—N1—N3—C9	0.3 (2)	C9—N3—C13—C12	−3.3 (3)
C8—N1—N3—C13	174.42 (17)	N1—N3—C13—C12	−176.31 (16)
C6—C1—C2—C3	0.3 (5)	C10—C12—C13—N3	0.6 (3)
C1—C2—C3—C4	0.5 (5)	C20—C12—C13—N3	−179.11 (18)
C2—C3—C4—C5	−0.1 (5)	C10—C12—C13—C14	−119.4 (2)
C3—C4—C5—C6	−1.1 (4)	C20—C12—C13—C14	60.9 (2)
C2—C1—C6—C5	−1.5 (4)	N3—C13—C14—C19	113.7 (2)
C2—C1—C6—C7	179.0 (2)	C12—C13—C14—C19	−127.3 (2)
C4—C5—C6—C1	1.9 (4)	N3—C13—C14—C15	−65.7 (2)
C4—C5—C6—C7	−178.6 (2)	C12—C13—C14—C15	53.3 (2)
C1—C6—C7—S1	−91.0 (3)	C19—C14—C15—C16	0.5 (3)
C5—C6—C7—S1	89.5 (3)	C13—C14—C15—C16	179.9 (2)
N3—N1—C8—N2	−0.1 (2)	C14—C15—C16—C17	−0.4 (4)
N3—N1—C8—S1	−177.04 (14)	C15—C16—C17—C18	−0.4 (4)
C9—N2—C8—N1	−0.2 (2)	C16—C17—C18—C19	1.1 (4)
C9—N2—C8—S1	176.97 (14)	C17—C18—C19—C14	−1.0 (4)
C8—N2—C9—N3	0.3 (2)	C17—C18—C19—Cl1	178.3 (2)
C8—N2—C9—N4	−179.2 (2)	C15—C14—C19—C18	0.3 (3)
N1—N3—C9—N2	−0.4 (2)	C13—C14—C19—C18	−179.2 (2)
C13—N3—C9—N2	−174.21 (17)	C15—C14—C19—Cl1	−179.04 (16)
N1—N3—C9—N4	179.18 (18)	C13—C14—C19—Cl1	1.5 (3)
C13—N3—C9—N4	5.4 (3)	C10—C12—C20—O2	12.7 (4)
C10—N4—C9—N2	175.17 (19)	C13—C12—C20—O2	−167.6 (3)
C10—N4—C9—N3	−4.3 (3)	C10—C12—C20—O1	−169.8 (2)
C9—N4—C10—C12	1.9 (3)	C13—C12—C20—O1	9.9 (3)
C9—N4—C10—C11	−177.66 (19)	O2—C20—O1—C21	7.1 (4)
N4—C10—C12—C20	179.6 (2)	C12—C20—O1—C21	−170.5 (2)
C11—C10—C12—C20	−1.0 (4)	C22—C21—O1—C20	85.4 (3)
N4—C10—C12—C13	−0.1 (3)	N1—C8—S1—C7	5.3 (2)
C11—C10—C12—C13	179.4 (2)	N2—C8—S1—C7	−171.56 (17)
C9—N3—C13—C14	119.3 (2)	C6—C7—S1—C8	154.37 (19)
N1—N3—C13—C14	−53.7 (2)

Experimental details

Crystal data
Chemical formula	C₂₂H₂₁ClN₄O₂S
M_r	440.94
Crystal system, space group	Triclinic, P1
Temperature (K)	292
a, b, c (Å)	7.5884 (9), 10.7303 (12), 14.8825 (16)
α, β, γ (°)	70.655 (2), 86.097 (2), 70.032 (2)
V (Å³)	1073.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART 4K CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7183, 4374, 3305
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.143, 1.07
No. of reflections	4374
No. of parameters	277
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25

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

Acknowledgements

This work was supported by NNSFC grants (Nos. 20572030, 20432010 and 20528201), the Cultivation Fund of the Key Scientific and Technical Innovation Project, Ministry of Education of China (grant No. 705039), and the Programme for Excellent Research Groups of Hubei Province (grant No. 2004ABC002).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Bruker (2001). SHELXTL (Version 6.12), SMART (Version 5.628) and SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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