N′2,N′5-Bis[(E)-2-hy­droxy­benzyl­idene]-3,4-dimethyl­thio­phene-2,5-dicarbohydrazide

Zhang, S.-L.; Zhang, L.; Wen, Q.-M.; Geng, R.-X.; Zhou, C.-H.

doi:10.1107/S1600536812020260

organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1752

doi:10.1107/S1600536812020260

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N′²,N′⁵-Bis[(E)-2-hydroxybenzylidene]-3,4-dimethylthiophene-2,5-dicarbohydrazide

Shao-Lin Zhang,^a Ling Zhang,^a Qin-Mei Wen,^a Rong-Xia Geng ^a ^* and Cheng-He Zhou ^a ^*

^aLaboratory of Bioorganic & Medicinal Chemistry, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China
^*Correspondence e-mail: geng0712@swu.edu.cn, zhouch@swu.edu.cn

(Received 23 April 2012; accepted 5 May 2012; online 16 May 2012)

In the title molecule, C₂₂H₂₀N₄O₄S, both C=N bonds are in an E conformation. The benzene rings form dihedral angles of 12.10 (13) and 25.17 (12)° with the thiophene ring. The dihedral angle between the two benzene rings is 17.59 (14)°. There are two intramolecular O—H⋯N hydrogen bonds. In the crystal, N—H⋯O hydrogen bonds connect molecules into chains along [010].

Related literature

For the medicinal properties of thiophene derivatives, see: Bondock et al. (2010 ); Geng & Zhou (2008 ). For a related structure, see: Tang et al. (2010 ).

Experimental

Crystal data

C₂₂H₂₀N₄O₄S
M_r = 436.48
Triclinic, $[P \overline 1]$
a = 8.392 (8) Å
b = 9.511 (9) Å
c = 12.937 (8) Å
α = 99.853 (17)°
β = 90.804 (18)°
γ = 92.374 (18)°
V = 1016.2 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 296 K
0.19 × 0.18 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.963, T_max = 0.969
5573 measured reflections
3925 independent reflections
2660 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.128
S = 1.02
3925 reflections
283 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.91	2.626 (4)	145
N2—H2⋯O3ⁱ	0.86	1.97	2.789 (4)	159
N4—H4⋯O2ⁱⁱ	0.86	1.97	2.812 (4)	165
O4—H4B⋯N3	0.82	1.85	2.569 (4)	146
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812020260/lh5463sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020260/lh5463Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020260/lh5463Isup3.cml

checkCIF report

Comment top

Thiophene is a electron-rich five-membered aromatic heterocycle containing a sulfur atom whose derivatives display various biological activities. Much effort has been devoted to the researches of thiophene-based compounds as medicinal agents (Geng et al., 2008; Bondock et al., 2010). Our interest is to develop novel thiophene compounds with high bioactivities especially broad antimicrobial spectrum. We have already prepared a thiophene compound incorporating Schiff base moieties and determined its crystal structure (Tang et al., 2010). Herein, the crystal structure of title compound (I) is reported.

The molecular structure of (I) is shown in Fig. 1. Both C═N bonds are in an E conformation. The benzene rings form dihedral angles of 12.10 (13)° (C17-C22) and 25.17 (12) ° (C1-C6) with the thiophene ring (S1/C9/C10/C12/C14). The dihedral angle between the two benzene rings is 17.59 (14)°. There are two intramolecular O—H···N hydrogen bonds. In the crystal, N—H···O hydrogen bonds connect molecules into chains along [010].

Related literature top

For the medicinal properties of thiophene derivatives, see: Bondock et al. (2010); Geng & Zhou (2008). For a related structure, see: Tang et al. (2010).

Experimental top

A mixture of 3,4-dimethylthiophene-2,5-dicarbohydrazide (0.11 g, 0.5 mmol) and 2-hydroxybenzaldehyde (0.24 g, 2 mmol) in methanol (10.0 ml) was stirred at room temperature. Upon the completion of the reaction (monitored by TLC, eluent, ethyl acetate), the formed precipitate was filtered and then washed with cold methanol to afford a yellow solid of the title compound (0.35 g). A crystal suitable for X-ray analysis was grown from a mixed solution of (I) in chloroform and methanol by slow evaporation at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing the displacement ellipsoids drawn at the 50% probability level.

N'²,N'⁵-Bis[(E)-2-hydroxybenzylidene]- 3,4-dimethylthiophene-2,5-dicarbohydrazide top

Crystal data top

C₂₂H₂₀N₄O₄S	Z = 2
M_r = 436.48	F(000) = 456
Triclinic, P1	D_x = 1.426 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.392 (8) Å	Cell parameters from 1480 reflections
b = 9.511 (9) Å	θ = 2.9–24.4°
c = 12.937 (8) Å	µ = 0.20 mm⁻¹
α = 99.853 (17)°	T = 296 K
β = 90.804 (18)°	Block, yellow
γ = 92.374 (18)°	0.19 × 0.18 × 0.16 mm
V = 1016.2 (15) Å³

Data collection top

Bruker APEXII CCD diffractometer	3925 independent reflections
Radiation source: fine-focus sealed tube	2660 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→10
T_min = 0.963, T_max = 0.969	k = −11→10
5573 measured reflections	l = −15→15

Refinement top

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)] = 0.047	H-atom parameters constrained
wR(F²) = 0.128	w = 1/[σ²(F_o²) + (0.0604P)² + 0.0881P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3925 reflections	Δρ_max = 0.23 e Å⁻³
283 parameters	Δρ_min = −0.30 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0062 (17)

Crystal data top

C₂₂H₂₀N₄O₄S	γ = 92.374 (18)°
M_r = 436.48	V = 1016.2 (15) Å³
Triclinic, P1	Z = 2
a = 8.392 (8) Å	Mo Kα radiation
b = 9.511 (9) Å	µ = 0.20 mm⁻¹
c = 12.937 (8) Å	T = 296 K
α = 99.853 (17)°	0.19 × 0.18 × 0.16 mm
β = 90.804 (18)°

Data collection top

Bruker APEXII CCD diffractometer	3925 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2660 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.969	R_int = 0.019
5573 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.02	Δρ_max = 0.23 e Å⁻³
3925 reflections	Δρ_min = −0.30 e Å⁻³
283 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
N1	0.9005 (2)	0.2862 (2)	0.73465 (15)	0.0457 (5)
N2	0.8176 (2)	0.32288 (19)	0.65213 (15)	0.0463 (6)
H2	0.8112	0.4109	0.6455	0.056*
N3	0.0145 (2)	0.15155 (19)	0.30284 (15)	0.0423 (5)
N4	0.1633 (2)	0.16130 (19)	0.34807 (16)	0.0448 (5)
H4	0.1990	0.0926	0.3759	0.054*
C1	1.0429 (3)	0.2314 (3)	0.92331 (19)	0.0473 (6)
C2	1.1287 (4)	0.2087 (3)	1.0091 (2)	0.0631 (8)
H2A	1.1110	0.1251	1.0363	0.076*
C3	1.2397 (4)	0.3085 (4)	1.0542 (2)	0.0702 (9)
H3A	1.2992	0.2919	1.1118	0.084*
C4	1.2661 (4)	0.4336 (4)	1.0168 (2)	0.0658 (8)
H4A	1.3424	0.5014	1.0488	0.079*
C5	1.1795 (3)	0.4575 (3)	0.9320 (2)	0.0524 (7)
H5A	1.1958	0.5429	0.9071	0.063*
C6	1.0681 (3)	0.3567 (3)	0.88285 (18)	0.0424 (6)
C7	0.9818 (3)	0.3853 (3)	0.79290 (18)	0.0432 (6)
H7A	0.9854	0.4772	0.7771	0.052*
C8	0.7473 (3)	0.2195 (2)	0.5826 (2)	0.0438 (6)
C9	0.6441 (3)	0.2671 (2)	0.50316 (18)	0.0392 (6)
C10	0.6698 (3)	0.3655 (2)	0.44024 (17)	0.0365 (5)
C11	0.8216 (3)	0.4475 (3)	0.4339 (2)	0.0482 (6)
H11A	0.8974	0.4238	0.4837	0.072*
H11B	0.8035	0.5479	0.4493	0.072*
H11C	0.8626	0.4242	0.3644	0.072*
C12	0.5355 (3)	0.3773 (2)	0.37593 (16)	0.0348 (5)
C13	0.5400 (3)	0.4737 (3)	0.29632 (19)	0.0482 (6)
H13A	0.4382	0.4681	0.2607	0.072*
H13B	0.6210	0.4448	0.2464	0.072*
H13C	0.5636	0.5702	0.3306	0.072*
C14	0.4126 (3)	0.2878 (2)	0.39320 (17)	0.0356 (5)
C15	0.2514 (3)	0.2808 (2)	0.34768 (17)	0.0364 (5)
C16	−0.0755 (3)	0.0451 (2)	0.31184 (19)	0.0454 (6)
H16A	−0.0433	−0.0200	0.3532	0.055*
C17	−0.2275 (3)	0.0243 (3)	0.25834 (19)	0.0452 (6)
C18	−0.2791 (3)	0.1158 (3)	0.1937 (2)	0.0490 (7)
C19	−0.4226 (4)	0.0886 (4)	0.1412 (2)	0.0686 (9)
H19A	−0.4569	0.1500	0.0975	0.082*
C20	−0.5150 (4)	−0.0277 (4)	0.1529 (3)	0.0798 (11)
H20A	−0.6133	−0.0446	0.1179	0.096*
C21	−0.4657 (4)	−0.1201 (4)	0.2151 (3)	0.0795 (10)
H21A	−0.5291	−0.2005	0.2218	0.095*
C22	−0.3236 (4)	−0.0936 (3)	0.2669 (2)	0.0639 (8)
H22A	−0.2900	−0.1568	0.3094	0.077*
O1	0.9338 (3)	0.13019 (19)	0.88189 (15)	0.0640 (6)
H1	0.8908	0.1536	0.8305	0.096*
O2	0.7611 (2)	0.09444 (16)	0.58491 (16)	0.0683 (6)
O3	0.1986 (2)	0.38046 (15)	0.31228 (12)	0.0443 (4)
O4	−0.1926 (2)	0.2321 (2)	0.17967 (17)	0.0681 (6)
H4B	−0.1073	0.2355	0.2119	0.102*
S1	0.46125 (8)	0.18434 (6)	0.48365 (5)	0.0450 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0422 (13)	0.0467 (11)	0.0497 (12)	0.0023 (10)	−0.0194 (10)	0.0140 (9)
N2	0.0483 (13)	0.0348 (10)	0.0563 (13)	−0.0007 (9)	−0.0264 (11)	0.0116 (9)
N3	0.0329 (11)	0.0371 (10)	0.0555 (13)	0.0001 (9)	−0.0143 (10)	0.0054 (9)
N4	0.0351 (12)	0.0350 (10)	0.0654 (14)	−0.0012 (9)	−0.0191 (10)	0.0139 (9)
C1	0.0444 (16)	0.0562 (15)	0.0425 (14)	0.0076 (13)	−0.0018 (12)	0.0105 (12)
C2	0.068 (2)	0.0745 (19)	0.0507 (17)	0.0153 (17)	−0.0077 (15)	0.0200 (15)
C3	0.066 (2)	0.100 (2)	0.0455 (17)	0.022 (2)	−0.0139 (15)	0.0112 (17)
C4	0.0513 (18)	0.090 (2)	0.0512 (17)	0.0001 (17)	−0.0179 (14)	−0.0003 (16)
C5	0.0446 (16)	0.0620 (16)	0.0495 (15)	−0.0029 (13)	−0.0072 (13)	0.0081 (13)
C6	0.0372 (14)	0.0525 (14)	0.0378 (13)	0.0056 (12)	−0.0054 (11)	0.0087 (11)
C7	0.0417 (15)	0.0443 (13)	0.0445 (14)	0.0030 (12)	−0.0087 (12)	0.0103 (11)
C8	0.0358 (14)	0.0387 (12)	0.0574 (15)	−0.0030 (11)	−0.0172 (12)	0.0126 (11)
C9	0.0329 (13)	0.0339 (11)	0.0493 (14)	−0.0015 (10)	−0.0148 (11)	0.0053 (10)
C10	0.0332 (13)	0.0350 (11)	0.0390 (13)	0.0008 (10)	−0.0045 (10)	0.0007 (10)
C11	0.0361 (14)	0.0584 (15)	0.0488 (15)	−0.0058 (12)	−0.0059 (12)	0.0083 (12)
C12	0.0338 (13)	0.0354 (11)	0.0338 (12)	0.0009 (10)	−0.0044 (10)	0.0031 (9)
C13	0.0444 (15)	0.0530 (14)	0.0494 (15)	−0.0021 (12)	−0.0073 (12)	0.0169 (12)
C14	0.0347 (13)	0.0327 (11)	0.0390 (13)	0.0016 (10)	−0.0090 (10)	0.0057 (9)
C15	0.0369 (13)	0.0328 (11)	0.0380 (12)	0.0016 (10)	−0.0082 (10)	0.0028 (10)
C16	0.0406 (15)	0.0412 (13)	0.0547 (15)	−0.0008 (12)	−0.0119 (12)	0.0107 (11)
C17	0.0340 (14)	0.0495 (14)	0.0494 (15)	−0.0022 (12)	−0.0052 (12)	0.0028 (12)
C18	0.0382 (15)	0.0529 (15)	0.0542 (16)	0.0047 (13)	−0.0055 (12)	0.0039 (12)
C19	0.0429 (18)	0.091 (2)	0.069 (2)	0.0100 (18)	−0.0190 (15)	0.0056 (17)
C20	0.0352 (17)	0.114 (3)	0.079 (2)	−0.0092 (19)	−0.0133 (16)	−0.011 (2)
C21	0.050 (2)	0.096 (2)	0.086 (2)	−0.0327 (18)	−0.0060 (18)	0.008 (2)
C22	0.0540 (19)	0.0697 (18)	0.0668 (19)	−0.0183 (15)	−0.0059 (15)	0.0136 (15)
O1	0.0706 (15)	0.0566 (11)	0.0683 (14)	−0.0086 (11)	−0.0167 (11)	0.0253 (10)
O2	0.0728 (15)	0.0334 (9)	0.0996 (15)	−0.0046 (9)	−0.0467 (12)	0.0197 (9)
O3	0.0427 (10)	0.0366 (8)	0.0548 (10)	0.0001 (8)	−0.0179 (8)	0.0135 (7)
O4	0.0557 (13)	0.0601 (11)	0.0935 (16)	0.0018 (10)	−0.0228 (11)	0.0293 (11)
S1	0.0398 (4)	0.0391 (3)	0.0577 (4)	−0.0084 (3)	−0.0212 (3)	0.0167 (3)

Geometric parameters (Å, º) top

N1—C7	1.270 (3)	C11—H11A	0.9600
N1—N2	1.368 (3)	C11—H11B	0.9600
N2—C8	1.326 (3)	C11—H11C	0.9600
N2—H2	0.8600	C12—C14	1.355 (3)
N3—C16	1.261 (3)	C12—C13	1.491 (3)
N3—N4	1.365 (3)	C13—H13A	0.9600
N4—C15	1.331 (3)	C13—H13B	0.9600
N4—H4	0.8600	C13—H13C	0.9600
C1—O1	1.337 (3)	C14—C15	1.462 (3)
C1—C2	1.368 (3)	C14—S1	1.708 (2)
C1—C6	1.391 (4)	C15—O3	1.217 (3)
C2—C3	1.354 (4)	C16—C17	1.432 (3)
C2—H2A	0.9300	C16—H16A	0.9300
C3—C4	1.370 (4)	C17—C22	1.375 (4)
C3—H3A	0.9300	C17—C18	1.384 (4)
C4—C5	1.364 (4)	C18—O4	1.338 (3)
C4—H4A	0.9300	C18—C19	1.367 (4)
C5—C6	1.377 (3)	C19—C20	1.355 (5)
C5—H5A	0.9300	C19—H19A	0.9300
C6—C7	1.433 (3)	C20—C21	1.361 (5)
C7—H7A	0.9300	C20—H20A	0.9300
C8—O2	1.205 (3)	C21—C22	1.354 (4)
C8—C9	1.476 (3)	C21—H21A	0.9300
C9—C10	1.355 (3)	C22—H22A	0.9300
C9—S1	1.690 (3)	O1—H1	0.8200
C10—C12	1.411 (3)	O4—H4B	0.8200
C10—C11	1.477 (4)

C7—N1—N2	117.0 (2)	H11A—C11—H11C	109.5
C8—N2—N1	118.42 (19)	H11B—C11—H11C	109.5
C8—N2—H2	120.8	C14—C12—C10	111.9 (2)
N1—N2—H2	120.8	C14—C12—C13	126.7 (2)
C16—N3—N4	118.1 (2)	C10—C12—C13	121.3 (2)
C15—N4—N3	117.69 (19)	C12—C13—H13A	109.5
C15—N4—H4	121.2	C12—C13—H13B	109.5
N3—N4—H4	121.2	H13A—C13—H13B	109.5
O1—C1—C2	117.5 (3)	C12—C13—H13C	109.5
O1—C1—C6	122.1 (2)	H13A—C13—H13C	109.5
C2—C1—C6	120.4 (3)	H13B—C13—H13C	109.5
C3—C2—C1	119.6 (3)	C12—C14—C15	126.6 (2)
C3—C2—H2A	120.2	C12—C14—S1	112.18 (17)
C1—C2—H2A	120.2	C15—C14—S1	121.11 (18)
C2—C3—C4	121.3 (3)	O3—C15—N4	121.2 (2)
C2—C3—H3A	119.4	O3—C15—C14	121.7 (2)
C4—C3—H3A	119.4	N4—C15—C14	117.08 (19)
C5—C4—C3	119.3 (3)	N3—C16—C17	119.9 (2)
C5—C4—H4A	120.3	N3—C16—H16A	120.0
C3—C4—H4A	120.3	C17—C16—H16A	120.0
C4—C5—C6	120.9 (3)	C22—C17—C18	118.1 (3)
C4—C5—H5A	119.6	C22—C17—C16	119.6 (2)
C6—C5—H5A	119.6	C18—C17—C16	122.3 (2)
C5—C6—C1	118.5 (2)	O4—C18—C19	117.7 (3)
C5—C6—C7	119.0 (2)	O4—C18—C17	122.2 (2)
C1—C6—C7	122.6 (2)	C19—C18—C17	120.1 (3)
N1—C7—C6	120.5 (2)	C20—C19—C18	120.0 (3)
N1—C7—H7A	119.8	C20—C19—H19A	120.0
C6—C7—H7A	119.8	C18—C19—H19A	120.0
O2—C8—N2	123.2 (2)	C19—C20—C21	120.9 (3)
O2—C8—C9	121.3 (2)	C19—C20—H20A	119.6
N2—C8—C9	115.5 (2)	C21—C20—H20A	119.6
C10—C9—C8	131.5 (2)	C22—C21—C20	119.2 (3)
C10—C9—S1	112.63 (17)	C22—C21—H21A	120.4
C8—C9—S1	115.89 (19)	C20—C21—H21A	120.4
C9—C10—C12	112.1 (2)	C21—C22—C17	121.6 (3)
C9—C10—C11	125.2 (2)	C21—C22—H22A	119.2
C12—C10—C11	122.6 (2)	C17—C22—H22A	119.2
C10—C11—H11A	109.5	C1—O1—H1	109.5
C10—C11—H11B	109.5	C18—O4—H4B	109.5
H11A—C11—H11B	109.5	C9—S1—C14	91.09 (12)
C10—C11—H11C	109.5

C7—N1—N2—C8	172.0 (2)	C11—C10—C12—C13	0.5 (3)
C16—N3—N4—C15	−173.2 (2)	C10—C12—C14—C15	174.1 (2)
O1—C1—C2—C3	−179.5 (3)	C13—C12—C14—C15	−9.0 (4)
C6—C1—C2—C3	−0.5 (4)	C10—C12—C14—S1	−2.3 (2)
C1—C2—C3—C4	1.1 (5)	C13—C12—C14—S1	174.64 (18)
C2—C3—C4—C5	−0.4 (5)	N3—N4—C15—O3	3.1 (3)
C3—C4—C5—C6	−1.1 (4)	N3—N4—C15—C14	−178.0 (2)
C4—C5—C6—C1	1.6 (4)	C12—C14—C15—O3	−20.8 (4)
C4—C5—C6—C7	−178.9 (2)	S1—C14—C15—O3	155.27 (18)
O1—C1—C6—C5	178.1 (2)	C12—C14—C15—N4	160.2 (2)
C2—C1—C6—C5	−0.9 (4)	S1—C14—C15—N4	−23.7 (3)
O1—C1—C6—C7	−1.3 (4)	N4—N3—C16—C17	−174.8 (2)
C2—C1—C6—C7	179.7 (2)	N3—C16—C17—C22	178.7 (2)
N2—N1—C7—C6	178.1 (2)	N3—C16—C17—C18	1.8 (4)
C5—C6—C7—N1	167.1 (2)	C22—C17—C18—O4	−179.2 (3)
C1—C6—C7—N1	−13.4 (4)	C16—C17—C18—O4	−2.2 (4)
N1—N2—C8—O2	−4.8 (4)	C22—C17—C18—C19	0.6 (4)
N1—N2—C8—C9	172.8 (2)	C16—C17—C18—C19	177.6 (2)
O2—C8—C9—C10	−133.2 (3)	O4—C18—C19—C20	−179.9 (3)
N2—C8—C9—C10	49.2 (4)	C17—C18—C19—C20	0.3 (4)
O2—C8—C9—S1	45.7 (3)	C18—C19—C20—C21	−1.1 (5)
N2—C8—C9—S1	−132.0 (2)	C19—C20—C21—C22	1.0 (5)
C8—C9—C10—C12	−179.5 (2)	C20—C21—C22—C17	0.0 (5)
S1—C9—C10—C12	1.6 (2)	C18—C17—C22—C21	−0.8 (4)
C8—C9—C10—C11	3.4 (4)	C16—C17—C22—C21	−177.8 (3)
S1—C9—C10—C11	−175.46 (18)	C10—C9—S1—C14	−2.47 (18)
C9—C10—C12—C14	0.4 (3)	C8—C9—S1—C14	178.49 (18)
C11—C10—C12—C14	177.6 (2)	C12—C14—S1—C9	2.72 (17)
C9—C10—C12—C13	−176.7 (2)	C15—C14—S1—C9	−173.90 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.91	2.626 (4)	145
N2—H2···O3ⁱ	0.86	1.97	2.789 (4)	159
N4—H4···O2ⁱⁱ	0.86	1.97	2.812 (4)	165
O4—H4B···N3	0.82	1.85	2.569 (4)	146

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₀N₄O₄S
M_r	436.48
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.392 (8), 9.511 (9), 12.937 (8)
α, β, γ (°)	99.853 (17), 90.804 (18), 92.374 (18)
V (Å³)	1016.2 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.19 × 0.18 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.963, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	5573, 3925, 2660
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.128, 1.02
No. of reflections	3925
No. of parameters	283
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.30

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.91	2.626 (4)	145
N2—H2···O3ⁱ	0.86	1.97	2.789 (4)	159
N4—H4···O2ⁱⁱ	0.86	1.97	2.812 (4)	165
O4—H4B···N3	0.82	1.85	2.569 (4)	146

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

Acknowledgements

This work was partially supported by the National Natural Science Foundation of China (No. 21172181), the Key Program of the Natural Science Foundation of Chongqing (CSTC2012jjB10026), the Specialized Research Fund for the Doctoral Program of Higher Education of China (SRFDP 20110182110007) and the Research Funds for the Central Universities (XDJK2011D007, XDJK2012B026).

References

Bondock, S., Metwally, M. A. & Fadaly, W. (2010). Eur. J. Med. Chem. 45, 3692–3701. Web of Science CrossRef CAS PubMed Google Scholar
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Geng, R.-X. & Zhou, C.-H. (2008). Chin. J. Org. Chem. 24, 163–168. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tang, Y.-D., Geng, R.-X. & Zhou, C.-H. (2010). Acta Cryst. E66, o100. Web of Science CSD CrossRef IUCr Journals Google Scholar

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