Bis(2-amino-6-methyl-1,3-benzothia­zole-κN3)bis­(4-nitro­benzoato-κO1)zinc

Sun, X.-T.; Wang, X.-G.; Zhao, X.-J.

doi:10.1107/S1600536811022331

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m933

doi:10.1107/S1600536811022331

Open

access

Bis(2-amino-6-methyl-1,3-benzothiazole-κN³)bis(4-nitrobenzoato-κO¹)zinc

Xue-Tong Sun,^a Xiu-Guang Wang ^a and Xiao-Jun Zhao ^a ^*

^aCollege of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, Tianjin Normal University, Tianjin 300387, People's Republic of China
^*Correspondence e-mail: xiaojun_zhao15@yahoo.com.cn

(Received 26 May 2011; accepted 9 June 2011; online 18 June 2011)

In the title mononuclear complex, [Zn(C₇H₄NO₄)₂(C₈H₈N₂S)₂], the Zn^II atom is coordinated by two N atoms from two 2-amino-6-methyl-1,3-benzothiazole and by two carboxylate O atoms from two 4-nitrobenzoate ligands, adopting a slightly distorted tetrahedral coordination geometry. In the crystal, intermolecular N—H⋯O hydrogen bonds between the amino group of 2-amino-6-methyl-1,3-benzothiazole and the carboxylate group of 4-nitrobenzoate link these discrete mononuclear units into a one-dimensional supramolecular chain extending parallel to [100].

Related literature

For the properties of metal complexes with aminobenzothiazole and its derivatives, see: Sun & Cui (2008 ); Chen et al. (2008 ); Kovalska et al. (2006 ); Batista et al. (2007 ); Marconato et al. (1998 ).

Experimental

Crystal data

[Zn(C₇H₄NO₄)₂(C₈H₈N₂S)₂]
M_r = 726.04
Monoclinic, P 2₁ /c
a = 13.2240 (8) Å
b = 10.7369 (7) Å
c = 21.8863 (13) Å
β = 96.099 (1)°
V = 3089.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.99 mm⁻¹
T = 296 K
0.05 × 0.04 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.952, T_max = 0.971
15119 measured reflections
5418 independent reflections
4724 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.101
S = 1.05
5418 reflections
426 parameters
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O6	1.9489 (18)
Zn1—O1	1.9717 (18)
Zn1—N3	2.036 (2)
Zn1—N1	2.054 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	2.27	3.008 (3)	144
N2—H2B⋯O5ⁱ	0.86	2.05	2.845 (3)	153
N4—H4A⋯O6	0.86	2.20	2.971 (3)	149
N4—H4B⋯O2ⁱⁱ	0.86	2.05	2.860 (3)	156
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y, -z+1.

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001 ); 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) and DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811022331/go2014sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022331/go2014Isup2.hkl

checkCIF report

Comment top

Organic compounds containing benzothiazole and their metal complexes are of optical, biological, and pharmaceutical importance used extensively as electroluminescent device, fluorescent probes for DNA and corrosion inhibitors (Kovalska et al. 2006; Batista et al. 2007; Marconato et al. 1998). As our continuing investigation on the coordination behavior of the benzothiazole ligand (Chen et al. 2008), herein, we report the structure of a mononuclear complex, I.

The molecular structure of the title mononuclear complex is shown in Fig.1 and selected bond lengths and angles are listed in Table 1. The Zn^II atom in the mononuclear stucture of I exhibits a slightly distorted tetrahedral coordination geometry involving two thiazole N atoms from two different 2-amino-6-methyl-1,3-benzothiazole ligands and two monodentate carboxylate O atoms from two separate 4-nitrobenzolate anions. Both ligands act as typically terminal ligands to coordinate to Zn^II ion in monodentate mode with the intramolecular N—H···O hydrogen bonds between amino group of neutral 2-amino-6-methyl-1,3-benzothiazole and anionic 4-nitrobenzolate ligand stabilized the molecular structure.

In the crystal structure, intermolecular N—H···O hydrogen bonds between amino group of neutral 2-amino-6-methyl-1,3-benzothiazole and anionic 4-nitrobenzolate ligands link the discrete mononuclear entities into a one-dimensional supramolecular chain (Fig.2 and Table 2).

Related literature top

For the properties of metal complexes with aminobenzothiazole and its derivatives, see: Sun & Cui (2008); Chen et al. (2008); Kovalska et al. (2006); Batista et al. (2007); Marconato et al. (1998).

Experimental top

To an ethanol solution (6.0 ml) containing 2-amino-6-methyl-1,3-benzothiazole (32.8 mg, 0.2 mmol) and 4-nitrobenzoic acid (33.4 mg, 0.2 mmol) was dropwise added an aqueous solution (4.0 ml) of ZnCl₂ (13.6 mg, 0.1 mmol) with constant stirring. The reaction was stirred at room temperature for about 20 min and the precipitate was filtered off, leaving the filtrate to evaporate at room temperature. Yellow block-shaped crystals were obtained with five days. Yield: 50% based on Zn^II salt. Anal. Calcd. for C₃₀H₂₄N₆O₈S₂Zn: C, 49.63; H, 3.33; N, 11.57%. Found: C, 49.60; H, 3.31; N, 11.61%.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate hydrogen bonds.
	Fig. 2. Part of the one-dimensional chain of (I) formed by N—H···O hydrogen bonds interactions. Only H atoms involving hydrogen bonds are included.

Bis(2-amino-6-methyl-1,3-benzothiazole-κN³)bis(4-nitrobenzoato- κO¹)zinc top

Crystal data top

[Zn(C₇H₄NO₄)₂(C₈H₈N₂S)₂]	F(000) = 1488
M_r = 726.04	D_x = 1.561 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.2240 (8) Å	Cell parameters from 7342 reflections
b = 10.7369 (7) Å	θ = 2.7–27.7°
c = 21.8863 (13) Å	µ = 0.99 mm⁻¹
β = 96.099 (1)°	T = 296 K
V = 3089.9 (3) Å³	Block, yellow
Z = 4	0.05 × 0.04 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	5418 independent reflections
Radiation source: fine-focus sealed tube	4724 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→11
T_min = 0.952, T_max = 0.971	k = −10→12
15119 measured reflections	l = −22→26

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0476P)² + 4.110P] where P = (F_o² + 2F_c²)/3
5418 reflections	(Δ/σ)_max = 0.001
426 parameters	Δρ_max = 1.24 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Zn(C₇H₄NO₄)₂(C₈H₈N₂S)₂]	V = 3089.9 (3) Å³
M_r = 726.04	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.2240 (8) Å	µ = 0.99 mm⁻¹
b = 10.7369 (7) Å	T = 296 K
c = 21.8863 (13) Å	0.05 × 0.04 × 0.03 mm
β = 96.099 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5418 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4724 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.971	R_int = 0.028
15119 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.05	Δρ_max = 1.24 e Å⁻³
5418 reflections	Δρ_min = −0.42 e Å⁻³
426 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.

A small void of about 37Å3 was ignored and was not dealt with SQUEEZE in PLATON, because it is so small that no solvent molecules can be kept in.

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

	x	y	z	U_iso*/U_eq
Zn1	0.26944 (2)	0.00802 (3)	0.480986 (13)	0.02098 (11)
S1	0.47182 (6)	0.30130 (7)	0.40799 (3)	0.03297 (19)
S2	−0.01802 (5)	0.24653 (7)	0.48211 (3)	0.02783 (17)
O1	0.34638 (13)	−0.01142 (17)	0.56266 (8)	0.0247 (4)
O2	0.19228 (14)	−0.0698 (2)	0.58293 (9)	0.0302 (5)
O3	0.5423 (2)	−0.2293 (3)	0.84770 (12)	0.0759 (10)
O4	0.40207 (17)	−0.3229 (2)	0.85604 (10)	0.0459 (6)
O5	0.30961 (15)	−0.27205 (19)	0.47934 (9)	0.0323 (5)
O6	0.20619 (13)	−0.12869 (17)	0.43234 (8)	0.0244 (4)
O7	−0.0259 (2)	−0.5840 (3)	0.24530 (15)	0.0772 (10)
O8	0.0226 (2)	−0.7233 (3)	0.31379 (15)	0.0694 (8)
N1	0.36676 (16)	0.1045 (2)	0.43113 (10)	0.0233 (5)
N2	0.49494 (17)	0.1583 (2)	0.50904 (10)	0.0294 (5)
H2A	0.4785	0.0988	0.5323	0.035*
H2B	0.5445	0.2072	0.5214	0.035*
N3	0.15791 (16)	0.1385 (2)	0.48208 (10)	0.0226 (5)
N4	0.02296 (17)	0.0328 (2)	0.42585 (11)	0.0272 (5)
H4A	0.0622	−0.0258	0.4156	0.033*
H4B	−0.0410	0.0308	0.4135	0.033*
N5	0.4538 (2)	−0.2505 (3)	0.83008 (12)	0.0405 (7)
N6	0.0226 (2)	−0.6164 (3)	0.29378 (15)	0.0495 (8)
C1	0.3274 (2)	0.1474 (3)	0.37255 (12)	0.0244 (6)
C2	0.3728 (2)	0.2560 (3)	0.35280 (13)	0.0284 (6)
C3	0.3393 (2)	0.3119 (3)	0.29694 (14)	0.0358 (7)
H3	0.3691	0.3853	0.2852	0.043*
C4	0.2610 (2)	0.2571 (3)	0.25899 (15)	0.0381 (7)
C5	0.2186 (2)	0.1459 (3)	0.27823 (14)	0.0345 (7)
H5	0.1673	0.1078	0.2525	0.041*
C6	0.2504 (2)	0.0908 (3)	0.33415 (13)	0.0282 (6)
H6	0.2208	0.0172	0.3458	0.034*
C7	0.44390 (19)	0.1748 (3)	0.45406 (12)	0.0257 (6)
C8	0.2202 (3)	0.3160 (4)	0.19792 (16)	0.0505 (9)
H8A	0.2012	0.4008	0.2046	0.076*
H8B	0.1617	0.2703	0.1804	0.076*
H8C	0.2718	0.3139	0.1703	0.076*
C9	0.1747 (2)	0.2472 (3)	0.51684 (12)	0.0243 (6)
C10	0.0875 (2)	0.3181 (3)	0.52264 (13)	0.0266 (6)
C11	0.0913 (2)	0.4282 (3)	0.55639 (13)	0.0308 (6)
H11	0.0323	0.4733	0.5602	0.037*
C12	0.1845 (2)	0.4698 (3)	0.58424 (14)	0.0339 (7)
C13	0.2717 (2)	0.3993 (3)	0.57735 (14)	0.0359 (7)
H13	0.3343	0.4279	0.5953	0.043*
C14	0.2679 (2)	0.2894 (3)	0.54497 (13)	0.0312 (7)
H14	0.3269	0.2437	0.5419	0.037*
C15	0.06120 (19)	0.1267 (2)	0.46081 (12)	0.0228 (6)
C16	0.1951 (3)	0.5880 (3)	0.62144 (16)	0.0459 (8)
H16A	0.1288	0.6198	0.6269	0.069*
H16B	0.2317	0.6487	0.6003	0.069*
H16C	0.2314	0.5709	0.6609	0.069*
C17	0.32872 (19)	−0.0954 (3)	0.66182 (12)	0.0228 (6)
C18	0.4305 (2)	−0.0734 (3)	0.68280 (12)	0.0267 (6)
H18	0.4710	−0.0274	0.6589	0.032*
C19	0.4716 (2)	−0.1198 (3)	0.73917 (13)	0.0306 (6)
H19	0.5390	−0.1041	0.7539	0.037*
C20	0.4098 (2)	−0.1901 (3)	0.77294 (12)	0.0300 (6)
C21	0.3074 (2)	−0.2099 (3)	0.75424 (13)	0.0305 (6)
H21	0.2670	−0.2555	0.7784	0.037*
C22	0.2671 (2)	−0.1600 (3)	0.69863 (13)	0.0277 (6)
H22	0.1982	−0.1697	0.6858	0.033*
C23	0.2843 (2)	−0.0555 (3)	0.59863 (12)	0.0236 (6)
C25	0.18095 (19)	−0.3394 (3)	0.40249 (12)	0.0230 (6)
C26	0.1996 (2)	−0.4654 (3)	0.41508 (13)	0.0271 (6)
H26	0.2463	−0.4882	0.4479	0.032*
C27	0.1490 (2)	−0.5567 (3)	0.37901 (14)	0.0336 (7)
H27	0.1611	−0.6407	0.3873	0.040*
C28	0.0805 (2)	−0.5203 (3)	0.33078 (15)	0.0364 (7)
C29	0.0623 (2)	−0.3960 (3)	0.31583 (14)	0.0364 (7)
H29	0.0177	−0.3741	0.2818	0.044*
C30	0.1120 (2)	−0.3053 (3)	0.35279 (13)	0.0285 (6)
H30	0.0993	−0.2215	0.3444	0.034*
C31	0.23768 (19)	−0.2413 (3)	0.44193 (12)	0.0231 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01631 (17)	0.02239 (18)	0.02357 (18)	0.00094 (12)	−0.00095 (12)	−0.00048 (12)
S1	0.0306 (4)	0.0337 (4)	0.0346 (4)	−0.0124 (3)	0.0033 (3)	−0.0041 (3)
S2	0.0185 (3)	0.0242 (4)	0.0404 (4)	0.0044 (3)	0.0012 (3)	0.0016 (3)
O1	0.0204 (9)	0.0301 (11)	0.0233 (9)	0.0020 (8)	0.0007 (8)	0.0001 (8)
O2	0.0186 (10)	0.0376 (12)	0.0328 (11)	0.0003 (8)	−0.0050 (8)	0.0015 (9)
O3	0.0495 (16)	0.119 (3)	0.0528 (16)	−0.0286 (17)	−0.0247 (13)	0.0367 (17)
O4	0.0456 (13)	0.0576 (16)	0.0341 (12)	−0.0051 (12)	0.0026 (10)	0.0146 (11)
O5	0.0272 (10)	0.0308 (11)	0.0360 (11)	−0.0024 (9)	−0.0101 (9)	0.0026 (9)
O6	0.0221 (9)	0.0225 (10)	0.0284 (10)	−0.0001 (8)	0.0010 (8)	−0.0011 (8)
O7	0.082 (2)	0.065 (2)	0.075 (2)	0.0077 (16)	−0.0390 (17)	−0.0271 (16)
O8	0.0672 (19)	0.0440 (17)	0.095 (2)	−0.0024 (14)	−0.0005 (16)	−0.0192 (16)
N1	0.0185 (11)	0.0266 (12)	0.0244 (11)	−0.0008 (9)	0.0000 (9)	−0.0019 (9)
N2	0.0215 (11)	0.0353 (14)	0.0303 (13)	−0.0038 (10)	−0.0016 (10)	−0.0061 (11)
N3	0.0181 (11)	0.0233 (12)	0.0261 (11)	0.0027 (9)	0.0010 (9)	0.0011 (9)
N4	0.0157 (11)	0.0276 (13)	0.0373 (13)	0.0010 (9)	−0.0026 (9)	−0.0018 (10)
N5	0.0344 (15)	0.0565 (18)	0.0290 (14)	−0.0043 (13)	−0.0041 (11)	0.0049 (13)
N6	0.0456 (17)	0.0400 (18)	0.061 (2)	0.0002 (14)	−0.0041 (15)	−0.0193 (15)
C1	0.0217 (13)	0.0252 (14)	0.0268 (14)	0.0011 (11)	0.0049 (11)	−0.0009 (11)
C2	0.0268 (14)	0.0284 (15)	0.0305 (15)	−0.0046 (12)	0.0059 (12)	−0.0063 (12)
C3	0.0393 (17)	0.0306 (17)	0.0376 (17)	−0.0060 (14)	0.0049 (14)	0.0050 (13)
C4	0.0400 (17)	0.0360 (18)	0.0377 (17)	−0.0017 (14)	0.0010 (14)	0.0054 (14)
C5	0.0320 (16)	0.0353 (17)	0.0344 (16)	−0.0044 (13)	−0.0049 (13)	0.0024 (13)
C6	0.0258 (14)	0.0262 (15)	0.0316 (15)	−0.0035 (12)	−0.0010 (12)	0.0025 (12)
C7	0.0188 (13)	0.0304 (15)	0.0285 (14)	−0.0008 (11)	0.0057 (11)	−0.0068 (12)
C8	0.058 (2)	0.051 (2)	0.0410 (19)	−0.0048 (18)	0.0004 (17)	0.0123 (17)
C9	0.0240 (14)	0.0223 (14)	0.0265 (14)	0.0023 (11)	0.0018 (11)	0.0017 (11)
C10	0.0242 (14)	0.0240 (14)	0.0312 (15)	0.0035 (11)	0.0009 (11)	0.0040 (12)
C11	0.0322 (15)	0.0265 (15)	0.0334 (15)	0.0103 (12)	0.0024 (12)	0.0006 (12)
C12	0.0378 (17)	0.0258 (15)	0.0367 (17)	0.0067 (13)	−0.0034 (13)	−0.0024 (13)
C13	0.0318 (16)	0.0333 (17)	0.0402 (17)	0.0016 (13)	−0.0069 (13)	−0.0046 (14)
C14	0.0246 (14)	0.0326 (16)	0.0348 (16)	0.0072 (12)	−0.0036 (12)	−0.0041 (13)
C15	0.0209 (13)	0.0213 (14)	0.0263 (14)	0.0025 (11)	0.0028 (11)	0.0049 (11)
C16	0.051 (2)	0.0349 (18)	0.048 (2)	0.0092 (16)	−0.0126 (16)	−0.0103 (15)
C17	0.0212 (13)	0.0246 (14)	0.0225 (13)	0.0039 (11)	0.0014 (10)	−0.0048 (11)
C18	0.0223 (13)	0.0327 (16)	0.0252 (14)	0.0001 (12)	0.0038 (11)	−0.0009 (12)
C19	0.0219 (14)	0.0403 (17)	0.0283 (15)	−0.0017 (12)	−0.0031 (11)	−0.0027 (13)
C20	0.0325 (15)	0.0352 (17)	0.0216 (14)	0.0010 (13)	0.0000 (12)	0.0001 (12)
C21	0.0282 (15)	0.0379 (17)	0.0261 (14)	−0.0029 (13)	0.0052 (12)	−0.0007 (13)
C22	0.0222 (13)	0.0322 (16)	0.0281 (14)	−0.0008 (12)	−0.0005 (11)	−0.0039 (12)
C23	0.0227 (14)	0.0214 (14)	0.0258 (14)	0.0037 (11)	−0.0007 (11)	−0.0031 (11)
C25	0.0190 (13)	0.0241 (14)	0.0260 (14)	0.0006 (11)	0.0029 (10)	−0.0008 (11)
C26	0.0234 (14)	0.0285 (15)	0.0288 (15)	0.0040 (12)	0.0006 (11)	0.0007 (12)
C27	0.0309 (16)	0.0258 (15)	0.0434 (17)	0.0043 (13)	0.0009 (13)	−0.0067 (13)
C28	0.0322 (16)	0.0332 (17)	0.0423 (18)	0.0004 (13)	−0.0027 (14)	−0.0130 (14)
C29	0.0338 (16)	0.0376 (18)	0.0349 (16)	0.0050 (14)	−0.0103 (13)	−0.0052 (14)
C30	0.0263 (14)	0.0263 (15)	0.0317 (15)	0.0020 (12)	−0.0024 (12)	−0.0011 (12)
C31	0.0195 (13)	0.0263 (15)	0.0235 (13)	−0.0012 (11)	0.0020 (11)	0.0010 (11)

Geometric parameters (Å, º) top

Zn1—O6	1.9489 (18)	C8—H8A	0.9600
Zn1—O1	1.9717 (18)	C8—H8B	0.9600
Zn1—N3	2.036 (2)	C8—H8C	0.9600
Zn1—N1	2.054 (2)	C9—C14	1.393 (4)
S1—C2	1.754 (3)	C9—C10	1.399 (4)
S1—C7	1.755 (3)	C10—C11	1.392 (4)
S2—C10	1.750 (3)	C11—C12	1.389 (4)
S2—C15	1.754 (3)	C11—H11	0.9300
O1—C23	1.287 (3)	C12—C13	1.401 (4)
O2—C23	1.238 (3)	C12—C16	1.507 (4)
O3—N5	1.214 (3)	C13—C14	1.375 (4)
O4—N5	1.216 (3)	C13—H13	0.9300
O5—C31	1.232 (3)	C14—H14	0.9300
O6—C31	1.289 (3)	C16—H16A	0.9600
O7—N6	1.230 (4)	C16—H16B	0.9600
O8—N6	1.229 (4)	C16—H16C	0.9600
N1—C7	1.324 (3)	C17—C22	1.390 (4)
N1—C1	1.409 (3)	C17—C18	1.396 (4)
N2—C7	1.327 (3)	C17—C23	1.506 (4)
N2—H2A	0.8600	C18—C19	1.387 (4)
N2—H2B	0.8600	C18—H18	0.9300
N3—C15	1.320 (3)	C19—C20	1.383 (4)
N3—C9	1.398 (3)	C19—H19	0.9300
N4—C15	1.332 (4)	C20—C21	1.388 (4)
N4—H4A	0.8600	C21—C22	1.384 (4)
N4—H4B	0.8600	C21—H21	0.9300
N5—C20	1.472 (4)	C22—H22	0.9300
N6—C28	1.474 (4)	C25—C30	1.392 (4)
C1—C6	1.389 (4)	C25—C26	1.397 (4)
C1—C2	1.401 (4)	C25—C31	1.510 (4)
C2—C3	1.391 (4)	C26—C27	1.386 (4)
C3—C4	1.388 (4)	C26—H26	0.9300
C3—H3	0.9300	C27—C28	1.373 (4)
C4—C5	1.403 (4)	C27—H27	0.9300
C4—C8	1.525 (4)	C28—C29	1.389 (4)
C5—C6	1.384 (4)	C29—C30	1.387 (4)
C5—H5	0.9300	C29—H29	0.9300
C6—H6	0.9300	C30—H30	0.9300

O6—Zn1—O1	124.45 (8)	C12—C11—H11	120.5
O6—Zn1—N3	104.78 (8)	C10—C11—H11	120.5
O1—Zn1—N3	111.52 (8)	C11—C12—C13	118.8 (3)
O6—Zn1—N1	110.27 (8)	C11—C12—C16	122.3 (3)
O1—Zn1—N1	104.06 (8)	C13—C12—C16	118.9 (3)
N3—Zn1—N1	98.91 (9)	C14—C13—C12	122.3 (3)
C2—S1—C7	89.64 (13)	C14—C13—H13	118.9
C10—S2—C15	89.45 (13)	C12—C13—H13	118.9
C23—O1—Zn1	106.99 (16)	C13—C14—C9	119.3 (3)
C31—O6—Zn1	120.34 (16)	C13—C14—H14	120.4
C7—N1—C1	110.8 (2)	C9—C14—H14	120.4
C7—N1—Zn1	125.95 (18)	N3—C15—N4	124.7 (2)
C1—N1—Zn1	117.15 (16)	N3—C15—S2	114.8 (2)
C7—N2—H2A	120.0	N4—C15—S2	120.4 (2)
C7—N2—H2B	120.0	C12—C16—H16A	109.5
H2A—N2—H2B	120.0	C12—C16—H16B	109.5
C15—N3—C9	111.4 (2)	H16A—C16—H16B	109.5
C15—N3—Zn1	127.29 (19)	C12—C16—H16C	109.5
C9—N3—Zn1	120.47 (17)	H16A—C16—H16C	109.5
C15—N4—H4A	120.0	H16B—C16—H16C	109.5
C15—N4—H4B	120.0	C22—C17—C18	119.9 (2)
H4A—N4—H4B	120.0	C22—C17—C23	118.6 (2)
O3—N5—O4	122.9 (3)	C18—C17—C23	121.5 (2)
O3—N5—C20	118.0 (3)	C19—C18—C17	120.3 (3)
O4—N5—C20	119.1 (2)	C19—C18—H18	119.8
O8—N6—O7	123.4 (3)	C17—C18—H18	119.8
O8—N6—C28	118.5 (3)	C20—C19—C18	118.2 (3)
O7—N6—C28	118.0 (3)	C20—C19—H19	120.9
C6—C1—C2	119.2 (3)	C18—C19—H19	120.9
C6—C1—N1	125.7 (2)	C19—C20—C21	122.6 (3)
C2—C1—N1	115.1 (2)	C19—C20—N5	119.4 (3)
C3—C2—C1	121.6 (3)	C21—C20—N5	117.9 (3)
C3—C2—S1	129.1 (2)	C22—C21—C20	118.2 (3)
C1—C2—S1	109.4 (2)	C22—C21—H21	120.9
C4—C3—C2	119.4 (3)	C20—C21—H21	120.9
C4—C3—H3	120.3	C21—C22—C17	120.5 (3)
C2—C3—H3	120.3	C21—C22—H22	119.7
C3—C4—C5	118.5 (3)	C17—C22—H22	119.7
C3—C4—C8	121.4 (3)	O2—C23—O1	123.2 (2)
C5—C4—C8	120.0 (3)	O2—C23—C17	119.7 (2)
C6—C5—C4	122.4 (3)	O1—C23—C17	117.0 (2)
C6—C5—H5	118.8	C30—C25—C26	119.7 (3)
C4—C5—H5	118.8	C30—C25—C31	120.5 (2)
C5—C6—C1	118.9 (3)	C26—C25—C31	119.8 (2)
C5—C6—H6	120.6	C27—C26—C25	120.6 (3)
C1—C6—H6	120.6	C27—C26—H26	119.7
N1—C7—N2	124.4 (3)	C25—C26—H26	119.7
N1—C7—S1	115.1 (2)	C28—C27—C26	118.4 (3)
N2—C7—S1	120.4 (2)	C28—C27—H27	120.8
C4—C8—H8A	109.5	C26—C27—H27	120.8
C4—C8—H8B	109.5	C27—C28—C29	122.6 (3)
H8A—C8—H8B	109.5	C27—C28—N6	119.0 (3)
C4—C8—H8C	109.5	C29—C28—N6	118.4 (3)
H8A—C8—H8C	109.5	C30—C29—C28	118.6 (3)
H8B—C8—H8C	109.5	C30—C29—H29	120.7
C14—C9—N3	126.5 (2)	C28—C29—H29	120.7
C14—C9—C10	118.8 (3)	C29—C30—C25	120.1 (3)
N3—C9—C10	114.7 (2)	C29—C30—H30	120.0
C11—C10—C9	121.8 (3)	C25—C30—H30	120.0
C11—C10—S2	128.6 (2)	O5—C31—O6	124.9 (2)
C9—C10—S2	109.6 (2)	O5—C31—C25	119.6 (2)
C12—C11—C10	119.1 (3)	O6—C31—C25	115.4 (2)

O6—Zn1—O1—C23	−61.77 (19)	S2—C10—C11—C12	−178.7 (2)
N3—Zn1—O1—C23	65.32 (18)	C10—C11—C12—C13	0.0 (5)
N1—Zn1—O1—C23	171.00 (17)	C10—C11—C12—C16	179.9 (3)
O1—Zn1—O6—C31	−22.1 (2)	C11—C12—C13—C14	−1.2 (5)
N3—Zn1—O6—C31	−151.97 (19)	C16—C12—C13—C14	178.9 (3)
N1—Zn1—O6—C31	102.47 (19)	C12—C13—C14—C9	1.3 (5)
O6—Zn1—N1—C7	−157.5 (2)	N3—C9—C14—C13	179.5 (3)
O1—Zn1—N1—C7	−21.9 (2)	C10—C9—C14—C13	−0.2 (4)
N3—Zn1—N1—C7	93.1 (2)	C9—N3—C15—N4	179.4 (2)
O6—Zn1—N1—C1	52.8 (2)	Zn1—N3—C15—N4	−11.3 (4)
O1—Zn1—N1—C1	−171.65 (18)	C9—N3—C15—S2	−0.7 (3)
N3—Zn1—N1—C1	−56.7 (2)	Zn1—N3—C15—S2	168.56 (13)
O6—Zn1—N3—C15	7.2 (2)	C10—S2—C15—N3	0.1 (2)
O1—Zn1—N3—C15	−129.9 (2)	C10—S2—C15—N4	−180.0 (2)
N1—Zn1—N3—C15	121.1 (2)	C22—C17—C18—C19	2.5 (4)
O6—Zn1—N3—C9	175.59 (19)	C23—C17—C18—C19	−174.8 (3)
O1—Zn1—N3—C9	38.5 (2)	C17—C18—C19—C20	1.4 (4)
N1—Zn1—N3—C9	−70.6 (2)	C18—C19—C20—C21	−3.7 (5)
C7—N1—C1—C6	175.9 (3)	C18—C19—C20—N5	174.2 (3)
Zn1—N1—C1—C6	−29.9 (3)	O3—N5—C20—C19	4.8 (5)
C7—N1—C1—C2	−3.3 (3)	O4—N5—C20—C19	−172.1 (3)
Zn1—N1—C1—C2	150.81 (19)	O3—N5—C20—C21	−177.2 (3)
C6—C1—C2—C3	3.2 (4)	O4—N5—C20—C21	5.9 (4)
N1—C1—C2—C3	−177.5 (3)	C19—C20—C21—C22	1.9 (5)
C6—C1—C2—S1	−176.4 (2)	N5—C20—C21—C22	−176.0 (3)
N1—C1—C2—S1	2.9 (3)	C20—C21—C22—C17	2.1 (4)
C7—S1—C2—C3	179.2 (3)	C18—C17—C22—C21	−4.3 (4)
C7—S1—C2—C1	−1.3 (2)	C23—C17—C22—C21	173.1 (3)
C1—C2—C3—C4	−1.8 (5)	Zn1—O1—C23—O2	−5.9 (3)
S1—C2—C3—C4	177.7 (2)	Zn1—O1—C23—C17	171.76 (18)
C2—C3—C4—C5	−0.5 (5)	C22—C17—C23—O2	7.0 (4)
C2—C3—C4—C8	178.8 (3)	C18—C17—C23—O2	−175.7 (3)
C3—C4—C5—C6	1.6 (5)	C22—C17—C23—O1	−170.7 (2)
C8—C4—C5—C6	−177.7 (3)	C18—C17—C23—O1	6.6 (4)
C4—C5—C6—C1	−0.3 (5)	C30—C25—C26—C27	−0.9 (4)
C2—C1—C6—C5	−2.1 (4)	C31—C25—C26—C27	−179.4 (2)
N1—C1—C6—C5	178.7 (3)	C25—C26—C27—C28	0.1 (4)
C1—N1—C7—N2	178.7 (2)	C26—C27—C28—C29	1.9 (5)
Zn1—N1—C7—N2	27.3 (4)	C26—C27—C28—N6	−177.2 (3)
C1—N1—C7—S1	2.3 (3)	O8—N6—C28—C27	13.7 (5)
Zn1—N1—C7—S1	−149.09 (14)	O7—N6—C28—C27	−168.6 (3)
C2—S1—C7—N1	−0.6 (2)	O8—N6—C28—C29	−165.4 (3)
C2—S1—C7—N2	−177.2 (2)	O7—N6—C28—C29	12.2 (5)
C15—N3—C9—C14	−178.7 (3)	C27—C28—C29—C30	−2.9 (5)
Zn1—N3—C9—C14	11.2 (4)	N6—C28—C29—C30	176.2 (3)
C15—N3—C9—C10	1.0 (3)	C28—C29—C30—C25	2.0 (5)
Zn1—N3—C9—C10	−169.03 (19)	C26—C25—C30—C29	−0.2 (4)
C14—C9—C10—C11	−1.0 (4)	C31—C25—C30—C29	178.3 (3)
N3—C9—C10—C11	179.3 (2)	Zn1—O6—C31—O5	−2.6 (4)
C14—C9—C10—S2	178.9 (2)	Zn1—O6—C31—C25	178.49 (16)
N3—C9—C10—S2	−0.9 (3)	C30—C25—C31—O5	−168.5 (3)
C15—S2—C10—C11	−179.8 (3)	C26—C25—C31—O5	10.0 (4)
C15—S2—C10—C9	0.4 (2)	C30—C25—C31—O6	10.5 (4)
C9—C10—C11—C12	1.0 (4)	C26—C25—C31—O6	−171.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.27	3.008 (3)	144
N2—H2B···O5ⁱ	0.86	2.05	2.845 (3)	153
N4—H4A···O6	0.86	2.20	2.971 (3)	149
N4—H4B···O2ⁱⁱ	0.86	2.05	2.860 (3)	156

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₄NO₄)₂(C₈H₈N₂S)₂]
M_r	726.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.2240 (8), 10.7369 (7), 21.8863 (13)
β (°)	96.099 (1)
V (Å³)	3089.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.99
Crystal size (mm)	0.05 × 0.04 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.952, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	15119, 5418, 4724
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.101, 1.05
No. of reflections	5418
No. of parameters	426
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.24, −0.42

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg & Berndt, 1999).

Selected bond lengths (Å) top

Zn1—O6	1.9489 (18)	Zn1—N3	2.036 (2)
Zn1—O1	1.9717 (18)	Zn1—N1	2.054 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.86	2.27	3.008 (3)	144.4
N2—H2B···O5ⁱ	0.86	2.05	2.845 (3)	152.8
N4—H4A···O6	0.86	2.20	2.971 (3)	149.3
N4—H4B···O2ⁱⁱ	0.86	2.05	2.860 (3)	155.8

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

Acknowledgements

The authors gratefully acknowledge financial support from Tianjin Normal University.

References

Batista, R. M. F., Costa, S. P. G., Malheiro, E. L., Belsley, M. & Raposo, M. M. M. (2007). Tetrahedron, 63, 4258–4265. Web of Science CrossRef CAS Google Scholar
Brandenburg, K. & Berndt, M. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, Q., Yang, E.-C., Zhang, R.-W., Wang, X.-G. & Zhao, X.-J. (2008). J. Coord. Chem. 12, 1951–1962. Web of Science CSD CrossRef Google Scholar
Kovalska, V. B., Volkova, K. D., Losytskyy, M. Y., Tolmachev, O. I., Balanda, A. O. & Yarmoluk, S. M. (2006). Spectrochim. Acta Part A, 65, 271–277. CrossRef Google Scholar
Marconato, J. C., Bulhoes, L. O. & Temperini, M. L. (1998). Electrochim. Acta, 43, 771–780. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, Y. F. & Cui, Y. P. (2008). Chin. J. Struct. Chem. 27, 1526–1532. CAS Google Scholar