Poly[(μ2-benzene-1,3-dicarboxyl­ato-κ2O1:O3){μ2-1,2-bis­[(1H-imidazol-1-yl)meth­yl]benzene-κ2N3:N3′}zinc]

Chen, H.; Xu, H.

doi:10.1107/S1600536812022544

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page m826

doi:10.1107/S1600536812022544

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Poly[(μ₂-benzene-1,3-dicarboxylato-κ²O¹:O³){μ₂-1,2-bis[(1H-imidazol-1-yl)methyl]benzene-κ²N³:N^3′}zinc]

Hong Chen ^a and Heng Xu ^b ^*

^aDepartment of Chemistry, Chaohu University, Chaohu 238000, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246003, People's Republic of China
^*Correspondence e-mail: aqliugx@sohu.com

(Received 5 May 2012; accepted 17 May 2012; online 26 May 2012)

In the two-dimensional title coordination polymer, [Zn(C₈H₄O₄)(C₁₄H₁₄N₄)]_n, the Zn^II atom adopts a distorted tetrahedral geometry, being ligated by two O atoms from two different benzene-1,3-dicarboxylate dianions and two N atoms from two symmetry-related 1,2-bis(imidazol-1-ylmethyl)benzene molecules. The dihedral angles between the imidazole rings and the benzene ring in the neutral ligand are 76.31 (13) and 85.33 (15)°. The Zn^II atoms are bridged by dicarboxylate ligands, forming chains parallel to the a axis, which are further linked by 1,2-bis(imidazol-1-ylmethyl)benzene molecules, generating a two-dimensional layer structure parallel to the ac plane. The crystal structure is enforced by intralayer and interlayer C—H⋯O hydrogen bonds.

Related literature

For background to coordination polymers with bis(imidazole) ligands, see: Qi et al. (2008 ); Liu et al. (2009 ); Hu et al. (2008 ). For related structures, see: Liu et al. (2008 ).

Experimental

Crystal data

[Zn(C₈H₄O₄)(C₁₄H₁₄N₄)]
M_r = 467.77
Triclinic, $[P \overline 1]$
a = 10.2028 (14) Å
b = 10.2744 (14) Å
c = 11.4529 (16) Å
α = 75.405 (2)°
β = 83.480 (2)°
γ = 61.499 (2)°
V = 1021.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.24 mm⁻¹
T = 293 K
0.26 × 0.24 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.739, T_max = 0.790
5145 measured reflections
3564 independent reflections
3148 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.115
S = 1.02
3564 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O3ⁱ	0.93	2.38	3.188 (4)	145
C11—H11⋯O4ⁱⁱ	0.93	2.54	3.413 (4)	157
C14—H14⋯O1ⁱⁱ	0.93	2.38	3.306 (7)	171
C19—H19B⋯O2ⁱⁱⁱ	0.97	2.38	3.200 (4)	142
C20—H20⋯O1^iv	0.93	2.34	3.016 (4)	130
C21—H21⋯O4^v	0.93	2.54	3.092 (6)	119
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x, -y+2, -z+2; (iii) -x, -y+1, -z+2; (iv) x, y, z-1; (v) x-1, y, z-1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812022544/rz2755sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812022544/rz2755Isup2.hkl

checkCIF report

Comment top

Studies of coordination polymers are of considerable interest due to their fascinating network topologies and potential applications in storage, catalysis, molecular magnetism, recognition, and photoluminescence. Recently significant work has been carried out by using metal ions assembly with bis(imidazole) ligands interconnected by flexible spacers (Qi et al., 2008; Liu et al., 2008, 2009). From careful inspection of the reported cases, we found that the ligand exhibits a special ability to formulate the compounds, and different organic anions play an important role in directing the final structures and topologies (Hu et al., 2008). Inspired by the these considerations, 1,2-bis(imidazol-1-ylmethyl)benzene was chosen as neutral ligands, and benzene-1,3-dicarboxylate as co-ligand to construct the title complex.

The title compound is a two-dimensional layer coordination polymer. The zinc(II) atom adopts a distorted tetrahedral geometry, being ligated by two O atoms from two different benzene-1,3-dicarboxylate ligands and two N atoms from two 1,2-bis(imidazol-1-ylmethyl)benzene ligands, as shown in Fig. 1. In the neutral ligand, the N1/N2/C9-C11 and N3/N4/C20/C21 imidazole rings form a dihedral angle of 76.10 (13)° and are tilted by 76.31 (13) and 85.33 (15)° with respect to the benzene ring plane. The Zn atoms are bridged by benzene-1,3-dicarboxylate dianions to form one-dimensional chains running parallel to the a axis, which are further linked by 1,2-bis(imidazol-1-ylmethyl)benzene molecules to generate a two-dimensional layer structure parallel to the ac plane (Fig. 2). The crystal structure is enforced by intralayer and interlayer C—H···O hydrogen bonds (Table 1).

Related literature top

For background to coordination polymers with bis(imidazole) ligands, see: Qi et al. (2008); Liu et al. (2009); Hu et al. (2008). For related structures, see: Liu et al. (2008).

Experimental top

A mixture of Zn(NO₃)_2.6H₂O (29.1 mg, 0.1 mmol), benzene-1,3-dicarboxylate acid (16.4 mg, 0.1 mmol), 1,2-bis(imidazol-1-ylmethyl)benzene (23.8 mg, 0.1 mmol), NaOH (8 mg, 0.2 mmol) and H₂O (15 ml) was added in a Teflon-lined stainless steel vessel. The vessel was sealed and heated for 3 d at 140 °C. After the mixture was slowly cooled to room temperature, colourless block crystals were obtained in a yield of ca 59% based on Zn.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, extended to show the Zn coordination geometry. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Suffixes A and B denote symmetry operators (-1+x, y, z) and (x, y, 1+z), respectively.
	Fig. 2. The two-dimensional layer structure of the title compound. Hydrogen atoms are omitted for clarity.

Poly[(µ₂-benzene-1,3-dicarboxylato-κ²O¹:O³){µ₂- 1,2-bis[(1H-imidazol-1-yl)methyl]benzene- κ²N³:N^3'}zinc] top

Crystal data top

[Zn(C₈H₄O₄)(C₁₄H₁₄N₄)]	Z = 2
M_r = 467.77	F(000) = 480
Triclinic, P1	D_x = 1.522 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.2028 (14) Å	Cell parameters from 2793 reflections
b = 10.2744 (14) Å	θ = 2.3–27.9°
c = 11.4529 (16) Å	µ = 1.24 mm⁻¹
α = 75.405 (2)°	T = 293 K
β = 83.480 (2)°	Block, colourless
γ = 61.499 (2)°	0.26 × 0.24 × 0.20 mm
V = 1021.0 (2) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3564 independent reflections
Radiation source: sealed tube	3148 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
phi and ω scans	θ_max = 25.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→12
T_min = 0.739, T_max = 0.790	k = −12→11
5145 measured reflections	l = −12→13

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0534P)² + 0.6759P] where P = (F_o² + 2F_c²)/3
3564 reflections	(Δ/σ)_max < 0.001
280 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

[Zn(C₈H₄O₄)(C₁₄H₁₄N₄)]	γ = 61.499 (2)°
M_r = 467.77	V = 1021.0 (2) Å³
Triclinic, P1	Z = 2
a = 10.2028 (14) Å	Mo Kα radiation
b = 10.2744 (14) Å	µ = 1.24 mm⁻¹
c = 11.4529 (16) Å	T = 293 K
α = 75.405 (2)°	0.26 × 0.24 × 0.20 mm
β = 83.480 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3564 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3148 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.790	R_int = 0.062
5145 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.02	Δρ_max = 0.59 e Å⁻³
3564 reflections	Δρ_min = −0.52 e Å⁻³
280 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
Zn1	−0.12836 (4)	0.60720 (4)	1.18865 (3)	0.03331 (15)
N1	−0.1733 (3)	0.7657 (3)	1.0358 (2)	0.0304 (6)
N2	−0.1374 (3)	0.8927 (3)	0.8612 (2)	0.0342 (6)
N3	−0.1584 (3)	0.7322 (3)	0.5120 (3)	0.0420 (7)
N4	−0.1780 (3)	0.6676 (3)	0.3492 (3)	0.0394 (7)
O1	0.1045 (3)	0.6829 (3)	1.1935 (2)	0.0464 (6)
O2	0.0904 (2)	0.4788 (3)	1.1805 (2)	0.0392 (6)
O3	0.7971 (2)	0.4629 (3)	1.1786 (2)	0.0352 (5)
O4	0.5906 (3)	0.6760 (3)	1.1811 (2)	0.0400 (6)
C1	0.1634 (3)	0.5512 (4)	1.1811 (3)	0.0329 (7)
C2	0.3288 (3)	0.4676 (4)	1.1651 (3)	0.0294 (7)
C3	0.3983 (4)	0.3254 (4)	1.1412 (3)	0.0366 (8)
H3	0.3422	0.2771	1.1368	0.044*
C4	0.5505 (4)	0.2531 (4)	1.1234 (3)	0.0435 (9)
H4	0.5964	0.1573	1.1060	0.052*
C5	0.6341 (4)	0.3236 (4)	1.1315 (3)	0.0354 (7)
H5	0.7365	0.2752	1.1194	0.042*
C6	0.5668 (3)	0.4654 (3)	1.1575 (3)	0.0273 (6)
C7	0.4142 (3)	0.5373 (4)	1.1729 (3)	0.0288 (7)
H7	0.3680	0.6340	1.1887	0.035*
C8	0.6550 (3)	0.5425 (4)	1.1731 (3)	0.0292 (7)
C9	−0.0785 (3)	0.7650 (4)	0.9477 (3)	0.0338 (7)
H9	0.0174	0.6858	0.9458	0.041*
C10	−0.2999 (4)	0.9013 (4)	1.0029 (3)	0.0362 (7)
H10	−0.3871	0.9332	1.0477	0.043*
C11	−0.2793 (4)	0.9816 (4)	0.8960 (3)	0.0400 (8)
H11	−0.3474	1.0774	0.8544	0.048*
C12	−0.0539 (4)	0.9346 (4)	0.7587 (3)	0.0403 (8)
H12A	0.0289	0.8427	0.7412	0.048*
H12B	−0.0129	0.9931	0.7809	0.048*
C13	−0.1483 (4)	1.0259 (4)	0.6473 (3)	0.0363 (8)
C14	−0.2102 (5)	1.1822 (4)	0.6227 (4)	0.0497 (9)
H14	−0.1920	1.2278	0.6752	0.060*
C15	−0.2984 (5)	1.2723 (5)	0.5217 (4)	0.0604 (11)
H15	−0.3391	1.3776	0.5059	0.072*
C16	−0.3248 (5)	1.2046 (5)	0.4458 (4)	0.0608 (11)
H16	−0.3853	1.2643	0.3781	0.073*
C17	−0.2638 (4)	1.0504 (5)	0.4677 (3)	0.0493 (9)
H17	−0.2820	1.0065	0.4137	0.059*
C18	−0.1755 (4)	0.9577 (4)	0.5683 (3)	0.0352 (7)
C19	−0.1066 (4)	0.7864 (4)	0.5940 (3)	0.0443 (9)
H19A	0.0010	0.7444	0.5880	0.053*
H19B	−0.1297	0.7492	0.6761	0.053*
C20	−0.0952 (4)	0.6950 (4)	0.4103 (3)	0.0402 (8)
H20	−0.0031	0.6888	0.3846	0.048*
C21	−0.3031 (5)	0.6908 (5)	0.4175 (4)	0.0549 (11)
H21	−0.3831	0.6807	0.3974	0.066*
C22	−0.2927 (5)	0.7305 (5)	0.5184 (4)	0.0589 (11)
H22	−0.3624	0.7523	0.5799	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0290 (2)	0.0372 (2)	0.0396 (2)	−0.01929 (18)	−0.00090 (16)	−0.00993 (17)
N1	0.0260 (13)	0.0318 (14)	0.0338 (14)	−0.0133 (11)	−0.0016 (11)	−0.0075 (11)
N2	0.0324 (15)	0.0395 (15)	0.0329 (15)	−0.0183 (12)	0.0007 (11)	−0.0092 (12)
N3	0.0473 (18)	0.0478 (17)	0.0412 (17)	−0.0280 (15)	0.0012 (14)	−0.0152 (14)
N4	0.0390 (16)	0.0522 (18)	0.0384 (16)	−0.0280 (14)	0.0070 (13)	−0.0182 (14)
O1	0.0284 (12)	0.0502 (16)	0.0675 (17)	−0.0200 (12)	−0.0001 (12)	−0.0209 (13)
O2	0.0258 (11)	0.0460 (14)	0.0532 (15)	−0.0237 (11)	−0.0039 (10)	−0.0068 (11)
O3	0.0211 (11)	0.0402 (13)	0.0515 (14)	−0.0187 (10)	0.0002 (10)	−0.0128 (11)
O4	0.0328 (12)	0.0372 (14)	0.0594 (15)	−0.0217 (11)	0.0000 (11)	−0.0149 (11)
C1	0.0252 (16)	0.044 (2)	0.0337 (17)	−0.0203 (15)	−0.0024 (13)	−0.0053 (15)
C2	0.0244 (15)	0.0409 (18)	0.0284 (16)	−0.0203 (14)	−0.0020 (12)	−0.0054 (13)
C3	0.0340 (18)	0.048 (2)	0.0425 (19)	−0.0286 (16)	−0.0001 (14)	−0.0141 (16)
C4	0.0371 (19)	0.045 (2)	0.060 (2)	−0.0215 (16)	0.0027 (17)	−0.0268 (18)
C5	0.0242 (16)	0.0418 (19)	0.0441 (19)	−0.0166 (15)	0.0013 (14)	−0.0140 (15)
C6	0.0223 (15)	0.0335 (16)	0.0291 (16)	−0.0161 (13)	−0.0036 (12)	−0.0038 (13)
C7	0.0239 (15)	0.0309 (16)	0.0347 (17)	−0.0151 (13)	−0.0014 (13)	−0.0067 (13)
C8	0.0258 (16)	0.0408 (19)	0.0280 (16)	−0.0222 (15)	−0.0008 (12)	−0.0050 (13)
C9	0.0266 (16)	0.0360 (18)	0.0377 (18)	−0.0119 (14)	−0.0025 (14)	−0.0111 (15)
C10	0.0299 (17)	0.0364 (18)	0.0429 (19)	−0.0150 (15)	0.0055 (14)	−0.0134 (15)
C11	0.0320 (18)	0.0350 (18)	0.047 (2)	−0.0111 (15)	−0.0015 (15)	−0.0086 (15)
C12	0.0342 (18)	0.060 (2)	0.0368 (18)	−0.0294 (17)	0.0026 (14)	−0.0127 (16)
C13	0.0354 (18)	0.045 (2)	0.0365 (18)	−0.0272 (16)	0.0069 (14)	−0.0084 (15)
C14	0.057 (2)	0.050 (2)	0.055 (2)	−0.036 (2)	0.0094 (19)	−0.0143 (19)
C15	0.065 (3)	0.039 (2)	0.070 (3)	−0.026 (2)	0.004 (2)	0.002 (2)
C16	0.062 (3)	0.059 (3)	0.048 (2)	−0.027 (2)	−0.010 (2)	0.011 (2)
C17	0.058 (2)	0.059 (3)	0.0331 (19)	−0.030 (2)	−0.0040 (17)	−0.0056 (17)
C18	0.0381 (18)	0.0412 (19)	0.0303 (17)	−0.0231 (16)	0.0036 (14)	−0.0063 (14)
C19	0.053 (2)	0.047 (2)	0.0383 (19)	−0.0253 (18)	−0.0073 (16)	−0.0114 (16)
C20	0.0371 (19)	0.048 (2)	0.043 (2)	−0.0243 (17)	0.0016 (16)	−0.0150 (17)
C21	0.054 (2)	0.086 (3)	0.051 (2)	−0.050 (2)	0.0143 (19)	−0.029 (2)
C22	0.059 (3)	0.090 (3)	0.052 (2)	−0.050 (3)	0.019 (2)	−0.030 (2)

Geometric parameters (Å, º) top

Zn1—N1	1.990 (3)	C5—H5	0.9300
Zn1—O2	1.984 (2)	C6—C7	1.380 (4)
Zn1—O3ⁱ	1.993 (2)	C6—C8	1.502 (4)
Zn1—N4ⁱⁱ	2.022 (3)	C7—H7	0.9300
N1—C9	1.315 (4)	C9—H9	0.9300
N1—C10	1.371 (4)	C10—C11	1.350 (5)
N2—C9	1.338 (4)	C10—H10	0.9300
N2—C11	1.370 (4)	C11—H11	0.9300
N2—C12	1.469 (4)	C12—C13	1.501 (5)
N3—C20	1.318 (4)	C12—H12A	0.9700
N3—C22	1.372 (5)	C12—H12B	0.9700
N3—C19	1.459 (4)	C13—C14	1.380 (5)
N4—C20	1.320 (4)	C13—C18	1.396 (5)
N4—C21	1.369 (4)	C14—C15	1.380 (6)
N4—Zn1ⁱⁱⁱ	2.022 (3)	C14—H14	0.9300
O1—C1	1.231 (4)	C15—C16	1.360 (6)
O2—C1	1.281 (4)	C15—H15	0.9300
O3—C8	1.280 (4)	C16—C17	1.362 (6)
O3—Zn1^iv	1.993 (2)	C16—H16	0.9300
O4—C8	1.228 (4)	C17—C18	1.382 (5)
C1—C2	1.498 (4)	C17—H17	0.9300
C2—C3	1.372 (5)	C18—C19	1.511 (5)
C2—C7	1.388 (4)	C19—H19A	0.9700
C3—C4	1.382 (5)	C19—H19B	0.9700
C3—H3	0.9300	C20—H20	0.9300
C4—C5	1.380 (5)	C21—C22	1.349 (6)
C4—H4	0.9300	C21—H21	0.9300
C5—C6	1.379 (4)	C22—H22	0.9300

N1—Zn1—O2	102.90 (10)	N2—C9—H9	124.3
N1—Zn1—O3ⁱ	110.16 (10)	C11—C10—N1	110.0 (3)
O2—Zn1—O3ⁱ	101.36 (9)	C11—C10—H10	125.0
N1—Zn1—N4ⁱⁱ	120.15 (11)	N1—C10—H10	125.0
O2—Zn1—N4ⁱⁱ	108.84 (11)	C10—C11—N2	105.8 (3)
O3ⁱ—Zn1—N4ⁱⁱ	111.41 (10)	C10—C11—H11	127.1
C9—N1—C10	105.4 (3)	N2—C11—H11	127.1
C9—N1—Zn1	125.4 (2)	N2—C12—C13	112.8 (3)
C10—N1—Zn1	129.0 (2)	N2—C12—H12A	109.0
C9—N2—C11	107.3 (3)	C13—C12—H12A	109.0
C9—N2—C12	124.5 (3)	N2—C12—H12B	109.0
C11—N2—C12	127.7 (3)	C13—C12—H12B	109.0
C20—N3—C22	107.2 (3)	H12A—C12—H12B	107.8
C20—N3—C19	126.6 (3)	C14—C13—C18	119.2 (3)
C22—N3—C19	125.7 (3)	C14—C13—C12	118.6 (3)
C20—N4—C21	105.0 (3)	C18—C13—C12	122.1 (3)
C20—N4—Zn1ⁱⁱⁱ	126.6 (2)	C13—C14—C15	121.3 (4)
C21—N4—Zn1ⁱⁱⁱ	128.4 (2)	C13—C14—H14	119.4
C1—O2—Zn1	112.6 (2)	C15—C14—H14	119.4
C8—O3—Zn1^iv	104.77 (19)	C16—C15—C14	118.9 (4)
O1—C1—O2	123.4 (3)	C16—C15—H15	120.5
O1—C1—C2	119.9 (3)	C14—C15—H15	120.5
O2—C1—C2	116.6 (3)	C15—C16—C17	120.8 (4)
C3—C2—C7	118.9 (3)	C15—C16—H16	119.6
C3—C2—C1	122.2 (3)	C17—C16—H16	119.6
C7—C2—C1	118.9 (3)	C16—C17—C18	121.4 (4)
C2—C3—C4	120.8 (3)	C16—C17—H17	119.3
C2—C3—H3	119.6	C18—C17—H17	119.3
C4—C3—H3	119.6	C17—C18—C13	118.3 (3)
C3—C4—C5	119.7 (3)	C17—C18—C19	122.2 (3)
C3—C4—H4	120.2	C13—C18—C19	119.5 (3)
C5—C4—H4	120.2	N3—C19—C18	113.3 (3)
C6—C5—C4	120.5 (3)	N3—C19—H19A	108.9
C6—C5—H5	119.8	C18—C19—H19A	108.9
C4—C5—H5	119.8	N3—C19—H19B	108.9
C5—C6—C7	119.1 (3)	C18—C19—H19B	108.9
C5—C6—C8	122.0 (3)	H19A—C19—H19B	107.7
C7—C6—C8	118.9 (3)	N3—C20—N4	112.2 (3)
C2—C7—C6	121.0 (3)	N3—C20—H20	123.9
C2—C7—H7	119.5	N4—C20—H20	123.9
C6—C7—H7	119.5	C22—C21—N4	109.7 (3)
O4—C8—O3	122.7 (3)	C22—C21—H21	125.2
O4—C8—C6	120.2 (3)	N4—C21—H21	125.2
O3—C8—C6	117.1 (3)	C21—C22—N3	106.0 (3)
N1—C9—N2	111.5 (3)	C21—C22—H22	127.0
N1—C9—H9	124.3	N3—C22—H22	127.0

O2—Zn1—N1—C9	8.3 (3)	C12—N2—C9—N1	172.1 (3)
O3ⁱ—Zn1—N1—C9	−99.1 (3)	C9—N1—C10—C11	−0.7 (4)
N4ⁱⁱ—Zn1—N1—C9	129.4 (2)	Zn1—N1—C10—C11	174.3 (2)
O2—Zn1—N1—C10	−165.8 (3)	N1—C10—C11—N2	0.7 (4)
O3ⁱ—Zn1—N1—C10	86.8 (3)	C9—N2—C11—C10	−0.5 (4)
N4ⁱⁱ—Zn1—N1—C10	−44.7 (3)	C12—N2—C11—C10	−172.2 (3)
N1—Zn1—O2—C1	63.6 (2)	C9—N2—C12—C13	148.5 (3)
O3ⁱ—Zn1—O2—C1	177.6 (2)	C11—N2—C12—C13	−41.2 (5)
N4ⁱⁱ—Zn1—O2—C1	−64.9 (2)	N2—C12—C13—C14	96.4 (4)
Zn1—O2—C1—O1	4.6 (4)	N2—C12—C13—C18	−83.5 (4)
Zn1—O2—C1—C2	−175.2 (2)	C18—C13—C14—C15	0.1 (5)
O1—C1—C2—C3	−174.6 (3)	C12—C13—C14—C15	−179.8 (3)
O2—C1—C2—C3	5.2 (5)	C13—C14—C15—C16	0.3 (6)
O1—C1—C2—C7	4.3 (5)	C14—C15—C16—C17	−0.9 (7)
O2—C1—C2—C7	−175.8 (3)	C15—C16—C17—C18	1.1 (7)
C7—C2—C3—C4	−0.9 (5)	C16—C17—C18—C13	−0.7 (6)
C1—C2—C3—C4	178.1 (3)	C16—C17—C18—C19	−179.9 (4)
C2—C3—C4—C5	1.0 (6)	C14—C13—C18—C17	0.1 (5)
C3—C4—C5—C6	0.2 (5)	C12—C13—C18—C17	−180.0 (3)
C4—C5—C6—C7	−1.3 (5)	C14—C13—C18—C19	179.3 (3)
C4—C5—C6—C8	177.0 (3)	C12—C13—C18—C19	−0.8 (5)
C3—C2—C7—C6	−0.3 (5)	C20—N3—C19—C18	92.4 (4)
C1—C2—C7—C6	−179.3 (3)	C22—N3—C19—C18	−78.1 (5)
C5—C6—C7—C2	1.4 (5)	C17—C18—C19—N3	−7.6 (5)
C8—C6—C7—C2	−176.9 (3)	C13—C18—C19—N3	173.3 (3)
Zn1^iv—O3—C8—O4	−4.1 (4)	C22—N3—C20—N4	−0.5 (5)
Zn1^iv—O3—C8—C6	176.6 (2)	C19—N3—C20—N4	−172.4 (3)
C5—C6—C8—O4	170.8 (3)	C21—N4—C20—N3	0.6 (4)
C7—C6—C8—O4	−10.8 (5)	Zn1ⁱⁱⁱ—N4—C20—N3	179.9 (2)
C5—C6—C8—O3	−9.9 (5)	C20—N4—C21—C22	−0.4 (5)
C7—C6—C8—O3	168.4 (3)	Zn1ⁱⁱⁱ—N4—C21—C22	−179.7 (3)
C10—N1—C9—N2	0.3 (3)	N4—C21—C22—N3	0.2 (5)
Zn1—N1—C9—N2	−174.91 (19)	C20—N3—C22—C21	0.2 (5)
C11—N2—C9—N1	0.1 (4)	C19—N3—C22—C21	172.2 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O3^v	0.93	2.38	3.188 (4)	145
C11—H11···O4^vi	0.93	2.54	3.413 (4)	157
C14—H14···O1^vi	0.93	2.38	3.306 (7)	171
C19—H19B···O2^vii	0.97	2.38	3.200 (4)	142
C20—H20···O1ⁱⁱⁱ	0.93	2.34	3.016 (4)	130
C21—H21···O4^viii	0.93	2.54	3.092 (6)	119

Symmetry codes: (iii) x, y, z−1; (v) −x+1, −y+1, −z+2; (vi) −x, −y+2, −z+2; (vii) −x, −y+1, −z+2; (viii) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₄O₄)(C₁₄H₁₄N₄)]
M_r	467.77
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.2028 (14), 10.2744 (14), 11.4529 (16)
α, β, γ (°)	75.405 (2), 83.480 (2), 61.499 (2)
V (Å³)	1021.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.24
Crystal size (mm)	0.26 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.739, 0.790
No. of measured, independent and observed [I > 2σ(I)] reflections	5145, 3564, 3148
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.115, 1.02
No. of reflections	3564
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.52

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O3ⁱ	0.93	2.38	3.188 (4)	145
C11—H11···O4ⁱⁱ	0.93	2.54	3.413 (4)	157
C14—H14···O1ⁱⁱ	0.93	2.38	3.306 (7)	171
C19—H19B···O2ⁱⁱⁱ	0.97	2.38	3.200 (4)	142
C20—H20···O1^iv	0.93	2.34	3.016 (4)	130
C21—H21···O4^v	0.93	2.54	3.092 (6)	119

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

Acknowledgements

This work was supported by the Natural Science Foundation of Anhui Province (No. KJ2012A204).

References

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