Poly[bis­(1H-imidazole)bis­(μ2-1H-imidazolido)bis­(μ2-7-oxabicyclo­[2.2.1]heptane-2,3-dicarboxyl­ato)trizinc(II)]

Lin, Q.-Y.; Wang, N.; Wu, Y.-Z.

doi:10.1107/S1600536810017915

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages m705-m706

https://doi.org/10.1107/S1600536810017915

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Poly[bis(1H-imidazole)bis(μ₂-1H-imidazolido)bis(μ₂-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato)trizinc(II)]

Qiu-Yue Lin,^a,^b Na Wang ^a,^b and Yi-Zhou Wu ^c ^*

^aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China, ^bCollege of Chemistry and Life Science, Zhejiang Normal University, Jinhua 321004, Zhejiang, People's Republic of China, and ^cCollege of Public Administration, Zhejiang University, Hangzhou, Zhejiang 310027, People's Republic of China
^*Correspondence e-mail: zjuwyz@126.com

(Received 21 April 2010; accepted 14 May 2010; online 22 May 2010)

The title polymer, [Zn₃(C₈H₈O₅)₂(C₃H₃N₂)₂(C₃H₄N₂)₂]_n, was formed by the reaction of zinc acetate with imidazole and 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (norcantharidine). One of the two crystallographically unique Zn^II atoms is four-coordinated by three N atoms of three imidazole ligands, two of which are deprotonated, and by one carboxylate O atom of the demethylcantharate anion. The second Zn^II atom is situated on an inversion centre and is six-coordinated by the bridging O atoms of two symmetry-related demethylcantharate anions and by four carboxylate O atoms of the corresponding carboxylate groups. The polymeric crystal structure is additionally stabilized by N—H⋯O hydrogen bonding between the imidazole ligands and carboxylate O atoms.

Related literature

7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (norcantharidin) is a lower toxicity anticancer drug, see: Shimi et al. (1982 ). For cobalt complexes of norcantharidin, see: Wang et al. (1988 ) and for those including imidazole ligands, see: Furenlid et al. (1986 ); Zhu et al. (2003 ).

Experimental

Crystal data

[Zn₃(C₈H₈O₅)₂(C₃H₃N₂)₂(C₃H₄N₂)₂]
M_r = 834.71
Monoclinic, P 2₁ /c
a = 7.9993 (1) Å
b = 22.3923 (2) Å
c = 9.7586 (1) Å
β = 112.633 (1)°
V = 1613.37 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.28 mm⁻¹
T = 296 K
0.28 × 0.17 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.629, T_max = 0.822
13439 measured reflections
3714 independent reflections
3197 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.060
S = 1.03
3714 reflections
223 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O2	1.9570 (12)
Zn1—N1	1.9686 (14)
Zn1—N2ⁱ	1.9944 (14)
Zn1—N3	1.9968 (16)
Zn2—O5	2.0266 (12)
Zn2—O4	2.0819 (12)
Zn2—O1	2.1862 (12)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯O5ⁱⁱ	0.86	1.91	2.756 (2)	167
Symmetry code: (ii) -x+1, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810017915/wm2332sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017915/wm2332Isup2.hkl

checkCIF report

Comment top

7-oxabicyclo[2,2,1] heptane-2,3-dicarboxylic anhydride (norcantharidin) derived from cantharidin is a lower toxicity anticancer drug (Shimi et al., 1982). Imidazole is reputed as biocatalyst and biological ligand. Several cobalt complexes of norcantharidin (Wang et al., 1988) and of imidazole (Furenlid et al., 1986; Zhu et al., 2003) have been reported previously.

In the structure of the title compound, the Zn1(II) cation is four-coordinated by three nitrogen atoms of three imidazoles ligands, two of which are deprotonated, and by one carboxylate oxygen atom of the demethylcantharate anion. The deprotonated imidazole rings are responsible for bridging neighbouring Zn1 atoms. The Zn2(II) cation is located on a crystallographic centre of inversion. Two bridge oxygen atoms of two symmetry-related demethylcantharate anions and four carboxylate oxygen atoms give rise to a slightly distorted octahedral ZnO₆ coordination environment. Each demethylcantharate anion adopts simultaneously a bridging coordination mode (O2 towards Zn1, O4 towards Zn2) and a monodentate coordination mode (through O5 towards Zn2).

The crystal lattice is stabilized through N—H···O hydrogen bonds between the uncoordinated nitrogen atom (N4) of the imidazole molecule and one of the carboxylate oxygen atoms (O3) of the demethylcantharate anion.

Related literature top

7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (norcantharidin) is a lower toxicity anticancer drug, see: Shimi et al. (1982). For cobalt complexes of norcantharidin, see: Wang et al. (1988) and for those including imidazole ligands, see: Furenlid et al. (1986); Zhu et al. (2003).

Experimental top

7-oxabicyclo[2,2,1] heptane-2,3-dicarboxylic anhydride, zinc acetate and imidazole were dissolved in 15 mL distilled water. The mixture was sealed in a 25 mL Teflon-lined stainless vessel and heated at 443 K for 3 d, then cooled slowly to room temperature. Crystals suitable for X-ray diffraction were obtained.

Structure description top

7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride (norcantharidin) is a lower toxicity anticancer drug, see: Shimi et al. (1982). For cobalt complexes of norcantharidin, see: Wang et al. (1988) and for those including imidazole ligands, see: Furenlid et al. (1986); Zhu et al. (2003).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A view of the molecule of the title compound showing the atom-labelling and connectivity of the Zn^II atoms. Displacement ellipsoids drawn at the 30% probability level.

Poly[bis(1H-imidazole)bis(µ₂-1H-imidazolido)bis(µ₂- 7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylato)trizinc(II)] top

Crystal data top

[Zn₃(C₈H₈O₅)₂(C₃H₃N₂)₂(C₃H₄N₂)₂]	F(000) = 848
M_r = 834.71	D_x = 1.718 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5397 reflections
a = 7.9993 (1) Å	θ = 1.8–27.6°
b = 22.3923 (2) Å	µ = 2.28 mm⁻¹
c = 9.7586 (1) Å	T = 296 K
β = 112.633 (1)°	Block, colourless
V = 1613.37 (3) Å³	0.28 × 0.17 × 0.09 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3714 independent reflections
Radiation source: fine-focus sealed tube	3197 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 27.6°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.629, T_max = 0.822	k = −29→28
13439 measured reflections	l = −12→12

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.060	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0306P)² + 0.4382P] where P = (F_o² + 2F_c²)/3
3714 reflections	(Δ/σ)_max = 0.001
223 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Zn₃(C₈H₈O₅)₂(C₃H₃N₂)₂(C₃H₄N₂)₂]	V = 1613.37 (3) Å³
M_r = 834.71	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.9993 (1) Å	µ = 2.28 mm⁻¹
b = 22.3923 (2) Å	T = 296 K
c = 9.7586 (1) Å	0.28 × 0.17 × 0.09 mm
β = 112.633 (1)°

Data collection top

Bruker APEXII CCD diffractometer	3714 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3197 reflections with I > 2σ(I)
T_min = 0.629, T_max = 0.822	R_int = 0.023
13439 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.060	H-atom parameters constrained
S = 1.03	Δρ_max = 0.36 e Å⁻³
3714 reflections	Δρ_min = −0.28 e Å⁻³
223 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.02705 (3)	0.327653 (8)	0.68480 (2)	0.02488 (7)
Zn2	0.0000	0.5000	1.0000	0.02427 (8)
C1	0.5856 (3)	0.35035 (11)	0.8423 (3)	0.0508 (6)
H1A	0.7015	0.3415	0.8476	0.061*
C2	0.4334 (3)	0.31994 (10)	0.7673 (3)	0.0471 (5)
H2A	0.4259	0.2860	0.7103	0.057*
C3	0.3601 (3)	0.39293 (9)	0.8744 (2)	0.0391 (5)
H3A	0.2943	0.4196	0.9073	0.047*
C4	−0.1719 (3)	0.18968 (8)	0.8571 (2)	0.0333 (4)
H4A	−0.2451	0.1565	0.8488	0.040*
C5	−0.1783 (3)	0.22588 (8)	0.7447 (2)	0.0325 (4)
H5A	−0.2566	0.2218	0.6459	0.039*
C6	0.0280 (3)	0.25794 (8)	0.94487 (19)	0.0293 (4)
H6A	0.1206	0.2810	1.0110	0.035*
C7	−0.1093 (2)	0.44234 (7)	0.70651 (18)	0.0222 (3)
C8	−0.1796 (2)	0.50314 (7)	0.64085 (19)	0.0230 (3)
H8A	−0.2375	0.5001	0.5325	0.028*
C9	−0.3146 (2)	0.52910 (8)	0.70277 (19)	0.0267 (4)
H9A	−0.3937	0.4991	0.7198	0.032*
C10	−0.4169 (3)	0.58168 (8)	0.6063 (2)	0.0364 (4)
H10A	−0.5217	0.5927	0.6277	0.044*
H10B	−0.4555	0.5726	0.5015	0.044*
C11	−0.2716 (3)	0.63123 (8)	0.6539 (2)	0.0395 (5)
H11A	−0.2465	0.6459	0.5702	0.047*
H11B	−0.3078	0.6644	0.7003	0.047*
C12	−0.1090 (3)	0.59822 (8)	0.7649 (2)	0.0296 (4)
H12A	−0.0177	0.6248	0.8336	0.036*
C13	−0.0311 (2)	0.55369 (7)	0.68508 (19)	0.0250 (4)
H13A	−0.0282	0.5722	0.5950	0.030*
C14	0.1603 (2)	0.53377 (8)	0.78551 (19)	0.0265 (4)
N1	−0.0501 (2)	0.26968 (6)	0.80047 (16)	0.0281 (3)
N2	−0.0394 (2)	0.20990 (6)	0.98546 (16)	0.0288 (3)
N3	0.2899 (2)	0.34675 (7)	0.78774 (18)	0.0333 (4)
N4	0.5372 (2)	0.39636 (8)	0.9085 (2)	0.0429 (4)
H4B	0.6087	0.4232	0.9632	0.051*
O1	−0.19478 (17)	0.55896 (5)	0.83772 (13)	0.0271 (3)
O2	−0.09952 (19)	0.40346 (5)	0.61684 (13)	0.0326 (3)
O3	0.2753 (2)	0.52710 (8)	0.73430 (17)	0.0515 (4)
O4	−0.06572 (18)	0.43224 (5)	0.84191 (13)	0.0293 (3)
O5	0.19131 (16)	0.52692 (6)	0.92484 (13)	0.0299 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03053 (12)	0.02231 (11)	0.02322 (11)	−0.00257 (8)	0.01193 (9)	−0.00100 (7)
Zn2	0.02831 (15)	0.02813 (15)	0.01822 (14)	−0.00145 (11)	0.01100 (12)	−0.00224 (10)
C1	0.0314 (11)	0.0607 (14)	0.0607 (15)	−0.0008 (10)	0.0180 (11)	−0.0062 (12)
C2	0.0400 (12)	0.0476 (13)	0.0559 (14)	0.0009 (9)	0.0209 (11)	−0.0142 (10)
C3	0.0339 (10)	0.0342 (10)	0.0435 (12)	0.0002 (8)	0.0085 (9)	−0.0071 (9)
C4	0.0360 (10)	0.0285 (9)	0.0353 (11)	−0.0069 (8)	0.0135 (9)	0.0026 (8)
C5	0.0348 (10)	0.0339 (10)	0.0254 (9)	−0.0060 (8)	0.0077 (8)	0.0002 (7)
C6	0.0355 (10)	0.0247 (9)	0.0267 (9)	−0.0021 (7)	0.0107 (8)	0.0007 (7)
C7	0.0217 (8)	0.0222 (8)	0.0228 (9)	−0.0034 (6)	0.0088 (7)	−0.0027 (6)
C8	0.0265 (9)	0.0228 (8)	0.0185 (8)	−0.0016 (6)	0.0075 (7)	−0.0007 (6)
C9	0.0256 (9)	0.0266 (9)	0.0275 (9)	−0.0022 (7)	0.0096 (7)	−0.0005 (7)
C10	0.0303 (10)	0.0353 (10)	0.0400 (11)	0.0077 (8)	0.0095 (9)	0.0041 (8)
C11	0.0435 (12)	0.0266 (10)	0.0465 (12)	0.0070 (8)	0.0154 (10)	0.0055 (8)
C12	0.0342 (10)	0.0217 (8)	0.0334 (10)	−0.0031 (7)	0.0134 (8)	−0.0021 (7)
C13	0.0287 (9)	0.0253 (8)	0.0229 (8)	−0.0028 (7)	0.0121 (7)	0.0023 (6)
C14	0.0271 (9)	0.0272 (9)	0.0270 (9)	−0.0059 (7)	0.0124 (8)	−0.0009 (7)
N1	0.0341 (8)	0.0252 (7)	0.0249 (8)	−0.0016 (6)	0.0114 (7)	0.0028 (6)
N2	0.0376 (9)	0.0254 (8)	0.0256 (8)	0.0013 (6)	0.0148 (7)	0.0035 (6)
N3	0.0301 (8)	0.0309 (8)	0.0371 (9)	−0.0032 (7)	0.0110 (7)	−0.0046 (7)
N4	0.0319 (9)	0.0396 (9)	0.0461 (11)	−0.0091 (7)	0.0028 (8)	−0.0045 (8)
O1	0.0316 (7)	0.0272 (6)	0.0250 (6)	0.0010 (5)	0.0136 (5)	−0.0020 (5)
O2	0.0497 (8)	0.0243 (6)	0.0235 (6)	0.0059 (5)	0.0137 (6)	−0.0031 (5)
O3	0.0368 (8)	0.0864 (12)	0.0406 (9)	0.0114 (8)	0.0249 (7)	0.0152 (8)
O4	0.0439 (8)	0.0233 (6)	0.0203 (6)	0.0005 (5)	0.0120 (6)	−0.0004 (5)
O5	0.0258 (6)	0.0419 (7)	0.0226 (6)	−0.0049 (5)	0.0099 (5)	−0.0012 (5)

Geometric parameters (Å, º) top

Zn1—O2	1.9570 (12)	C6—H6A	0.9300
Zn1—N1	1.9686 (14)	C7—O4	1.251 (2)
Zn1—N2ⁱ	1.9944 (14)	C7—O2	1.2578 (19)
Zn1—N3	1.9968 (16)	C7—C8	1.518 (2)
Zn2—O5ⁱⁱ	2.0266 (12)	C8—C9	1.540 (2)
Zn2—O5	2.0266 (12)	C8—C13	1.576 (2)
Zn2—O4	2.0819 (12)	C8—H8A	0.9800
Zn2—O4ⁱⁱ	2.0819 (12)	C9—O1	1.459 (2)
Zn2—O1ⁱⁱ	2.1862 (12)	C9—C10	1.533 (2)
Zn2—O1	2.1862 (12)	C9—H9A	0.9800
C1—C2	1.340 (3)	C10—C11	1.543 (3)
C1—N4	1.350 (3)	C10—H10A	0.9700
C1—H1A	0.9300	C10—H10B	0.9700
C2—N3	1.376 (3)	C11—C12	1.525 (3)
C2—H2A	0.9300	C11—H11A	0.9700
C3—N3	1.317 (2)	C11—H11B	0.9700
C3—N4	1.327 (3)	C12—O1	1.457 (2)
C3—H3A	0.9300	C12—C13	1.537 (2)
C4—C5	1.349 (3)	C12—H12A	0.9800
C4—N2	1.369 (2)	C13—C14	1.533 (2)
C4—H4A	0.9300	C13—H13A	0.9800
C5—N1	1.371 (2)	C14—O3	1.213 (2)
C5—H5A	0.9300	C14—O5	1.294 (2)
C6—N1	1.329 (2)	N2—Zn1ⁱⁱⁱ	1.9944 (14)
C6—N2	1.330 (2)	N4—H4B	0.8600

O2—Zn1—N1	122.06 (6)	C10—C9—C8	109.78 (15)
O2—Zn1—N2ⁱ	97.25 (6)	O1—C9—H9A	113.8
N1—Zn1—N2ⁱ	104.86 (6)	C10—C9—H9A	113.8
O2—Zn1—N3	106.98 (6)	C8—C9—H9A	113.8
N1—Zn1—N3	110.76 (7)	C9—C10—C11	101.84 (15)
N2ⁱ—Zn1—N3	114.52 (7)	C9—C10—H10A	111.4
O5ⁱⁱ—Zn2—O5	180.000 (1)	C11—C10—H10A	111.4
O5ⁱⁱ—Zn2—O4	92.34 (5)	C9—C10—H10B	111.4
O5—Zn2—O4	87.66 (5)	C11—C10—H10B	111.4
O5ⁱⁱ—Zn2—O4ⁱⁱ	87.66 (5)	H10A—C10—H10B	109.3
O5—Zn2—O4ⁱⁱ	92.34 (5)	C12—C11—C10	101.71 (15)
O4—Zn2—O4ⁱⁱ	180.0	C12—C11—H11A	111.4
O5ⁱⁱ—Zn2—O1ⁱⁱ	89.15 (5)	C10—C11—H11A	111.4
O5—Zn2—O1ⁱⁱ	90.85 (5)	C12—C11—H11B	111.4
O4—Zn2—O1ⁱⁱ	90.17 (4)	C10—C11—H11B	111.4
O4ⁱⁱ—Zn2—O1ⁱⁱ	89.83 (4)	H11A—C11—H11B	109.3
O5ⁱⁱ—Zn2—O1	90.85 (5)	O1—C12—C11	101.88 (15)
O5—Zn2—O1	89.15 (5)	O1—C12—C13	102.39 (13)
O4—Zn2—O1	89.83 (4)	C11—C12—C13	110.85 (16)
O4ⁱⁱ—Zn2—O1	90.17 (4)	O1—C12—H12A	113.5
O1ⁱⁱ—Zn2—O1	180.0	C11—C12—H12A	113.5
C2—C1—N4	106.4 (2)	C13—C12—H12A	113.5
C2—C1—H1A	126.8	C14—C13—C12	111.41 (14)
N4—C1—H1A	126.8	C14—C13—C8	115.37 (13)
C1—C2—N3	109.4 (2)	C12—C13—C8	101.21 (13)
C1—C2—H2A	125.3	C14—C13—H13A	109.5
N3—C2—H2A	125.3	C12—C13—H13A	109.5
N3—C3—N4	110.88 (18)	C8—C13—H13A	109.5
N3—C3—H3A	124.6	O3—C14—O5	123.32 (17)
N4—C3—H3A	124.6	O3—C14—C13	120.10 (16)
C5—C4—N2	108.61 (16)	O5—C14—C13	116.54 (15)
C5—C4—H4A	125.7	C6—N1—C5	104.69 (15)
N2—C4—H4A	125.7	C6—N1—Zn1	127.96 (13)
C4—C5—N1	108.57 (16)	C5—N1—Zn1	126.56 (12)
C4—C5—H5A	125.7	C6—N2—C4	104.75 (14)
N1—C5—H5A	125.7	C6—N2—Zn1ⁱⁱⁱ	130.16 (12)
N1—C6—N2	113.37 (16)	C4—N2—Zn1ⁱⁱⁱ	125.09 (12)
N1—C6—H6A	123.3	C3—N3—C2	105.22 (17)
N2—C6—H6A	123.3	C3—N3—Zn1	126.68 (14)
O4—C7—O2	122.91 (15)	C2—N3—Zn1	127.52 (14)
O4—C7—C8	121.03 (15)	C3—N4—C1	108.14 (17)
O2—C7—C8	116.06 (15)	C3—N4—H4B	125.9
C7—C8—C9	112.03 (14)	C1—N4—H4B	125.9
C7—C8—C13	114.24 (14)	C12—O1—C9	96.04 (12)
C9—C8—C13	100.96 (13)	C12—O1—Zn2	112.31 (10)
C7—C8—H8A	109.8	C9—O1—Zn2	114.50 (9)
C9—C8—H8A	109.8	C7—O2—Zn1	121.81 (11)
C13—C8—H8A	109.8	C7—O4—Zn2	122.65 (10)
O1—C9—C10	102.25 (14)	C14—O5—Zn2	123.34 (11)
O1—C9—C8	102.16 (13)

N4—C1—C2—N3	−0.5 (3)	C1—C2—N3—C3	0.3 (3)
N2—C4—C5—N1	−0.1 (2)	C1—C2—N3—Zn1	171.94 (17)
O4—C7—C8—C9	−42.3 (2)	O2—Zn1—N3—C3	38.44 (19)
O2—C7—C8—C9	137.10 (16)	N1—Zn1—N3—C3	−96.74 (18)
O4—C7—C8—C13	71.7 (2)	N2ⁱ—Zn1—N3—C3	144.95 (17)
O2—C7—C8—C13	−108.87 (17)	O2—Zn1—N3—C2	−131.53 (18)
C7—C8—C9—O1	86.39 (15)	N1—Zn1—N3—C2	93.29 (19)
C13—C8—C9—O1	−35.59 (15)	N2ⁱ—Zn1—N3—C2	−25.0 (2)
C7—C8—C9—C10	−165.65 (14)	N3—C3—N4—C1	−0.4 (3)
C13—C8—C9—C10	72.37 (16)	C2—C1—N4—C3	0.5 (3)
O1—C9—C10—C11	33.06 (18)	C11—C12—O1—C9	57.35 (15)
C8—C9—C10—C11	−74.84 (18)	C13—C12—O1—C9	−57.40 (14)
C9—C10—C11—C12	2.0 (2)	C11—C12—O1—Zn2	176.96 (11)
C10—C11—C12—O1	−36.52 (18)	C13—C12—O1—Zn2	62.21 (13)
C10—C11—C12—C13	71.83 (19)	C10—C9—O1—C12	−55.89 (15)
O1—C12—C13—C14	−88.49 (16)	C8—C9—O1—C12	57.76 (14)
C11—C12—C13—C14	163.49 (15)	C10—C9—O1—Zn2	−173.78 (11)
O1—C12—C13—C8	34.66 (16)	C8—C9—O1—Zn2	−60.13 (13)
C11—C12—C13—C8	−73.36 (17)	O5ⁱⁱ—Zn2—O1—C12	170.75 (10)
C7—C8—C13—C14	0.5 (2)	O5—Zn2—O1—C12	−9.25 (10)
C9—C8—C13—C14	120.96 (15)	O4—Zn2—O1—C12	−96.91 (10)
C7—C8—C13—C12	−119.84 (15)	O4ⁱⁱ—Zn2—O1—C12	83.09 (10)
C9—C8—C13—C12	0.57 (16)	O5ⁱⁱ—Zn2—O1—C9	−81.07 (11)
C12—C13—C14—O3	−140.91 (18)	O5—Zn2—O1—C9	98.93 (11)
C8—C13—C14—O3	104.4 (2)	O4—Zn2—O1—C9	11.27 (11)
C12—C13—C14—O5	36.7 (2)	O4ⁱⁱ—Zn2—O1—C9	−168.73 (11)
C8—C13—C14—O5	−77.90 (19)	O4—C7—O2—Zn1	−11.7 (2)
N2—C6—N1—C5	0.4 (2)	C8—C7—O2—Zn1	168.88 (11)
N2—C6—N1—Zn1	−169.85 (12)	N1—Zn1—O2—C7	61.89 (16)
C4—C5—N1—C6	−0.2 (2)	N2ⁱ—Zn1—O2—C7	174.51 (14)
C4—C5—N1—Zn1	170.27 (13)	N3—Zn1—O2—C7	−67.06 (15)
O2—Zn1—N1—C6	−105.18 (16)	O2—C7—O4—Zn2	159.29 (13)
N2ⁱ—Zn1—N1—C6	146.15 (16)	C8—C7—O4—Zn2	−21.3 (2)
N3—Zn1—N1—C6	22.12 (17)	O5ⁱⁱ—Zn2—O4—C7	124.12 (14)
O2—Zn1—N1—C5	86.57 (16)	O5—Zn2—O4—C7	−55.88 (14)
N2ⁱ—Zn1—N1—C5	−22.11 (17)	O1ⁱⁱ—Zn2—O4—C7	−146.73 (14)
N3—Zn1—N1—C5	−146.14 (15)	O1—Zn2—O4—C7	33.27 (14)
N1—C6—N2—C4	−0.5 (2)	O3—C14—O5—Zn2	−150.62 (16)
N1—C6—N2—Zn1ⁱⁱⁱ	179.67 (12)	C13—C14—O5—Zn2	31.8 (2)
C5—C4—N2—C6	0.3 (2)	O4—Zn2—O5—C14	47.74 (14)
C5—C4—N2—Zn1ⁱⁱⁱ	−179.80 (13)	O4ⁱⁱ—Zn2—O5—C14	−132.26 (14)
N4—C3—N3—C2	0.1 (2)	O1ⁱⁱ—Zn2—O5—C14	137.88 (14)
N4—C3—N3—Zn1	−171.69 (14)	O1—Zn2—O5—C14	−42.12 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O5^iv	0.86	1.91	2.756 (2)	167

Symmetry code: (iv) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Zn₃(C₈H₈O₅)₂(C₃H₃N₂)₂(C₃H₄N₂)₂]
M_r	834.71
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.9993 (1), 22.3923 (2), 9.7586 (1)
β (°)	112.633 (1)
V (Å³)	1613.37 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.28
Crystal size (mm)	0.28 × 0.17 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.629, 0.822
No. of measured, independent and observed [I > 2σ(I)] reflections	13439, 3714, 3197
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.652

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.060, 1.03
No. of reflections	3714
No. of parameters	223
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.28

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Zn1—O2	1.9570 (12)	Zn2—O5	2.0266 (12)
Zn1—N1	1.9686 (14)	Zn2—O4	2.0819 (12)
Zn1—N2ⁱ	1.9944 (14)	Zn2—O1	2.1862 (12)
Zn1—N3	1.9968 (16)

Symmetry code: (i) x, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O5ⁱⁱ	0.86	1.91	2.756 (2)	166.9

Symmetry code: (ii) −x+1, −y+1, −z+2.

Acknowledgements

The authors acknowledge financial support from the Natural Science Foundation of Zhejiang Province, China (grant No. Y407301).

References

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