Poly[bis-(1H-imidazole)bis-(μ(2)-1H-imidazolido)bis-(μ(2)-7-oxabicyclo-[2.2.1]heptane-2,3-dicarboxyl-ato)trizinc(II)].

The title polymer, [Zn(3)(C(8)H(8)O(5))(2)(C(3)H(3)N(2))(2)(C(3)H(4)N(2))(2)](n), was formed by the reaction of zinc acetate with imidazole and 7-oxabicyclo-[2.2.1]heptane-2,3-dicarboxylic anhydride (norcan-tharidine). 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 carboxyl-ate O atom of the demethyl-cantharate 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 demethyl-cantharate anions and by four carboxyl-ate O atoms of the corresponding carboxyl-ate groups. The polymeric crystal structure is additionally stabilized by N-H⋯O hydrogen bonding between the imidazole ligands and carboxyl-ate 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 = 834.71

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.060

S = 1.03

3714 reflections

223 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.28 e Å−3

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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017915/wm2332Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn3(C8H8O5)2(C3H3N2)2(C3H4N2)2]	F(000) = 848
Mr = 834.71	Dx = 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

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

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(Fo2) + (0.0306P)2 + 0.4382P] where P = (Fo2 + 2Fc2)/3
3714 reflections	(Δ/σ)max = 0.001
223 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···O5iv	0.86	1.91	2.756 (2)	167

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) .

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) .