catena-Poly[[dichloridozinc(II)]-μ-1,1′-(butane-1,4-di­yl)diimidazole-κ2N3:N3′]

He, R.-L.; Meng, F.-J.; Wang, G.-H.; Yang, W.; Xu, J.-W.

doi:10.1107/S1600536810018246

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page m750

doi:10.1107/S1600536810018246

Open

access

catena-Poly[[dichloridozinc(II)]-μ-1,1′-(butane-1,4-diyl)diimidazole-κ²N³:N^3′]

Ren-Ling He,^a Fan-Jin Meng,^a Guan-Hua Wang,^a Wei Yang ^a and Jing-Wei Xu ^a ^*

^aThe State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China
^*Correspondence e-mail: jwxu@ciac.jl.cn

(Received 2 February 2010; accepted 17 May 2010; online 5 June 2010)

The title compound, [ZnCl₂(C₁₀H₁₄N₄)]_n, is a coordination polymer consisting of zigzag chains propagating in [001], in which the metal cation exhibits a distorted tetrahedral ZnCl₂N₂ coordination. Adjacent chains are linked by intermolecular C—H⋯Cl hydrogen bonds, forming a three-dimensional supramolecular network.

Related literature

For general background to metal complexes of N-heterocyclic compounds, see: Hu et al. (2003 ); Ohmori et al. (2005 ); Chen et al. (2004 ); Hu et al. (2005 ). For related structures, see: Li et al. (2006 ); Liu et al. (2007 ); Jin et al. (2007 ); Yang et al. (2009 ); Qi et al. (2008 ).

Experimental

Crystal data

[ZnCl₂(C₁₀H₁₄N₄)]
M_r = 326.52
Monoclinic, P 2₁ /c
a = 7.8090 (9) Å
b = 11.6001 (13) Å
c = 15.8047 (18) Å
β = 92.908 (2)°
V = 1429.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.08 mm⁻¹
T = 185 K
0.29 × 0.22 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.585, T_max = 0.742
7827 measured reflections
2820 independent reflections
2174 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.107
S = 1.06
2820 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl1ⁱ	0.93	2.63	3.538 (2)	166
C5—H5⋯Cl2ⁱⁱ	0.93	2.78	3.599 (5)	147
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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 Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018246/ez2200sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810018246/ez2200Isup2.hkl

checkCIF report

Comment top

N-heterocyclic compounds have been extensively studied in coordination chemistry research for their excellent bridging ability (Hu et al., 2003; Ohmori et al., 2005; Chen et al., 2004; Hu et al., 2005). The compound 1,1'-(1,4-butanediyl)bis(imidazole) (bbi), as a flexible nitrogenous ligand with a long -CH₂CH₂CH₂CH₂- spacer, can link discrete clusters into an extended network and is a good candidate to form highly connected 3D frameworks. A number of metal-bbi coordination polymers have been reported (Li et al., 2006; Liu et al., 2007; Jin et al., 2007; Yang et al., 2009; Qi et al., 2008). Here we present a new polymeric compound, [ZnCl₂(bbi)]_n, (I), with a zigzag chain structure, synthesized under solvothermal conditions.

In the title compound, (I), the Zn centers are four-coordinated by two N atoms from two bbi ligands [Zn(1)—N(1) = 2.005 (3) Å and Zn(1)—N(3) = 2.013 (3) Å] and two Cl atoms [Zn(1)—Cl(1) = 2.2557 (11) Å and Zn(1)—Cl(2) =2.2321 (12) Å], resulting in a distorted tetrahedral geometry (Fig. 1). Each bbi coordinates to two Zn atoms through its two aromatic N atoms and acts as a bridging bidentate ligand to form a one-dimensional zigzag chain (Fig. 2). The adjacent Zn···Zn distance is 14.290 Å, which is similar to that observed in [Cu₂(bbi)₂Cl₂] (Qi et al., 2008). In addition, these one-dimensional chains are further connected by weak intermolecular C—H···Cl hydrogen bonds to construct a three-dimensional supramolecular network (Fig. 2).

Related literature top

For general background to metal complexes of N-heterocyclic compounds, see: Hu et al. (2003); Ohmori et al. (2005); Chen et al. (2004); Hu et al. (2005). For related structures, see: Li et al. (2006); Liu et al. (2007); Jin et al. (2007); Yang et al. (2009); Qi et al. (2008).

Experimental top

The title compound was solvothermally prepared from a reaction mixture of ZnCl₂ (0.3 mmol), bbi (0.1 mmol), ethanol (3 ml) and distilled water (7 ml); the pH value was adjusted to 4.5 with triethylamine and acetic acid. The mixture was stirred for 20 min at room temperature, then sealed in a 20 ml teflon-lined stainless steel autoclave and heated at 433 K for 72 h under autogenous pressure. After cooling to room temperature, colorless block crystals were obtained (yield 83% based on Zn).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Partial molecular structure of the title compound showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Atoms marked with i or ii are at the symmetry positions (x+2, y+5/2, 3/2-z) and (x, y+5/2, 1/2-z) respectively.
	Fig. 2. The zigzag polymeric chain structure of the title compound. Dashed lines denote hydrogen bonds.

catena-Poly[[dichloridozinc(II)]-µ-1,1'-(butane-1,4-diyl)diimidazole- κ²N³:N^3'] top

Crystal data top

[ZnCl₂(C₁₀H₁₄N₄)]	F(000) = 664
M_r = 326.52	D_x = 1.517 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2763 reflections
a = 7.8090 (9) Å	θ = 2.2–26.1°
b = 11.6001 (13) Å	µ = 2.08 mm⁻¹
c = 15.8047 (18) Å	T = 185 K
β = 92.908 (2)°	Block, colorless
V = 1429.8 (3) Å³	0.29 × 0.22 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2820 independent reflections
Radiation source: fine-focus sealed tube	2174 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 26.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.585, T_max = 0.742	k = −11→14
7827 measured reflections	l = −19→19

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0437P)² + 0.2952P] where P = (F_o² + 2F_c²)/3
2820 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.68 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[ZnCl₂(C₁₀H₁₄N₄)]	V = 1429.8 (3) Å³
M_r = 326.52	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8090 (9) Å	µ = 2.08 mm⁻¹
b = 11.6001 (13) Å	T = 185 K
c = 15.8047 (18) Å	0.29 × 0.22 × 0.15 mm
β = 92.908 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	2820 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2174 reflections with I > 2σ(I)
T_min = 0.585, T_max = 0.742	R_int = 0.054
7827 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.06	Δρ_max = 0.68 e Å⁻³
2820 reflections	Δρ_min = −0.36 e Å⁻³
154 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	0.46384 (6)	0.61215 (4)	0.27801 (3)	0.02355 (16)
Cl1	0.33311 (13)	0.46729 (9)	0.34476 (7)	0.0299 (3)
Cl2	0.67102 (14)	0.55460 (11)	0.19540 (7)	0.0370 (3)
N2	0.1432 (4)	0.8426 (3)	0.1480 (2)	0.0244 (8)
N1	0.2770 (4)	0.6993 (3)	0.2141 (2)	0.0249 (8)
N3	0.5563 (4)	0.7158 (3)	0.3717 (2)	0.0289 (9)
N4	0.6711 (5)	0.8617 (3)	0.4421 (2)	0.0341 (10)
C1	0.1030 (5)	0.6818 (4)	0.2160 (3)	0.0319 (11)
H1	0.0509	0.6195	0.2413	0.038*
C2	0.0202 (6)	0.7689 (4)	0.1755 (3)	0.0342 (11)
H2	−0.0980	0.7776	0.1676	0.041*
C3	0.2941 (5)	0.7974 (4)	0.1726 (3)	0.0283 (10)
H3	0.3992	0.8307	0.1620	0.034*
C6	0.5363 (6)	0.6995 (4)	0.4562 (3)	0.0384 (12)
H6	0.4815	0.6368	0.4796	0.046*
C5	0.6077 (6)	0.7875 (4)	0.5003 (3)	0.0423 (13)
H5	0.6131	0.7965	0.5589	0.051*
C4	0.6379 (6)	0.8141 (4)	0.3661 (3)	0.0359 (11)
H4	0.6688	0.8468	0.3153	0.043*
C7	0.1145 (6)	0.9520 (4)	0.1043 (3)	0.0302 (11)
H7A	0.2243	0.9890	0.0974	0.036*
H7B	0.0478	1.0018	0.1393	0.036*
C8	0.0227 (5)	0.9402 (4)	0.0186 (3)	0.0261 (10)
H8A	−0.0814	0.8957	0.0238	0.031*
H8B	0.0952	0.8993	−0.0194	0.031*
C9	0.7655 (6)	0.9682 (4)	0.4623 (3)	0.0438 (13)
H9A	0.7132	1.0070	0.5089	0.053*
H9B	0.7574	1.0192	0.4136	0.053*
C10	0.9514 (6)	0.9456 (4)	0.4862 (3)	0.0423 (13)
H10A	1.0055	0.9121	0.4380	0.051*
H10B	0.9591	0.8899	0.5320	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0249 (3)	0.0224 (3)	0.0230 (3)	−0.0008 (2)	−0.00252 (19)	0.0021 (2)
Cl1	0.0288 (6)	0.0250 (6)	0.0366 (6)	−0.0026 (5)	0.0069 (5)	0.0052 (5)
Cl2	0.0349 (6)	0.0457 (8)	0.0311 (6)	0.0052 (6)	0.0072 (5)	0.0077 (5)
N2	0.0253 (19)	0.024 (2)	0.0237 (18)	0.0029 (16)	−0.0019 (15)	0.0046 (15)
N1	0.0265 (19)	0.023 (2)	0.0247 (19)	0.0014 (16)	−0.0006 (15)	0.0043 (16)
N3	0.031 (2)	0.028 (2)	0.027 (2)	−0.0034 (17)	−0.0035 (16)	0.0027 (16)
N4	0.039 (2)	0.031 (2)	0.031 (2)	−0.0085 (18)	−0.0086 (18)	−0.0007 (17)
C1	0.028 (2)	0.034 (3)	0.034 (3)	−0.001 (2)	0.002 (2)	0.015 (2)
C2	0.022 (2)	0.038 (3)	0.043 (3)	−0.002 (2)	0.003 (2)	0.012 (2)
C3	0.026 (2)	0.031 (3)	0.028 (2)	−0.003 (2)	−0.0038 (18)	0.004 (2)
C6	0.048 (3)	0.040 (3)	0.028 (3)	−0.018 (3)	0.000 (2)	0.001 (2)
C5	0.054 (3)	0.048 (3)	0.024 (2)	−0.011 (3)	−0.001 (2)	0.001 (2)
C4	0.045 (3)	0.035 (3)	0.027 (2)	−0.007 (2)	−0.006 (2)	0.005 (2)
C7	0.036 (3)	0.022 (3)	0.032 (3)	−0.001 (2)	−0.002 (2)	0.005 (2)
C8	0.024 (2)	0.030 (3)	0.025 (2)	0.005 (2)	0.0043 (18)	0.0050 (19)
C9	0.057 (3)	0.037 (3)	0.037 (3)	−0.018 (3)	−0.007 (2)	0.003 (2)
C10	0.052 (3)	0.034 (3)	0.039 (3)	−0.017 (3)	−0.008 (2)	0.002 (2)

Geometric parameters (Å, º) top

Zn1—N1	2.005 (3)	C3—H3	0.9300
Zn1—N3	2.013 (3)	C6—C5	1.342 (7)
Zn1—Cl2	2.2321 (12)	C6—H6	0.9300
Zn1—Cl1	2.2557 (11)	C5—H5	0.9300
N2—C3	1.330 (5)	C4—H4	0.9300
N2—C2	1.373 (5)	C7—C8	1.506 (6)
N2—C7	1.457 (5)	C7—H7A	0.9700
N1—C3	1.323 (5)	C7—H7B	0.9700
N1—C1	1.375 (5)	C8—C8ⁱ	1.540 (8)
N3—C4	1.312 (6)	C8—H8A	0.9700
N3—C6	1.364 (5)	C8—H8B	0.9700
N4—C4	1.336 (5)	C9—C10	1.504 (6)
N4—C5	1.369 (6)	C9—H9A	0.9700
N4—C9	1.466 (6)	C9—H9B	0.9700
C1—C2	1.344 (6)	C10—C10ⁱⁱ	1.524 (9)
C1—H1	0.9300	C10—H10A	0.9700
C2—H2	0.9300	C10—H10B	0.9700

N1—Zn1—N3	107.13 (14)	C6—C5—N4	106.5 (4)
N1—Zn1—Cl2	112.74 (10)	C6—C5—H5	126.8
N3—Zn1—Cl2	111.43 (11)	N4—C5—H5	126.8
N1—Zn1—Cl1	106.02 (10)	N3—C4—N4	111.7 (4)
N3—Zn1—Cl1	104.75 (11)	N3—C4—H4	124.1
Cl2—Zn1—Cl1	114.17 (5)	N4—C4—H4	124.1
C3—N2—C2	106.6 (4)	N2—C7—C8	113.7 (4)
C3—N2—C7	126.6 (4)	N2—C7—H7A	108.8
C2—N2—C7	126.8 (4)	C8—C7—H7A	108.8
C3—N1—C1	105.2 (4)	N2—C7—H7B	108.8
C3—N1—Zn1	126.4 (3)	C8—C7—H7B	108.8
C1—N1—Zn1	127.5 (3)	H7A—C7—H7B	107.7
C4—N3—C6	105.5 (4)	C7—C8—C8ⁱ	110.6 (5)
C4—N3—Zn1	128.8 (3)	C7—C8—H8A	109.5
C6—N3—Zn1	125.6 (3)	C8ⁱ—C8—H8A	109.5
C4—N4—C5	106.5 (4)	C7—C8—H8B	109.5
C4—N4—C9	128.0 (4)	C8ⁱ—C8—H8B	109.5
C5—N4—C9	125.3 (4)	H8A—C8—H8B	108.1
C2—C1—N1	109.3 (4)	N4—C9—C10	112.1 (4)
C2—C1—H1	125.3	N4—C9—H9A	109.2
N1—C1—H1	125.3	C10—C9—H9A	109.2
C1—C2—N2	106.9 (4)	N4—C9—H9B	109.2
C1—C2—H2	126.5	C10—C9—H9B	109.2
N2—C2—H2	126.5	H9A—C9—H9B	107.9
N1—C3—N2	112.0 (4)	C9—C10—C10ⁱⁱ	112.8 (5)
N1—C3—H3	124.0	C9—C10—H10A	109.0
N2—C3—H3	124.0	C10ⁱⁱ—C10—H10A	109.0
C5—C6—N3	109.7 (4)	C9—C10—H10B	109.0
C5—C6—H6	125.1	C10ⁱⁱ—C10—H10B	109.0
N3—C6—H6	125.1	H10A—C10—H10B	107.8

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱⁱⁱ	0.93	2.63	3.538 (2)	166
C5—H5···Cl2^iv	0.93	2.78	3.599 (5)	147

Symmetry codes: (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₀H₁₄N₄)]
M_r	326.52
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	185
a, b, c (Å)	7.8090 (9), 11.6001 (13), 15.8047 (18)
β (°)	92.908 (2)
V (Å³)	1429.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.08
Crystal size (mm)	0.29 × 0.22 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.585, 0.742
No. of measured, independent and observed [I > 2σ(I)] reflections	7827, 2820, 2174
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.107, 1.06
No. of reflections	2820
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.36

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱ	0.93	2.63	3.538 (2)	166
C5—H5···Cl2ⁱⁱ	0.93	2.78	3.599 (5)	147

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+3/2, z+1/2.

Acknowledgements

The authors thank Changchun Institute of Applied Chemistry for supporting this work.

References

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, Y.-B., Kang, Y., Qin, Y.-Y., Li, Z.-J., Cheng, J.-K., Hu, R.-F., Wen, Y.-H. & Yao, Y.-G. (2004). Acta Cryst. C60, m168–m169. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Hu, S., Chen, J.-C., Tong, M.-L., Wang, B., Yan, Y.-X. & Batten, S. R. (2005). Angew. Chem. Int. Ed. 44, 5471–5475. Web of Science CSD CrossRef CAS Google Scholar
Hu, X.-L., Tang, Y.-J., Gantzel, P. & Meyer, K. (2003). J. Am. Chem. Soc. 22, 612–614. CAS Google Scholar
Jin, S.-W., Wang, D.-Q. & Chen, W.-Z. (2007). Inorg. Chem. Commun. 10, 685–689. Web of Science CSD CrossRef CAS Google Scholar
Li, F.-F., Ma, J.-F., Song, S.-Y., Yang, J., Jia, H. Q. & Hu, N.-H. (2006). Cryst. Growth Des. 6, 209–215. Web of Science CSD CrossRef CAS Google Scholar
Liu, Y.-Y., Ma, J.-F. & Zhang, L.-P. (2007). Acta Cryst. E63, m2317. Web of Science CSD CrossRef IUCr Journals Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ohmori, O., Kawano, M. & Fujita, M. (2005). Angew. Chem. Int. Ed. 44, 1962–1964. Web of Science CSD CrossRef CAS Google Scholar
Qi, Y., Luo, F., Batten, S. R., Che, Y.-X. & Zheng, J.-M. (2008). Cryst. Growth Des. 8, 2806–2813. Web of Science CSD 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
Yang, J., Ma, J.-F., Liu, Y.-Y. & Batten, S. R. (2009). CrystEngComm, 11, 151–159. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.