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

Lin, J.; Cai, W.-L.; Li, X.-Z.; Huang, S.-K.

doi:10.1107/S1600536810046611

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1580

https://doi.org/10.1107/S1600536810046611

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

Jing Lin,^a Wen-Lian Cai,^b Xi-Zhong Li ^b ^* and Sen-Ke Huang ^b

^aDepartment of Pharmacy, Xiamen University, Xiamen, Fujian 363105, People's Republic of China, and ^bDepartment of Chemistry and Environmental Science, Zhangzhou Normal University, Zhangzhou, Fujian,363000, People's Republic of China
^*Correspondence e-mail: xizhonglifjzs@yahoo.cn

(Received 24 October 2010; accepted 10 November 2010; online 17 November 2010)

The title one-dimensional coordination polymer, [ZnCl₂(C₁₀H₁₄N₄)]_n, was synthesized by hydrothermal methods from ZnCl₂ and 1,1′-(butane-1,4-diyl)diimidazole. The Zn atom is coordinated by two chloride ions and two N atoms from two symmetry-independent organic ligands and shows a distorted tetrahedral coordination geometry. The 1,1′-(butane-1,4-diyl)diimidazole ligands are located around two sets of inversion centers and bridge Zn^II ions, forming a zigzag polymeric chain. C—H⋯Cl hydrogen bonding results in the formation of a three-dimensional supramolecular network

Related literature

For general background to this work, see: Hamada et al. (2004 ); Wang et al. (2006 ).

Experimental

Crystal data

[ZnCl₂(C₁₀H₁₄N₄)]
M_r = 326.52
Monoclinic, P 2₁ /c
a = 7.8583 (16) Å
b = 11.689 (2) Å
c = 15.882 (3) Å
β = 93.82 (3)°
V = 1455.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.04 mm⁻¹
T = 293 K
0.34 × 0.27 × 0.22 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.428, T_max = 0.731
13865 measured reflections
3309 independent reflections
2701 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.126
S = 1.01
3309 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 1.33 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯Cl2ⁱ	0.93	2.77	3.601 (4)	149
C6—H6A⋯Cl1ⁱⁱ	0.93	2.65	3.553 (3)	164
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1994 ); cell refinement: SAINT (Siemens, 1994); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046611/gk2314sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046611/gk2314Isup2.hkl

checkCIF report

Comment top

The chemistry of novel metal–organic coordination complexes has attached more and more attention in recent years because of their interesting topologies and unexpected properties for potential applications . Recently, there has been increasing interest in zinc–halogen compounds because of their applications in molecular materials (Hamada et al. 2004; Wang et al., 2006). In this communication, we have introduced 1,1'-(butane-1,4-diyl)diimidazole (bbi) as a bridging ligand which favors crystal growth of the 1-D chain-like polymer. Through a mild-temperature hydrothermal process, we have successfully synthesized the title crystalline Cl-coordinated Zn complex, [ZnCl₂(C₁₀H₁₄N₄)]_n, (I).

The molecular structure of (I) is shown in Fig. 1. The compound features 1-D chain-like polymer complex, in which the Zn atom is coordinated by two Cl anions and two N atoms from two bbi ligands in a distorted tetrahedral geometry, in which the Zn—Cl (2.238 (1) and 2.2567 (9) Å) and Zn—N(2.010 (2) and 2.016 (3) Å) bond lengths are in the expected ranges. Each bbi ligand in the title compound is located on an inversion center and bridges Zn^II ions, forming a zigzag polymeric chain with the adjacent Zn···Zn separation of 13.971 Å.

The strong C—H···Cl hydrogen bonding results in the formation of a 3-D supramolecular network, as shown in Fig. 2.

Related literature top

For general background to this work, see: Hamada et al. (2004); Wang et al. (2006).

Experimental top

The hydrothermal reaction of ZnCl₂(0.041 g, 0.3 mmol), bbi (0.076 g, 0.4 mmol) and water (15.0 ml) was carried out at 423 K for 3 d. After cooling to room temperature at a rate of 5 K h^-1, block-shaped colorless crystals of the title compound suitable for X-ray analysis were obtained.

Structure description top

The strong C—H···Cl hydrogen bonding results in the formation of a 3-D supramolecular network, as shown in Fig. 2.

For general background to this work, see: Hamada et al. (2004); Wang et al. (2006).

Computing details top

Data collection: SMART (Siemens, 1994); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. View of the title coordination polymer showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level. Symmetry code: (i) -x, -1/2 + y, 1/2 - z; (ii) x, 3/2 - y, -1/2 + z.
	Fig. 2. Crystal packing viewed along the a axis. C-H···Cl contacts are shown with dashed lines

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 = 1.490 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13865 reflections
a = 7.8583 (16) Å	θ = 3.1–27.4°
b = 11.689 (2) Å	µ = 2.04 mm⁻¹
c = 15.882 (3) Å	T = 293 K
β = 93.82 (3)°	Block, colorless
V = 1455.6 (5) Å³	0.34 × 0.27 × 0.22 mm
Z = 4

Data collection top

Siemens SMART CCD area-detector diffractometer	3309 independent reflections
Radiation source: fine-focus sealed tube	2701 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 0 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
φ and ω scans	h = −10→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→15
T_min = 0.428, T_max = 0.731	l = −20→20
13865 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0822P)² + 0.5697P] where P = (F_o² + 2F_c²)/3
3309 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 1.33 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[ZnCl₂(C₁₀H₁₄N₄)]	V = 1455.6 (5) Å³
M_r = 326.52	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8583 (16) Å	µ = 2.04 mm⁻¹
b = 11.689 (2) Å	T = 293 K
c = 15.882 (3) Å	0.34 × 0.27 × 0.22 mm
β = 93.82 (3)°

Data collection top

Siemens SMART CCD area-detector diffractometer	3309 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2701 reflections with I > 2σ(I)
T_min = 0.428, T_max = 0.731	R_int = 0.036
13865 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.01	Δρ_max = 1.33 e Å⁻³
3309 reflections	Δρ_min = −0.35 e Å⁻³
154 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	0.03756 (4)	0.88757 (3)	0.221856 (19)	0.03812 (15)
Cl1	0.16460 (10)	1.03238 (7)	0.15605 (5)	0.0490 (2)
Cl2	−0.16703 (11)	0.94302 (9)	0.30450 (5)	0.0595 (3)
N1	−0.0583 (3)	0.7849 (2)	0.12834 (15)	0.0459 (6)
N2	−0.1741 (4)	0.6401 (3)	0.05838 (18)	0.0564 (7)
N3	0.2244 (3)	0.7996 (2)	0.28566 (15)	0.0414 (5)
N4	0.3570 (3)	0.6570 (2)	0.35199 (15)	0.0418 (5)
C1	−0.1396 (5)	0.6874 (3)	0.1340 (2)	0.0561 (9)
H1A	−0.1695	0.6554	0.1845	0.067*
C2	−0.0383 (5)	0.7996 (3)	0.0444 (2)	0.0604 (9)
H2A	0.0175	0.8607	0.0209	0.072*
C3	−0.1123 (6)	0.7112 (4)	0.0007 (2)	0.0692 (11)
H3A	−0.1192	0.7015	−0.0575	0.083*
C4	−0.2665 (6)	0.5326 (3)	0.0393 (3)	0.0721 (11)
H4A	−0.2590	0.4840	0.0890	0.087*
H4B	−0.2132	0.4926	−0.0055	0.087*
C5	−0.4511 (6)	0.5543 (3)	0.0128 (3)	0.0687 (11)
H5A	−0.4577	0.6072	−0.0344	0.082*
H5B	−0.5053	0.5904	0.0591	0.082*
C6	0.2058 (4)	0.7031 (3)	0.32738 (19)	0.0443 (7)
H6A	0.1011	0.6712	0.3383	0.053*
C7	0.3969 (4)	0.8154 (3)	0.2830 (2)	0.0539 (8)
H7A	0.4483	0.8769	0.2576	0.065*
C8	0.4809 (4)	0.7279 (3)	0.3232 (2)	0.0565 (9)
H8A	0.5984	0.7176	0.3299	0.068*
C9	0.3835 (4)	0.5474 (3)	0.3955 (2)	0.0487 (7)
H9A	0.4469	0.4969	0.3607	0.058*
H9B	0.2735	0.5123	0.4026	0.058*
C10	0.4794 (4)	0.5590 (3)	0.48174 (18)	0.0437 (7)
H10A	0.5842	0.6014	0.4762	0.052*
H10B	0.4102	0.6010	0.5195	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0373 (2)	0.0380 (2)	0.0379 (2)	−0.00093 (13)	−0.00600 (14)	0.00377 (12)
Cl1	0.0466 (4)	0.0420 (4)	0.0590 (5)	−0.0042 (3)	0.0084 (3)	0.0081 (3)
Cl2	0.0531 (5)	0.0777 (7)	0.0488 (4)	0.0073 (4)	0.0110 (4)	0.0122 (4)
N1	0.0504 (15)	0.0459 (14)	0.0400 (12)	−0.0080 (12)	−0.0086 (10)	0.0022 (11)
N2	0.0651 (19)	0.0498 (16)	0.0520 (15)	−0.0153 (14)	−0.0124 (14)	0.0002 (13)
N3	0.0360 (13)	0.0409 (13)	0.0460 (12)	0.0014 (10)	−0.0065 (10)	0.0084 (11)
N4	0.0400 (13)	0.0421 (14)	0.0422 (12)	0.0022 (11)	−0.0056 (10)	0.0072 (10)
C1	0.073 (2)	0.052 (2)	0.0418 (16)	−0.0170 (17)	−0.0112 (15)	0.0081 (14)
C2	0.073 (2)	0.064 (2)	0.0437 (16)	−0.0237 (19)	0.0012 (16)	0.0009 (16)
C3	0.087 (3)	0.077 (3)	0.0434 (17)	−0.028 (2)	0.0009 (18)	−0.0078 (18)
C4	0.087 (3)	0.051 (2)	0.074 (2)	−0.020 (2)	−0.022 (2)	0.0015 (19)
C5	0.081 (3)	0.057 (2)	0.065 (2)	−0.025 (2)	−0.0131 (19)	−0.0024 (18)
C6	0.0374 (15)	0.0431 (16)	0.0507 (16)	−0.0028 (13)	−0.0089 (12)	0.0069 (13)
C7	0.0449 (17)	0.057 (2)	0.0591 (19)	−0.0017 (15)	0.0001 (14)	0.0220 (16)
C8	0.0363 (16)	0.066 (2)	0.067 (2)	0.0072 (15)	0.0039 (14)	0.0189 (18)
C9	0.0534 (19)	0.0411 (17)	0.0499 (17)	0.0026 (14)	−0.0097 (14)	0.0074 (13)
C10	0.0476 (17)	0.0436 (17)	0.0393 (15)	0.0059 (13)	−0.0007 (12)	0.0060 (12)

Geometric parameters (Å, º) top

Zn1—N3	2.010 (2)	C3—H3A	0.9300
Zn1—N1	2.016 (3)	C4—C5	1.505 (6)
Zn1—Cl2	2.2381 (11)	C4—H4A	0.9700
Zn1—Cl1	2.2567 (9)	C4—H4B	0.9700
N1—C1	1.312 (4)	C5—C5ⁱ	1.525 (7)
N1—C2	1.363 (4)	C5—H5A	0.9700
N2—C1	1.334 (4)	C5—H5B	0.9700
N2—C3	1.352 (5)	C6—H6A	0.9300
N2—C4	1.472 (5)	C7—C8	1.354 (5)
N3—C6	1.322 (4)	C7—H7A	0.9300
N3—C7	1.371 (4)	C8—H8A	0.9300
N4—C6	1.339 (4)	C9—C10	1.524 (4)
N4—C8	1.380 (4)	C9—H9A	0.9700
N4—C9	1.464 (4)	C9—H9B	0.9700
C1—H1A	0.9300	C10—C10ⁱⁱ	1.522 (6)
C2—C3	1.353 (5)	C10—H10A	0.9700
C2—H2A	0.9300	C10—H10B	0.9700

N3—Zn1—N1	106.94 (11)	N2—C4—H4B	109.3
N3—Zn1—Cl2	112.43 (8)	C5—C4—H4B	109.3
N1—Zn1—Cl2	110.90 (8)	H4A—C4—H4B	108.0
N3—Zn1—Cl1	106.64 (8)	C4—C5—C5ⁱ	113.2 (5)
N1—Zn1—Cl1	105.09 (8)	C4—C5—H5A	108.9
Cl2—Zn1—Cl1	114.31 (4)	C5ⁱ—C5—H5A	108.9
C1—N1—C2	105.3 (3)	C4—C5—H5B	108.9
C1—N1—Zn1	128.8 (2)	C5ⁱ—C5—H5B	108.9
C2—N1—Zn1	125.7 (2)	H5A—C5—H5B	107.8
C1—N2—C3	107.1 (3)	N3—C6—N4	111.4 (3)
C1—N2—C4	127.4 (3)	N3—C6—H6A	124.3
C3—N2—C4	125.5 (3)	N4—C6—H6A	124.3
C6—N3—C7	105.8 (2)	C8—C7—N3	109.6 (3)
C6—N3—Zn1	126.0 (2)	C8—C7—H7A	125.2
C7—N3—Zn1	127.3 (2)	N3—C7—H7A	125.2
C6—N4—C8	107.1 (3)	C7—C8—N4	106.1 (3)
C6—N4—C9	125.8 (3)	C7—C8—H8A	126.9
C8—N4—C9	127.0 (3)	N4—C8—H8A	126.9
N1—C1—N2	111.7 (3)	N4—C9—C10	113.1 (3)
N1—C1—H1A	124.2	N4—C9—H9A	109.0
N2—C1—H1A	124.2	C10—C9—H9A	109.0
C3—C2—N1	109.4 (3)	N4—C9—H9B	109.0
C3—C2—H2A	125.3	C10—C9—H9B	109.0
N1—C2—H2A	125.3	H9A—C9—H9B	107.8
N2—C3—C2	106.5 (3)	C10ⁱⁱ—C10—C9	110.0 (3)
N2—C3—H3A	126.8	C10ⁱⁱ—C10—H10A	109.7
C2—C3—H3A	126.8	C9—C10—H10A	109.7
N2—C4—C5	111.5 (3)	C10ⁱⁱ—C10—H10B	109.7
N2—C4—H4A	109.3	C9—C10—H10B	109.7
C5—C4—H4A	109.3	H10A—C10—H10B	108.2

N3—Zn1—N1—C1	64.7 (3)	C1—N2—C3—C2	1.2 (5)
Cl2—Zn1—N1—C1	−58.2 (3)	C4—N2—C3—C2	179.5 (4)
Cl1—Zn1—N1—C1	177.8 (3)	N1—C2—C3—N2	−1.7 (5)
N3—Zn1—N1—C2	−109.5 (3)	C1—N2—C4—C5	97.3 (5)
Cl2—Zn1—N1—C2	127.6 (3)	C3—N2—C4—C5	−80.7 (5)
Cl1—Zn1—N1—C2	3.6 (3)	N2—C4—C5—C5ⁱ	176.4 (4)
N1—Zn1—N3—C6	−62.4 (3)	C7—N3—C6—N4	0.4 (4)
Cl2—Zn1—N3—C6	59.6 (3)	Zn1—N3—C6—N4	170.4 (2)
Cl1—Zn1—N3—C6	−174.4 (2)	C8—N4—C6—N3	−0.8 (4)
N1—Zn1—N3—C7	105.5 (3)	C9—N4—C6—N3	−176.6 (3)
Cl2—Zn1—N3—C7	−132.6 (3)	C6—N3—C7—C8	0.1 (4)
Cl1—Zn1—N3—C7	−6.6 (3)	Zn1—N3—C7—C8	−169.7 (2)
C2—N1—C1—N2	−0.7 (4)	N3—C7—C8—N4	−0.6 (4)
Zn1—N1—C1—N2	−175.9 (2)	C6—N4—C8—C7	0.9 (4)
C3—N2—C1—N1	−0.3 (5)	C9—N4—C8—C7	176.6 (3)
C4—N2—C1—N1	−178.6 (4)	C6—N4—C9—C10	−120.0 (3)
C1—N1—C2—C3	1.5 (5)	C8—N4—C9—C10	65.1 (4)
Zn1—N1—C2—C3	176.8 (3)	N4—C9—C10—C10ⁱⁱ	−173.2 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···Cl2ⁱⁱⁱ	0.93	2.77	3.601 (4)	149
C6—H6A···Cl1^iv	0.93	2.65	3.553 (3)	164

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

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₀H₁₄N₄)]
M_r	326.52
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.8583 (16), 11.689 (2), 15.882 (3)
β (°)	93.82 (3)
V (Å³)	1455.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.04
Crystal size (mm)	0.34 × 0.27 × 0.22

Data collection
Diffractometer	Siemens SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.428, 0.731
No. of measured, independent and observed [I > 2σ(I)] reflections	13865, 3309, 2701
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.126, 1.01
No. of reflections	3309
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.33, −0.35

Computer programs: SMART (Siemens, 1994), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···Cl2ⁱ	0.93	2.77	3.601 (4)	149.0
C6—H6A···Cl1ⁱⁱ	0.93	2.65	3.553 (3)	163.8

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

Acknowledgements

We are grateful for financial support from the Natural Science Foundation of Fujian (2008 J0172) and the Foundation of Fujian Education Committee (JA10205).

References

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