Bis[μ2-1,2-bis­(imidazol-1-ylmeth­yl)benzene-κ2N3:N3′]bis­[dichloridozinc(II)]

Hu, M.; Zhang, S.

doi:10.1107/S1600536809027044

metal-organic compounds

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Volume 65| Part 8| August 2009| Page m970

doi:10.1107/S1600536809027044

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Bis[μ₂-1,2-bis(imidazol-1-ylmethyl)benzene-κ²N³:N^3′]bis[dichloridozinc(II)]

Meihong Hu ^a ^* and Shishen Zhang ^b

^aDepartment of Biochemistry, College of Technology, Xiaogan University, Xiaogan, Hubei 432000, People's Republic of China, and ^bDepartment of Applied Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China
^*Correspondence e-mail: h5399000@yahoo.cn

(Received 14 June 2009; accepted 10 July 2009; online 22 July 2009)

In the crystal structure of the centrosymmetric title compound, [Zn₂Cl₄(C₁₄H₁₄N₄)₂], the Zn^II atom is coordinated by two N atoms from two 1,2-bis(imidazol-1-ylmethyl)benzene ligands and two Cl atoms to confer a distorted tetrahedral geometry at the metal center.

Related literature

For conformationally flexible ligands and their metal complexes, see: Carlucci et al. (2004 ); Fan et al. (2005 ); Hennigar et al. (1997 ). For metal complexes of similar ligands, see: Liu et al. (2007 ); Moulton & Zaworotko (2001 ); Tan et al. (2004 ).

Experimental

Crystal data

[Zn₂Cl₄(C₁₄H₁₄N₄)₂]
M_r = 749.12
Triclinic, $[P \overline 1]$
a = 8.5502 (12) Å
b = 8.7267 (13) Å
c = 11.5726 (17) Å
α = 102.824 (2)°
β = 105.720 (2)°
γ = 91.763 (2)°
V = 806.6 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.85 mm⁻¹
T = 291 K
0.20 × 0.15 × 0.12 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.709, T_max = 0.809
6327 measured reflections
3130 independent reflections
2912 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.084
S = 1.09
3130 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—N1	2.000 (2)
Zn1—N2ⁱ	2.017 (2)
Zn1—Cl1	2.2309 (8)
Zn1—Cl2	2.2428 (8)

N1—Zn1—N2ⁱ	108.85 (9)
Cl1—Zn1—Cl2	116.46 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); 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: 10.1107/S1600536809027044/ng2598sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027044/ng2598Isup2.hkl

checkCIF report

Comment top

Conformationally non-rigid ligands, showing varied geometries that often lead to supramolecular isomers, (Moulton et al., 2001; Hennigar et al., 1997) can more easily produce new classes of compounds. 1,2-bis-(imidazol-1-ylmethyl)benzene, as one kind of those ligands, has usually been used to construct a great variety of structurally interesting entities, such as 1-D chain, 2-D and 3-D nets (Liu et al., 2007; Fan et al., 2005; Tan et al., 2004).

The coordination environment of the title compound(I) is illustrated in Fig.1. Single-crystal X-ray diffraction shows that the asymmetric unit contains one Zn crystallographically nonequivalent atom. The Zn atom is coordinated by two N atoms from 1,2-bis-(imidazol-1-ylmethyl)benzene and two Cl atom to give a slightly distorted tetrahedral geometry, forming a 0-D structrue. The crystal packing is stabilized by intermolecular π-π stacking interaction (Fig. 2).

Related literature top

For conformationally flexible ligands and their metal complexes, see; Carlucci et al. (2004); Fan et al. (2005); Hennigar et al. (1997). For metal complexes of similar ligands, see: Liu et al. (2007); Moulton & Zaworotko (2001); Tan et al. (2004).

Experimental top

To a test tube (f= 2 cm) containing 3 ml aqueous solution of ZnCl₂ (0.006 g, 0.05 mmol) was added carefully a layer of THF as a buffer and then 5 ml of methanol solution of 1,2-bis-(imidazol-1-ylmethyl)benzene(0.027 g, 0.1 mmol). The system was allowed to stand for days, during which white crystals were formed in yield of ca 45%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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. Ellipsoid plot.
	Fig. 2. Packing diagram.

Bis[µ₂-1,2-bis(imidazol-1-ylmethyl)benzene- κ²N³:N^3')]bis[dichloridozinc(II)] top

Crystal data top

[Zn₂Cl₄(C₁₄H₁₄N₄)₂]	Z = 1
M_r = 749.12	F(000) = 380
Triclinic, P1	D_x = 1.542 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5502 (12) Å	Cell parameters from 3130 reflections
b = 8.7267 (13) Å	θ = 1.9–26.0°
c = 11.5726 (17) Å	µ = 1.85 mm⁻¹
α = 102.824 (2)°	T = 291 K
β = 105.720 (2)°	Block, white
γ = 91.763 (2)°	0.20 × 0.15 × 0.12 mm
V = 806.6 (2) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	3130 independent reflections
Radiation source: fine-focus sealed tube	2912 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.709, T_max = 0.809	k = −10→10
6327 measured reflections	l = −13→14

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0401P)² + 0.3649P] where P = (F_o² + 2F_c²)/3
3130 reflections	(Δ/σ)_max = 0.001
190 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

[Zn₂Cl₄(C₁₄H₁₄N₄)₂]	γ = 91.763 (2)°
M_r = 749.12	V = 806.6 (2) Å³
Triclinic, P1	Z = 1
a = 8.5502 (12) Å	Mo Kα radiation
b = 8.7267 (13) Å	µ = 1.85 mm⁻¹
c = 11.5726 (17) Å	T = 291 K
α = 102.824 (2)°	0.20 × 0.15 × 0.12 mm
β = 105.720 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	3130 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2912 reflections with I > 2σ(I)
T_min = 0.709, T_max = 0.809	R_int = 0.019
6327 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.09	Δρ_max = 0.42 e Å⁻³
3130 reflections	Δρ_min = −0.27 e Å⁻³
190 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	0.77170 (3)	0.60926 (3)	0.29452 (3)	0.03231 (11)
Cl1	0.67332 (9)	0.68391 (9)	0.11848 (6)	0.04696 (19)
Cl2	1.02202 (9)	0.52603 (9)	0.32757 (7)	0.04806 (19)
N1	0.6030 (3)	0.4485 (3)	0.2991 (2)	0.0369 (5)
N2	0.2055 (3)	0.2012 (2)	0.56368 (19)	0.0345 (5)
N3	0.3737 (3)	0.2956 (2)	0.2378 (2)	0.0348 (5)
N4	0.1141 (3)	0.0502 (3)	0.37642 (19)	0.0355 (5)
C1	0.1171 (3)	−0.0585 (3)	0.1590 (2)	0.0354 (6)
C2	0.2061 (3)	0.0452 (3)	0.1196 (2)	0.0340 (6)
C3	0.1073 (3)	0.1879 (3)	0.4517 (2)	0.0360 (6)
H3	0.0415	0.2650	0.4282	0.043*
C4	0.2099 (3)	0.2226 (3)	0.1610 (3)	0.0397 (6)
H4A	0.1774	0.2663	0.0890	0.048*
H4B	0.1321	0.2479	0.2081	0.048*
C5	0.4628 (3)	0.4045 (3)	0.2123 (2)	0.0372 (6)
H5	0.4303	0.4445	0.1423	0.045*
C6	0.0157 (3)	−0.0051 (4)	0.2462 (2)	0.0444 (7)
H6A	−0.0454	0.0798	0.2214	0.053*
H6B	−0.0623	−0.0921	0.2393	0.053*
C7	0.2892 (3)	−0.0154 (4)	0.0350 (3)	0.0430 (7)
H7	0.3476	0.0535	0.0076	0.052*
C8	0.1177 (4)	−0.2205 (3)	0.1138 (3)	0.0466 (7)
H8	0.0601	−0.2909	0.1407	0.056*
C9	0.4618 (4)	0.2681 (4)	0.3476 (3)	0.0526 (8)
H9	0.4305	0.1979	0.3888	0.063*
C10	0.2212 (4)	−0.0315 (3)	0.4443 (3)	0.0493 (7)
H10	0.2497	−0.1322	0.4167	0.059*
C11	0.2777 (4)	0.0627 (3)	0.5594 (3)	0.0465 (7)
H11	0.3536	0.0377	0.6253	0.056*
C12	0.2873 (4)	−0.1759 (4)	−0.0095 (3)	0.0529 (8)
H12	0.3440	−0.2143	−0.0663	0.063*
C13	0.2020 (4)	−0.2781 (4)	0.0301 (3)	0.0536 (8)
H13	0.2008	−0.3864	0.0006	0.064*
C14	0.6028 (4)	0.3625 (4)	0.3844 (3)	0.0503 (8)
H14	0.6865	0.3682	0.4564	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03700 (18)	0.02838 (17)	0.02722 (17)	−0.00505 (12)	0.00577 (12)	0.00311 (12)
Cl1	0.0514 (4)	0.0511 (4)	0.0332 (4)	−0.0078 (3)	0.0000 (3)	0.0161 (3)
Cl2	0.0478 (4)	0.0450 (4)	0.0513 (4)	0.0128 (3)	0.0123 (3)	0.0126 (3)
N1	0.0403 (12)	0.0338 (12)	0.0311 (11)	−0.0096 (9)	0.0042 (9)	0.0056 (9)
N2	0.0405 (12)	0.0316 (11)	0.0282 (11)	0.0006 (9)	0.0081 (9)	0.0028 (9)
N3	0.0337 (11)	0.0323 (11)	0.0355 (12)	−0.0045 (9)	0.0059 (9)	0.0078 (9)
N4	0.0420 (12)	0.0327 (12)	0.0289 (11)	−0.0066 (9)	0.0111 (9)	0.0012 (9)
C1	0.0353 (13)	0.0378 (14)	0.0267 (12)	−0.0059 (11)	0.0060 (11)	−0.0004 (10)
C2	0.0315 (12)	0.0367 (14)	0.0289 (13)	0.0000 (11)	0.0036 (10)	0.0044 (11)
C3	0.0409 (14)	0.0315 (13)	0.0331 (14)	0.0015 (11)	0.0096 (11)	0.0041 (11)
C4	0.0315 (13)	0.0351 (14)	0.0472 (16)	−0.0006 (11)	0.0063 (12)	0.0057 (12)
C5	0.0425 (15)	0.0348 (14)	0.0312 (14)	−0.0041 (11)	0.0059 (11)	0.0079 (11)
C6	0.0414 (15)	0.0506 (17)	0.0320 (14)	−0.0166 (13)	0.0093 (12)	−0.0048 (12)
C7	0.0387 (14)	0.0509 (17)	0.0423 (16)	0.0027 (13)	0.0159 (12)	0.0119 (13)
C8	0.0583 (18)	0.0347 (15)	0.0396 (16)	−0.0110 (13)	0.0089 (14)	0.0028 (12)
C9	0.0502 (17)	0.0552 (19)	0.0521 (18)	−0.0132 (14)	0.0030 (14)	0.0290 (15)
C10	0.072 (2)	0.0315 (15)	0.0442 (17)	0.0105 (14)	0.0202 (15)	0.0037 (12)
C11	0.0595 (18)	0.0429 (16)	0.0372 (15)	0.0118 (14)	0.0102 (14)	0.0133 (13)
C12	0.0480 (17)	0.061 (2)	0.0457 (18)	0.0137 (15)	0.0163 (14)	0.0000 (15)
C13	0.065 (2)	0.0349 (16)	0.0481 (18)	0.0098 (14)	0.0053 (15)	−0.0028 (13)
C14	0.0486 (17)	0.0542 (19)	0.0399 (16)	−0.0125 (14)	−0.0049 (13)	0.0187 (14)

Geometric parameters (Å, º) top

Zn1—N1	2.000 (2)	C3—H3	0.9300
Zn1—N2ⁱ	2.017 (2)	C4—H4A	0.9700
Zn1—Cl1	2.2309 (8)	C4—H4B	0.9700
Zn1—Cl2	2.2428 (8)	C5—H5	0.9300
N1—C5	1.320 (3)	C6—H6A	0.9700
N1—C14	1.366 (4)	C6—H6B	0.9700
N2—C3	1.317 (3)	C7—C12	1.379 (4)
N2—C11	1.371 (4)	C7—H7	0.9300
N2—Zn1ⁱ	2.017 (2)	C8—C13	1.377 (5)
N3—C5	1.330 (3)	C8—H8	0.9300
N3—C9	1.366 (4)	C9—C14	1.348 (4)
N3—C4	1.475 (3)	C9—H9	0.9300
N4—C3	1.332 (3)	C10—C11	1.350 (4)
N4—C10	1.365 (4)	C10—H10	0.9300
N4—C6	1.476 (3)	C11—H11	0.9300
C1—C2	1.392 (4)	C12—C13	1.363 (5)
C1—C8	1.395 (4)	C12—H12	0.9300
C1—C6	1.509 (4)	C13—H13	0.9300
C2—C7	1.383 (4)	C14—H14	0.9300
C2—C4	1.512 (4)

N1—Zn1—N2ⁱ	108.85 (9)	N1—C5—N3	111.4 (2)
N1—Zn1—Cl1	106.18 (7)	N1—C5—H5	124.3
N2ⁱ—Zn1—Cl1	108.10 (7)	N3—C5—H5	124.3
N1—Zn1—Cl2	112.82 (7)	N4—C6—C1	113.2 (2)
N2ⁱ—Zn1—Cl2	104.18 (7)	N4—C6—H6A	108.9
Cl1—Zn1—Cl2	116.46 (3)	C1—C6—H6A	108.9
C5—N1—C14	105.8 (2)	N4—C6—H6B	108.9
C5—N1—Zn1	123.62 (18)	C1—C6—H6B	108.9
C14—N1—Zn1	130.57 (18)	H6A—C6—H6B	107.7
C3—N2—C11	105.6 (2)	C12—C7—C2	121.4 (3)
C3—N2—Zn1ⁱ	123.80 (18)	C12—C7—H7	119.3
C11—N2—Zn1ⁱ	130.53 (19)	C2—C7—H7	119.3
C5—N3—C9	107.0 (2)	C13—C8—C1	121.1 (3)
C5—N3—C4	125.4 (2)	C13—C8—H8	119.4
C9—N3—C4	127.6 (2)	C1—C8—H8	119.4
C3—N4—C10	107.1 (2)	C14—C9—N3	106.7 (2)
C3—N4—C6	125.6 (2)	C14—C9—H9	126.6
C10—N4—C6	127.2 (2)	N3—C9—H9	126.6
C2—C1—C8	118.8 (2)	C11—C10—N4	106.5 (2)
C2—C1—C6	123.4 (2)	C11—C10—H10	126.7
C8—C1—C6	117.8 (3)	N4—C10—H10	126.7
C7—C2—C1	119.0 (2)	C10—C11—N2	109.2 (3)
C7—C2—C4	118.3 (2)	C10—C11—H11	125.4
C1—C2—C4	122.7 (2)	N2—C11—H11	125.4
N2—C3—N4	111.5 (2)	C13—C12—C7	119.8 (3)
N2—C3—H3	124.3	C13—C12—H12	120.1
N4—C3—H3	124.3	C7—C12—H12	120.1
N3—C4—C2	111.8 (2)	C12—C13—C8	119.9 (3)
N3—C4—H4A	109.3	C12—C13—H13	120.1
C2—C4—H4A	109.3	C8—C13—H13	120.1
N3—C4—H4B	109.3	C9—C14—N1	109.1 (3)
C2—C4—H4B	109.3	C9—C14—H14	125.4
H4A—C4—H4B	107.9	N1—C14—H14	125.4

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Zn₂Cl₄(C₁₄H₁₄N₄)₂]
M_r	749.12
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	8.5502 (12), 8.7267 (13), 11.5726 (17)
α, β, γ (°)	102.824 (2), 105.720 (2), 91.763 (2)
V (Å³)	806.6 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.85
Crystal size (mm)	0.20 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.709, 0.809
No. of measured, independent and observed [I > 2σ(I)] reflections	6327, 3130, 2912
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.084, 1.09
No. of reflections	3130
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.27

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Zn1—N1	2.000 (2)	Zn1—Cl1	2.2309 (8)
Zn1—N2ⁱ	2.017 (2)	Zn1—Cl2	2.2428 (8)

N1—Zn1—N2ⁱ	108.85 (9)	Cl1—Zn1—Cl2	116.46 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the Foundation of Young Researchers of the Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education (grant No. 2007QN05).

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