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Acta Cryst. (2009). E65, m1239    [ doi:10.1107/S1600536809037696 ]

catena-Poly[[dichloridozinc(II)]-[mu]-1,1'-(hexane-1,6-diyl)diimidazole-[kappa]2N3:N3']

W.-L. Bao

Abstract top

In the structure of the polymeric title compound, [ZnCl2(C12H18N4)]n or [ZnCl2(L)]n, where L = 1,1'-(hexane-1,6-diyl)diimidazole, the ZnII centre is coordinated by two N atoms of two different L ligands and by two chloride anions in a distorted tetrahedral geometry. The organic ligand links adjacent metals to form a polymeric chain along the c axis. The chains are further connected into layers parallel to the bc plane by intermolecular C-H...Cl hydrogen bonds. Two C atoms of the central hexyl chain are disordered over two positions with site-occupancy factors of 0.5.

Comment top

The design and synthesis of metal-organic coordination polymers are of great interest due to their tremendous potential applications (Batten & Robson, 1998). The selection of the ligands is extremely important because changing their geometries can control the topologies of the resulting coordination frameworks. So far, the rigid rod-like spacer 4,4'-bipyridine is well known in the design of metal-organic polymers. However, flexible N-donor ligands such as 1,1'-(hexane-1,6-diyl)diimidazole (L) have not been so well explored (Yang et al., 2008).

The asymmetric unit of the title compound comprises a zinc(II) cation, a 1,1'-(hexane-1,6-diyl)diimidazole ligand, and two chloride anions (Fig. 1). The metal centre is coordinated by two N atoms of two different L ligands, and two Cl anions in a distorted tetrahedral geometry. The C4 and C5 carbon atoms of the hexyl chain are disordered over two positions with site occupancy factors of 0.5. The organic ligand links metal centers at (0.5-x, 1.-y, 0.5+z) and (0.5-x, 1.-y, -0.5+z) to form a polymeric one-dimensional chain (Fig. 2). Adjacent chains are connected by C—H···Cl hydrogen bonds (Table 1) into layers parallel to the bc plane.

Related literature top

For general background on coordination polymers, see: Batten & Robson (1998). For a related structure, see: Yang et al. (2008).

For related literature, see: Bruker (1998).

Experimental top

Zinc chloride (0.5 mmol) and L (0.5 mmol) were placed in water (12 ml), and triethylamine was added until the pH value of the solution was 5.5. The solution was heated in a 23-ml Teflon-lined stainless-steel autoclave at 450 K for 3 days. The autoclave was allowed to cool to room temperature over several hours. Colourless blocks were isolated in about 48% yield.

Refinement top

H atoms were generated geometrically and refined as riding atoms, with C—H = 0.93-0.96 Å and Uiso(H) = 1.2 Ueq(C). Disorder was noted in bridging L molecule. Two positions of equal site occupancy factor (0.5) were discerned for the C4 and C5 carbon atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound, showing the atomic numbering scheme and displacement ellipsoids drawn at the 30% probability level. Only one component of the disordered carbon atoms is shown. [Symmetry code: (i) 1/2-x, 1-y, 1/2+z].
[Figure 2] Fig. 2. View of the polymeric chain in the title compound. H atoms are omitted for clarity.
catena-Poly[[dichloridozinc(II)]-µ-1,1'-(hexane-1,6- diyl)diimidazole-κ2N3:N3'] top
Crystal data top
[ZnCl2(C12H18N4)]F(000) = 1456
Mr = 354.57Dx = 1.511 Mg m−3
Orthorhombic, PbcaCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ac 2abCell parameters from 2778 reflections
a = 11.255 (6) Åθ = 3.1–67.2°
b = 11.713 (8) ŵ = 5.27 mm−1
c = 23.653 (15) ÅT = 293 K
V = 3118 (3) Å3Block, colourless
Z = 80.31 × 0.25 × 0.22 mm
Data collection top
Oxford Diffraction Gemini R Ultra
diffractometer		2778 independent reflections
Radiation source: fine-focus sealed tube2080 reflections with I > 2σ(I)
graphiteRint = 0.053
Detector resolution: 10.0 pixels mm-1θmax = 67.2°, θmin = 5.4°
ω scansh = −12→13
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		k = −13→12
Tmin = 0.56, Tmax = 0.85l = −28→27
21446 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0617P)2 + 0.9261P]
where P = (Fo2 + 2Fc2)/3
2778 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.24 e Å−3
2 restraintsΔρmin = −0.39 e Å−3
Crystal data top
[ZnCl2(C12H18N4)]V = 3118 (3) Å3
Mr = 354.57Z = 8
Orthorhombic, PbcaCu Kα radiation
a = 11.255 (6) ŵ = 5.27 mm−1
b = 11.713 (8) ÅT = 293 K
c = 23.653 (15) Å0.31 × 0.25 × 0.22 mm
Data collection top
Oxford Diffraction Gemini R Ultra
diffractometer		2778 independent reflections
Absorption correction: multi-scan
(CrysAlis RED; Oxford Diffraction, 2006)		2080 reflections with I > 2σ(I)
Tmin = 0.56, Tmax = 0.85Rint = 0.053
21446 measured reflectionsθmax = 67.2°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.106Δρmax = 0.24 e Å−3
S = 1.02Δρmin = −0.39 e Å−3
2778 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
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 > 2sigma(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
xyzUiso*/UeqOcc. (<1)
C10.4404 (3)0.8003 (3)0.51805 (15)0.0642 (9)
H10.48920.86430.51670.077*
C20.4434 (4)0.7132 (4)0.48146 (17)0.0805 (12)
H20.49270.70610.45010.097*
C30.3080 (4)0.6823 (4)0.54427 (16)0.0786 (12)
H30.24600.64820.56400.094*
C40.3724 (8)0.5226 (7)0.4718 (3)0.0589 (17)0.50
H4A0.44250.51930.44800.071*0.50
H4B0.37660.46210.49980.071*0.50
C50.2614 (8)0.5143 (8)0.4375 (4)0.068 (2)0.50
H5A0.25800.57440.40940.082*0.50
H5B0.19160.51920.46150.082*0.50
C4'0.2942 (11)0.5275 (8)0.4825 (4)0.088 (3)0.50
H4'10.31110.46740.50950.105*0.50
H4'20.20910.54100.48230.105*0.50
C5'0.3341 (11)0.4935 (10)0.4261 (4)0.102 (4)0.50
H5'10.41910.48010.42670.122*0.50
H5'20.31830.55470.39950.122*0.50
C60.2708 (5)0.3860 (4)0.40691 (19)0.0887 (14)
H6A0.29730.33410.43630.106*
H6B0.18980.36410.39800.106*
C70.3336 (4)0.4423 (4)0.3080 (2)0.0847 (13)
H7A0.38630.41860.27780.102*
H7B0.36180.51560.32170.102*
C80.3429 (4)0.3571 (4)0.3554 (2)0.0870 (13)
H8A0.31780.28310.34150.104*
H8B0.42570.35060.36640.104*
C90.2099 (4)0.4585 (3)0.28368 (16)0.0683 (10)
H9A0.15630.48160.31370.082*
H9B0.21190.51930.25590.082*
C100.2002 (3)0.3110 (3)0.20743 (14)0.0615 (9)
H100.25830.34440.18490.074*
C110.0662 (3)0.1975 (3)0.23820 (14)0.0592 (8)
H110.01370.13640.24070.071*
C120.0775 (3)0.2814 (3)0.27673 (14)0.0615 (8)
H120.03520.28870.31030.074*
Zn10.31792 (3)0.87724 (3)0.625633 (16)0.04733 (16)
Cl10.43448 (8)1.03207 (8)0.61904 (4)0.0671 (2)
Cl20.12350 (7)0.91670 (9)0.63202 (3)0.0642 (2)
N10.3546 (2)0.7805 (2)0.55749 (10)0.0532 (6)
N20.3600 (5)0.6368 (3)0.49914 (15)0.0942 (13)
N30.1635 (3)0.3541 (2)0.25686 (11)0.0557 (7)
N40.1445 (2)0.2161 (3)0.19457 (10)0.0533 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0628 (19)0.069 (2)0.061 (2)0.0015 (17)0.0093 (16)−0.0059 (16)
C20.099 (3)0.080 (3)0.062 (2)0.024 (3)0.011 (2)−0.012 (2)
C30.121 (3)0.058 (2)0.057 (2)−0.023 (2)0.008 (2)−0.0031 (17)
C40.063 (4)0.060 (4)0.053 (4)0.013 (4)0.005 (4)−0.006 (3)
C50.065 (5)0.091 (6)0.050 (4)0.025 (4)0.000 (4)0.005 (4)
C4'0.107 (8)0.073 (6)0.084 (7)−0.017 (6)0.023 (6)−0.022 (5)
C5'0.089 (7)0.101 (8)0.116 (8)−0.031 (6)0.030 (6)−0.072 (7)
C60.123 (4)0.074 (3)0.069 (3)−0.021 (3)−0.019 (2)−0.0079 (19)
C70.078 (3)0.090 (3)0.087 (3)−0.021 (2)0.015 (2)−0.008 (2)
C80.064 (2)0.095 (3)0.103 (3)−0.007 (2)−0.012 (2)−0.003 (3)
C90.089 (3)0.052 (2)0.063 (2)−0.0029 (19)0.0126 (18)−0.0050 (15)
C100.073 (2)0.062 (2)0.0498 (17)−0.0024 (18)0.0185 (15)0.0018 (15)
C110.0557 (18)0.062 (2)0.0603 (19)−0.0009 (16)0.0095 (15)0.0014 (15)
C120.0626 (19)0.070 (2)0.0517 (18)0.0045 (19)0.0181 (15)−0.0010 (15)
Zn10.0504 (3)0.0487 (3)0.0429 (2)0.00272 (17)−0.00423 (16)−0.00345 (15)
Cl10.0643 (5)0.0595 (5)0.0776 (5)−0.0137 (4)−0.0092 (4)−0.0075 (4)
Cl20.0480 (4)0.0808 (6)0.0637 (5)0.0066 (4)−0.0064 (3)−0.0068 (4)
N10.0620 (15)0.0520 (16)0.0457 (13)−0.0003 (13)0.0016 (11)−0.0028 (11)
N20.176 (4)0.0519 (18)0.0544 (18)0.001 (2)0.001 (2)−0.0125 (14)
N30.0665 (16)0.0536 (16)0.0470 (14)0.0053 (13)0.0101 (12)−0.0004 (11)
N40.0555 (14)0.0562 (17)0.0481 (13)0.0054 (13)0.0080 (11)0.0016 (11)
Geometric parameters (Å, °) top
C1—C21.338 (6)C6—H6B0.9700
C1—N11.362 (4)C7—C81.505 (7)
C1—H10.9300C7—C91.519 (6)
C2—N21.362 (6)C7—H7A0.9700
C2—H20.9300C7—H7B0.9700
C3—N11.302 (5)C8—H8A0.9700
C3—N21.329 (6)C8—H8B0.9700
C3—H30.9300C9—N31.473 (5)
C4—C51.492 (12)C9—H9A0.9700
C4—N21.493 (8)C9—H9B0.9700
C4—H4A0.9700C10—N41.312 (5)
C4—H4B0.9700C10—N31.339 (4)
C5—C61.672 (10)C10—H100.9300
C5—H5A0.9700C11—C121.346 (5)
C5—H5B0.9700C11—N41.374 (4)
C4'—C5'1.464 (8)C11—H110.9300
C4'—N21.531 (7)C12—N31.372 (5)
C4'—H4'10.9700C12—H120.9300
C4'—H4'20.9700Zn1—N4i2.008 (3)
C5'—C61.516 (10)Zn1—N12.013 (3)
C5'—H5'10.9700Zn1—Cl22.2415 (13)
C5'—H5'20.9700Zn1—Cl12.2438 (12)
C6—C81.502 (7)N4—Zn1ii2.008 (3)
C6—H6A0.9700
C2—C1—N1109.3 (4)C8—C7—H7B108.4
C2—C1—H1125.3C9—C7—H7B108.4
N1—C1—H1125.3H7A—C7—H7B107.5
C1—C2—N2106.5 (4)C6—C8—C7114.6 (4)
C1—C2—H2126.7C6—C8—H8A108.6
N2—C2—H2126.7C7—C8—H8A108.6
N1—C3—N2111.7 (4)C6—C8—H8B108.6
N1—C3—H3124.1C7—C8—H8B108.6
N2—C3—H3124.1H8A—C8—H8B107.6
C5—C4—N2102.4 (6)N3—C9—C7112.7 (3)
C5—C4—H4A111.3N3—C9—H9A109.1
N2—C4—H4A111.3C7—C9—H9A109.1
C5—C4—H4B111.3N3—C9—H9B109.1
N2—C4—H4B111.3C7—C9—H9B109.1
H4A—C4—H4B109.2H9A—C9—H9B107.8
C4—C5—C6103.9 (6)N4—C10—N3112.0 (3)
C4—C5—H5A111.0N4—C10—H10124.0
C6—C5—H5A111.0N3—C10—H10124.0
C4—C5—H5B111.0C12—C11—N4109.4 (3)
C6—C5—H5B111.0C12—C11—H11125.3
H5A—C5—H5B109.0N4—C11—H11125.3
C5'—C4'—N2108.3 (7)C11—C12—N3106.7 (3)
C5'—C4'—H4'1110.0C11—C12—H12126.6
N2—C4'—H4'1110.0N3—C12—H12126.6
C5'—C4'—H4'2110.0N4i—Zn1—N1107.47 (11)
N2—C4'—H4'2110.0N4i—Zn1—Cl2105.25 (8)
H4'1—C4'—H4'2108.4N1—Zn1—Cl2111.74 (8)
C4'—C5'—C6110.8 (7)N4i—Zn1—Cl1111.93 (9)
C4'—C5'—H5'1109.5N1—Zn1—Cl1106.23 (9)
C6—C5'—H5'1109.5Cl2—Zn1—Cl1114.13 (5)
C4'—C5'—H5'2109.5C3—N1—C1105.8 (3)
C6—C5'—H5'2109.5C3—N1—Zn1127.4 (3)
H5'1—C5'—H5'2108.1C1—N1—Zn1126.7 (2)
C8—C6—C5'100.1 (5)C3—N2—C2106.7 (3)
C8—C6—C5126.0 (5)C3—N2—C4138.5 (5)
C8—C6—H6A105.8C2—N2—C4113.0 (5)
C5'—C6—H6A99.3C3—N2—C4'109.2 (5)
C5—C6—H6A105.8C2—N2—C4'143.5 (5)
C8—C6—H6B105.8C10—N3—C12106.5 (3)
C5'—C6—H6B136.6C10—N3—C9125.4 (3)
C5—C6—H6B105.8C12—N3—C9128.1 (3)
H6A—C6—H6B106.2C10—N4—C11105.5 (3)
C8—C7—C9115.4 (4)C10—N4—Zn1ii123.3 (2)
C8—C7—H7A108.4C11—N4—Zn1ii131.2 (3)
C9—C7—H7A108.4
Symmetry codes: (i) −x+1/2, −y+1, z+1/2; (ii) −x+1/2, −y+1, z−1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl1iii0.932.773.698 (5)176
Symmetry codes: (iii) −x+1/2, y−1/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···Cl1i0.932.773.698 (5)176
Symmetry codes: (i) −x+1/2, y−1/2, z.
Acknowledgements top

The author thanks the Jilin Public Security Academy for supporting this work.

references
References top

Batten, S. R. & Robson, R. (1998). Angew. Chem. Int. Ed. 37, 1460–1494.

Bruker (1998). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yang, J., Ma, J.-F., Batten, S. R. & Su, Z.-M. (2008). Chem. Commun. pp. 2233–2235.