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Acta Cryst. (2007). E63, m2875    [ doi:10.1107/S1600536807053159 ]

catena-Poly[[bis(1-ethylimidazole-[kappa]N3)zinc(II)]-[mu]-phthalato-[kappa]2O1:O2\]

R.-X. Li, S.-X. Li, L. Liu, G.-Y. Liu and F.-Q. Liu

Abstract top

In the solid state, the title compound, [Zn(C8H4O4)(C5H8N2)2]n, exhibits polymeric zigzag chains extended along th c axis. Each ZnII ion is coordinated by two N and two O atoms in a distorted tetrahedral geometry. Weak C-H...O interactions contribute to the crystal packing stability.

Comment top

In the title compound,(I)(Fig. 1), The zinc(II) centers are bridged by the carboxylate group of o-phthalate and saturated by 1-ethylimidazole. Each ZnII ion is coordinated by two N [Zn—N1 = 1.993 (8), Zn—N3 = 2.028 (8) Å] and two O [Zn—O2 = 1.974 (6), Zn—O3 = 1.976 (7) Å] atoms in a distorted tetrahedral geometry. All these values agree well with those observed in [Zn(phthalato)(1-H-imidazole)2] (Liu et al., 2002). Each o-phthalate dianion acts as a bidentate ligand to bridge two ZnII atoms through two monodentate carboxylate groups, building a zigzag infinite chain structure alonge the c axis. The metal-metal distances across each polymer backbone are 6.889 (3) Å. In the crystal, Weak C—H···O interactions contribute to the crystal packing stability.

Related literature top

For related literature, see: Liu et al. (2002).

Experimental top

The reaction of ZnCl2(0.68 g, 5 mmol) with o-phthalic acid (0.83 g, 5 mmol) in an aqueous-alcohol (3:1) solution (40 ml) at 363 K for 30 minutes produced a blue solution, to which 1-ethylimidazole (0.95 g,10 mmol) was added. The reaction solution was kept at room temperature after stirring for an hour at 333 K. colorless crystals were obtained after a few days.

Refinement top

H atoms were positioned geometrically(C—H = 0.93–0.97 Å) and allowed to ride on their parent atoms with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL (Sheldrick, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2001 and local programs.

Figures top
[Figure 1] Fig. 1. A portion of the polymeric chain in the title compound showing atomic numbering and 30% probability displacement ellipsoids [symmetry codes: (A) -x + 1/2,y,z - 1/2.
[Figure 2] Fig. 2. The packing of (I), viewed down the a axis.
catena-Poly[[bis(1-ethylimidazole-κN3)zinc(II)]-µ-phthalato-κ2O1:O2] top
Crystal data top
[Zn(C8H4O4)(C5H8N2)2]F(000) = 864
Mr = 419.75Dx = 1.450 Mg m−3
Orthorhombic, Pca21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2acCell parameters from 3025 reflections
a = 10.209 (2) Åθ = 2.5–25.1°
b = 13.870 (3) ŵ = 1.31 mm−1
c = 13.583 (3) ÅT = 293 K
V = 1923.3 (7) Å3Block, colorless
Z = 40.40 × 0.10 × 0.10 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2125 independent reflections
Radiation source: fine-focus sealed tube1404 reflections with I > 2σ(I)
graphiteRint = 0.012
thin–slice ω scansθmax = 26.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = 0→12
Tmin = 0.623, Tmax = 0.880k = 0→17
2616 measured reflectionsl = 0→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060H-atom parameters constrained
wR(F2) = 0.183 w = 1/[σ2(Fo2) + (0.0962P)2 + 2.22P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.006
2125 reflectionsΔρmax = 0.73 e Å−3
186 parametersΔρmin = −0.91 e Å−3
62 restraintsAbsolute structure: Flack (1983), 145 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.02 (5)
Crystal data top
[Zn(C8H4O4)(C5H8N2)2]V = 1923.3 (7) Å3
Mr = 419.75Z = 4
Orthorhombic, Pca21Mo Kα radiation
a = 10.209 (2) ŵ = 1.31 mm−1
b = 13.870 (3) ÅT = 293 K
c = 13.583 (3) Å0.40 × 0.10 × 0.10 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		2125 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1404 reflections with I > 2σ(I)
Tmin = 0.623, Tmax = 0.880Rint = 0.012
2616 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.060H-atom parameters constrained
wR(F2) = 0.183Δρmax = 0.73 e Å−3
S = 1.02Δρmin = −0.91 e Å−3
2125 reflectionsAbsolute structure: Flack (1983), 145 Friedel pairs
186 parametersFlack parameter: 0.02 (5)
62 restraints
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
xyzUiso*/Ueq
Zn0.19333 (9)0.74668 (7)0.75914 (15)0.0293 (3)
O10.3715 (7)0.7223 (5)0.5888 (5)0.0359 (16)
O20.3432 (6)0.8244 (5)0.7131 (5)0.0346 (15)
O30.1449 (7)0.8235 (5)0.8761 (5)0.0406 (17)
O4−0.0256 (8)0.7258 (5)0.8876 (6)0.0401 (17)
N10.2555 (9)0.6214 (5)0.8137 (7)0.0377 (17)
N20.3722 (10)0.4877 (7)0.8343 (9)0.060
N30.0552 (7)0.7507 (5)0.6519 (7)0.0294 (17)
N4−0.1320 (9)0.7819 (7)0.5765 (9)0.055
C10.4036 (12)0.4780 (9)1.0816 (11)0.060
H1A0.37770.46041.14710.090*
H1B0.42030.54611.07900.090*
H1C0.48170.44351.06400.090*
C20.2942 (11)0.4526 (9)1.0096 (10)0.055
H2B0.30160.38470.99350.066*
H2C0.21100.46161.04290.066*
C30.2910 (10)0.5061 (7)0.9196 (9)0.041
C40.3455 (9)0.5592 (7)0.7707 (9)0.045
H4B0.38140.56600.70820.054*
C50.2333 (10)0.5884 (7)0.9032 (8)0.042 (2)
H5A0.18220.62040.94950.051*
C6−0.1131 (13)0.7339 (10)0.3451 (11)0.062 (3)
H6A−0.09540.74360.27640.093*
H6B−0.20570.73780.35640.093*
H6C−0.08190.67150.36470.093*
C7−0.0448 (12)0.8101 (8)0.4040 (8)0.049 (3)
H7A0.04230.81960.37710.059*
H7B−0.09220.87030.39680.059*
C8−0.0330 (10)0.7880 (7)0.5088 (8)0.036
C90.0760 (10)0.7683 (6)0.5575 (8)0.035 (2)
H9A0.15850.76700.52850.042*
C10−0.0729 (10)0.7633 (8)0.6662 (9)0.045 (3)
H10A−0.11560.76000.72660.054*
C110.3983 (9)0.7972 (6)0.6299 (7)0.031 (2)
C120.0351 (9)0.7984 (7)0.9131 (7)0.031
C13−0.0231 (8)0.8647 (5)0.9879 (6)0.021
C14−0.1150 (10)0.9321 (7)0.9505 (8)0.042 (2)
H14A−0.13350.93340.88350.050*
C15−0.1767 (11)0.9953 (8)1.0126 (10)0.054 (3)
H15A−0.23931.03770.98810.065*
C16−0.1455 (12)0.9963 (9)1.1132 (10)0.056
H16A−0.18611.03991.15530.067*
C17−0.0560 (10)0.9333 (7)1.1485 (7)0.039 (2)
H17A−0.03590.93451.21530.046*
C180.0063 (8)0.8675 (6)1.0892 (7)0.0271 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.0352 (5)0.0290 (5)0.0237 (5)0.0015 (4)−0.0025 (6)0.0013 (5)
O10.046 (4)0.032 (3)0.030 (4)−0.010 (3)0.009 (3)−0.004 (3)
O20.047 (4)0.042 (4)0.015 (3)−0.002 (3)0.003 (3)0.004 (3)
O30.053 (4)0.037 (4)0.032 (4)0.001 (3)0.009 (3)−0.004 (3)
O40.051 (5)0.041 (4)0.029 (4)−0.010 (3)−0.006 (4)−0.009 (3)
N10.038 (4)0.040 (4)0.035 (4)0.003 (3)0.001 (4)−0.001 (3)
N20.0600.0600.0600.0000.0000.000
N30.022 (4)0.037 (4)0.029 (5)0.001 (3)−0.003 (3)−0.002 (3)
N40.0550.0550.0550.0000.0000.000
C10.0600.0600.0600.0000.0000.000
C20.0550.0550.0550.0000.0000.000
C30.0410.0410.0410.0000.0000.000
C40.0450.0450.0450.0000.0000.000
C50.042 (5)0.044 (4)0.041 (5)0.004 (4)−0.002 (4)0.004 (4)
C60.064 (7)0.087 (7)0.035 (6)−0.005 (5)0.000 (5)−0.011 (5)
C70.047 (5)0.059 (6)0.041 (5)0.000 (5)0.001 (5)0.004 (5)
C80.0360.0360.0360.0000.0000.000
C90.030 (5)0.044 (5)0.030 (6)0.000 (4)−0.004 (4)0.011 (4)
C100.029 (5)0.079 (8)0.027 (6)0.004 (5)0.003 (4)0.004 (5)
C110.043 (5)0.024 (4)0.026 (5)−0.004 (4)−0.004 (4)0.012 (4)
C120.0310.0310.0310.0000.0000.000
C130.0210.0210.0210.0000.0000.000
C140.055 (6)0.034 (5)0.036 (6)0.006 (5)−0.001 (5)0.012 (4)
C150.062 (7)0.031 (5)0.070 (9)0.011 (5)−0.014 (6)0.005 (6)
C160.0560.0560.0560.0000.0000.000
C170.054 (6)0.039 (5)0.023 (5)0.002 (4)0.004 (5)0.000 (4)
C180.029 (4)0.034 (4)0.019 (4)−0.003 (3)−0.007 (4)0.000 (4)
Geometric parameters (Å, °) top
Zn—O21.974 (6)C5—H5A0.9300
Zn—O31.976 (7)C6—C71.498 (18)
Zn—N11.993 (8)C6—H6A0.9600
Zn—N32.028 (8)C6—H6B0.9600
O1—C111.211 (12)C6—H6C0.9600
O2—C111.318 (12)C7—C81.461 (16)
O3—C121.277 (12)C7—H7A0.9700
O4—C121.232 (12)C7—H7B0.9700
N1—C51.318 (14)C8—C91.322 (14)
N1—C41.389 (13)C9—H9A0.9300
N2—C41.343 (15)C10—H10A0.9300
N2—C31.448 (16)C11—C18i1.485 (12)
N3—C91.323 (14)C12—C131.493 (12)
N3—C101.333 (14)C13—C181.409 (12)
N4—C81.369 (14)C13—C141.419 (13)
N4—C101.384 (15)C14—C151.370 (17)
C1—C21.526 (17)C14—H14A0.9300
C1—H1A0.9600C15—C161.403 (18)
C1—H1B0.9600C15—H15A0.9300
C1—H1C0.9600C16—C171.352 (15)
C2—C31.430 (17)C16—H16A0.9300
C2—H2B0.9700C17—C181.374 (13)
C2—H2C0.9700C17—H17A0.9300
C3—C51.305 (14)C18—C11ii1.485 (12)
C4—H4B0.9300
O2—Zn—O398.9 (3)H6A—C6—H6C109.5
O2—Zn—N1110.3 (3)H6B—C6—H6C109.5
O3—Zn—N1104.5 (3)C8—C7—C6114.3 (10)
O2—Zn—N3107.2 (3)C8—C7—H7A108.7
O3—Zn—N3112.9 (3)C6—C7—H7A108.7
N1—Zn—N3120.8 (3)C8—C7—H7B108.7
C11—O2—Zn116.5 (6)C6—C7—H7B108.7
C12—O3—Zn112.9 (6)H7A—C7—H7B107.6
C5—N1—C4106.6 (9)C9—C8—N4105.8 (10)
C5—N1—Zn126.2 (7)C9—C8—C7126.9 (10)
C4—N1—Zn126.6 (7)N4—C8—C7127.3 (10)
C4—N2—C3105.6 (9)C8—C9—N3112.8 (10)
C9—N3—C10105.9 (9)C8—C9—H9A123.6
C9—N3—Zn126.1 (7)N3—C9—H9A123.6
C10—N3—Zn125.5 (8)N3—C10—N4108.9 (10)
C8—N4—C10106.3 (9)N3—C10—H10A125.5
C2—C1—H1A109.5N4—C10—H10A125.5
C2—C1—H1B109.5O1—C11—O2123.0 (8)
H1A—C1—H1B109.5O1—C11—C18i122.7 (9)
C2—C1—H1C109.5O2—C11—C18i114.3 (8)
H1A—C1—H1C109.5O4—C12—O3123.6 (9)
H1B—C1—H1C109.5O4—C12—C13119.6 (8)
C3—C2—C1116.4 (10)O3—C12—C13116.7 (8)
C3—C2—H2B108.2C18—C13—C14118.2 (8)
C1—C2—H2B108.2C18—C13—C12126.6 (8)
C3—C2—H2C108.2C14—C13—C12115.2 (8)
C1—C2—H2C108.2C15—C14—C13120.4 (10)
H2B—C2—H2C107.3C15—C14—H14A119.8
C5—C3—C2127.6 (11)C13—C14—H14A119.8
C5—C3—N2106.0 (10)C14—C15—C16120.1 (11)
C2—C3—N2125.5 (10)C14—C15—H15A120.0
N2—C4—N1108.8 (10)C16—C15—H15A120.0
N2—C4—H4B125.6C17—C16—C15119.5 (12)
N1—C4—H4B125.6C17—C16—H16A120.2
C3—C5—N1112.6 (10)C15—C16—H16A120.2
C3—C5—H5A123.7C16—C17—C18122.3 (10)
N1—C5—H5A123.7C16—C17—H17A118.9
C7—C6—H6A109.5C18—C17—H17A118.9
C7—C6—H6B109.5C17—C18—C13119.5 (8)
H6A—C6—H6B109.5C17—C18—C11ii121.4 (8)
C7—C6—H6C109.5C13—C18—C11ii119.0 (8)
O3—Zn—O2—C11−176.2 (6)C10—N4—C8—C7−177.7 (11)
N1—Zn—O2—C1174.6 (7)C6—C7—C8—C9111.4 (13)
N3—Zn—O2—C11−58.8 (6)C6—C7—C8—N4−67.4 (15)
O2—Zn—O3—C12169.3 (6)N4—C8—C9—N3−0.6 (12)
N1—Zn—O3—C12−76.9 (7)C7—C8—C9—N3−179.6 (10)
N3—Zn—O3—C1256.3 (7)C10—N3—C9—C8−2.5 (12)
O2—Zn—N1—C5122.8 (9)Zn—N3—C9—C8−165.5 (7)
O3—Zn—N1—C517.4 (9)C9—N3—C10—N44.5 (12)
N3—Zn—N1—C5−111.1 (9)Zn—N3—C10—N4167.7 (7)
O2—Zn—N1—C4−47.0 (9)C8—N4—C10—N3−4.9 (13)
O3—Zn—N1—C4−152.4 (8)Zn—O2—C11—O1−9.0 (12)
N3—Zn—N1—C479.1 (9)Zn—O2—C11—C18i169.3 (6)
O2—Zn—N3—C923.5 (8)Zn—O3—C12—O49.5 (12)
O3—Zn—N3—C9131.3 (7)Zn—O3—C12—C13−167.5 (6)
N1—Zn—N3—C9−104.1 (8)O4—C12—C13—C1899.1 (12)
O2—Zn—N3—C10−136.4 (8)O3—C12—C13—C18−83.8 (11)
O3—Zn—N3—C10−28.6 (9)O4—C12—C13—C14−82.3 (11)
N1—Zn—N3—C1096.1 (9)O3—C12—C13—C1494.9 (10)
C1—C2—C3—C5−87.3 (16)C18—C13—C14—C15−2.5 (14)
C1—C2—C3—N280.3 (15)C12—C13—C14—C15178.7 (9)
C4—N2—C3—C5−5.0 (13)C13—C14—C15—C162.4 (17)
C4—N2—C3—C2−174.8 (10)C14—C15—C16—C17−1.1 (18)
C3—N2—C4—N11.7 (12)C15—C16—C17—C18−0.1 (17)
C5—N1—C4—N22.2 (12)C16—C17—C18—C130.0 (15)
Zn—N1—C4—N2173.6 (7)C16—C17—C18—C11ii−178.3 (9)
C2—C3—C5—N1176.2 (10)C14—C13—C18—C171.3 (13)
N2—C3—C5—N16.8 (13)C12—C13—C18—C17179.9 (8)
C4—N1—C5—C3−5.8 (12)C14—C13—C18—C11ii179.6 (8)
Zn—N1—C5—C3−177.2 (7)C12—C13—C18—C11ii−1.7 (13)
C10—N4—C8—C93.3 (12)
Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) −x+1/2, y, z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O1ii0.932.423.309 (13)159
C7—H7A···O2i0.972.523.317 (13)140
C9—H9A···O10.932.413.113 (12)133
C10—H10A···O40.932.423.090 (15)129
C16—H16A···O2iii0.932.593.478 (14)159
Symmetry codes: (ii) −x+1/2, y, z+1/2; (i) −x+1/2, y, z−1/2; (iii) −x, −y+2, z+1/2.
Table 1
Selected geometric parameters (Å) top
Zn—O21.974 (6)O1—C111.211 (12)
Zn—O31.976 (7)O2—C111.318 (12)
Zn—N11.993 (8)O3—C121.277 (12)
Zn—N32.028 (8)O4—C121.232 (12)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···O1i0.932.423.309 (13)159
C7—H7A···O2ii0.972.523.317 (13)140
C9—H9A···O10.932.413.113 (12)133
C10—H10A···O40.932.423.090 (15)129
C16—H16A···O2iii0.932.593.478 (14)159
Symmetry codes: (i) −x+1/2, y, z+1/2; (ii) −x+1/2, y, z−1/2; (iii) −x, −y+2, z+1/2.
Acknowledgements top

This work was supported by the Natural Science Foundation of Shandong Province (Y2006B12).

references
References top

Bruker (2001). SMART (Version 5.628) and SAINT (Version 6.45) . Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Liu, Q. Y., Liu, P., Wang, J. & Chen, Y. (2002). Chin. J. Struc. Chem. 21, 509–512.

Sheldrick, G. M. (2001). SHELXTL. Version 5.0. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.