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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): m1179.
Published online 2009 September 9. doi:  10.1107/S1600536809035168
PMCID: PMC2970416

Poly[(μ2-4,4′-bipyridine-κ2 N:N′)bis­(μ4-cyclo­hexane-1,3-dicarboxyl­ato-κ4 O:O′:O′′:O′′′)dizinc(II)]

Abstract

The cyclo­hexane-1,3-dicarboxyl­ate dianion in the title three-dimensional coordination polymer, [Zn2(C8H10O4)2(C10H8N2)]n, has one carboxyl­ate group in an equatorial position and the other in an axial position of the cyclo­hexane ring, which adopts a chair conformation. The carboxyl­ate groups function as bridges to two adjacent ZnII atoms, generating a layer motif. Adjacent layers are linked through the 4,4′-bipyridine N-heterocycle, forming a three-dimensional network; the geometry of ZnII is square-pyramidal with the N atom of the N-heterocycle occupying the apical position. The N-heterocycle lies about a center of inversion and is disordered in a 1:1 ratio with respect to the C atoms bearing H atoms.

Related literature

For the zinc cyclo­hexane-1,3-dicarboxyl­ate adduct of 1,10-phenanthroline, see: Bailey et al. (2008 [triangle]).

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Object name is e-65-m1179-scheme1.jpg

Experimental

Crystal data

  • [Zn2(C8H10O4)2(C10H8N2)]
  • M r = 313.64
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1179-efi1.jpg
  • a = 22.251 (2) Å
  • b = 13.436 (1) Å
  • c = 8.552 (1) Å
  • β = 104.446 (5)°
  • V = 2475.8 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 1.99 mm−1
  • T = 100 K
  • 0.12 × 0.02 × 0.02 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.557, T max = 1.000
  • 8536 measured reflections
  • 2175 independent reflections
  • 1407 reflections with I > 2σ(I)
  • R int = 0.116

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.123
  • S = 0.99
  • 2175 reflections
  • 184 parameters
  • 36 restraints
  • H-atom parameters constrained
  • Δρmax = 0.77 e Å−3
  • Δρmin = −0.65 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XSHELL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035168/tk2535sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035168/tk2535Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

Zinc acetate (0.15 g, 0.76 mmol), cyclohexane-1,3-dicarboxylic acid (mixture of cis- and trans-isomers) (0.13 g, 0.76 mmol) and 4,4'-bipyridine (0.12 g, 0.76 mmol) along with water (18 ml) were heated in a 23-ml Teflon-lined stainless-steel Parr bomb. The bomb was heated at 403 K for 3 days. The bomb was cooled to room temperature at 5 K per hour. Tiny crystals were isolated from the solution.

Refinement

Hydrogen atoms were included in the refinement in the riding model approximation with C–H 0.95–1.00 Å, and with U(H) 1.2Ueq(C). The 4,4'-bipyridine N-heterocycle is disordered about a center-of-inversion with respect to the carbon atoms bearing a hydrogen atom. As the disordered refined to nearly 50:50, the occupancy was fixed as 0.5. The distances of pairs of atoms were restrained to within 0.01 Å, and the pyridyl ring was restrained to near planarity. The displacement factors of the primed atoms were given those of the unprimed ones; the anisotropic behavior was restrained to be nearly isotropic.

Figures

Fig. 1.
50% Probability displacement ellipsoid plot of the asymmetric unit of Zn2(C10H8N2)(C8H10O4)2 extended to show the coordination environment of the zinc center and a full molecule of 4,4'-bipyridine. Hydrogen atoms are drawn as spheres of arbitrary radius. ...

Crystal data

[Zn2(C8H10O4)2(C10H8N2)]F(000) = 1288
Mr = 313.64Dx = 1.683 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 543 reflections
a = 22.251 (2) Åθ = 2.8–21.0°
b = 13.436 (1) ŵ = 1.99 mm1
c = 8.552 (1) ÅT = 100 K
β = 104.446 (5)°Prism, colorless
V = 2475.8 (3) Å30.12 × 0.02 × 0.02 mm
Z = 8

Data collection

Bruker SMART APEX diffractometer2175 independent reflections
Radiation source: fine-focus sealed tube1407 reflections with I > 2σ(I)
graphiteRint = 0.116
ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −26→25
Tmin = 0.557, Tmax = 1.000k = −15→15
8536 measured reflectionsl = −10→10

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-atom parameters constrained
S = 0.99w = 1/[σ2(Fo2) + (0.0478P)2] where P = (Fo2 + 2Fc2)/3
2175 reflections(Δ/σ)max = 0.001
184 parametersΔρmax = 0.77 e Å3
36 restraintsΔρmin = −0.65 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Zn10.30423 (3)0.80190 (5)0.58500 (8)0.0148 (2)
O10.33841 (19)0.7868 (3)0.3855 (5)0.0226 (10)
O20.25270 (18)0.7072 (3)0.2612 (4)0.0220 (10)
O30.24532 (18)0.4228 (3)0.0174 (4)0.0192 (9)
O40.33149 (18)0.3418 (3)0.1412 (5)0.0196 (10)
N10.3745 (2)0.8727 (3)0.7432 (5)0.0157 (11)
C10.3081 (3)0.7349 (4)0.2723 (7)0.0182 (14)
C20.3373 (3)0.7034 (4)0.1370 (7)0.0190 (13)
H20.32810.75630.05210.023*
C30.4082 (3)0.6950 (4)0.1978 (7)0.0207 (13)
H3A0.42650.68340.10520.025*
H3B0.42520.75810.25030.025*
C40.4259 (3)0.6096 (4)0.3182 (7)0.0218 (14)
H4A0.47160.60400.35300.026*
H4B0.41040.62390.41480.026*
C50.3985 (3)0.5113 (4)0.2433 (7)0.0232 (15)
H5A0.41820.49290.15560.028*
H5B0.40800.45840.32630.028*
C60.3287 (3)0.5179 (4)0.1755 (7)0.0183 (14)
H60.31080.53250.26930.022*
C70.3106 (3)0.6056 (4)0.0586 (7)0.0194 (14)
H7A0.32610.5935−0.03860.023*
H7B0.26480.61070.02400.023*
C80.3000 (3)0.4193 (4)0.1038 (7)0.0180 (14)
C90.4299 (6)0.8277 (15)0.8020 (17)0.015 (3)0.50
H90.43460.76070.77150.019*0.50
C100.4800 (11)0.8744 (6)0.9043 (19)0.022 (3)0.50
H100.51810.84000.94320.027*0.50
C9'0.4219 (6)0.8212 (16)0.8385 (15)0.015 (3)0.50
H9'0.42130.75060.83460.019*0.50
C10'0.4713 (10)0.8691 (6)0.942 (2)0.022 (3)0.50
H10'0.50400.83111.00760.027*0.50
C110.4734 (2)0.9726 (4)0.9490 (6)0.0155 (13)
C120.4164 (6)1.0188 (15)0.8894 (17)0.016 (3)0.50
H120.41021.08560.91840.019*0.50
C130.3687 (11)0.9669 (6)0.7878 (19)0.014 (2)0.50
H130.33010.99960.74770.017*0.50
C12'0.4238 (6)1.0236 (16)0.8504 (16)0.016 (3)0.50
H12'0.42301.09430.85240.019*0.50
C13'0.3758 (10)0.9721 (6)0.750 (2)0.014 (2)0.50
H13'0.34251.00850.68280.017*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0119 (4)0.0150 (4)0.0150 (3)−0.0020 (3)−0.0011 (2)−0.0008 (3)
O10.027 (2)0.021 (2)0.021 (2)−0.0065 (19)0.0087 (19)−0.0056 (18)
O20.019 (2)0.030 (3)0.017 (2)−0.002 (2)0.0051 (18)−0.0029 (18)
O30.011 (2)0.018 (2)0.023 (2)0.0018 (18)−0.0065 (19)0.0021 (18)
O40.021 (3)0.013 (2)0.021 (2)0.0026 (18)−0.0026 (19)−0.0014 (17)
N10.016 (3)0.018 (3)0.013 (2)0.001 (2)0.003 (2)−0.003 (2)
C10.024 (4)0.008 (3)0.022 (3)0.000 (2)0.005 (3)0.002 (2)
C20.023 (3)0.017 (3)0.016 (3)0.000 (3)0.004 (3)−0.002 (3)
C30.017 (3)0.020 (3)0.025 (3)−0.004 (3)0.006 (3)−0.005 (3)
C40.017 (4)0.027 (4)0.020 (3)0.003 (3)0.004 (3)−0.005 (3)
C50.020 (4)0.021 (3)0.027 (4)0.000 (3)0.003 (3)0.000 (3)
C60.015 (4)0.017 (3)0.021 (3)−0.002 (3)0.000 (3)0.002 (3)
C70.024 (4)0.019 (3)0.014 (3)−0.001 (3)0.003 (3)−0.003 (2)
C80.026 (4)0.015 (3)0.013 (3)−0.001 (3)0.005 (3)0.001 (3)
C90.025 (5)0.013 (4)0.011 (6)−0.001 (4)0.008 (4)0.005 (4)
C100.018 (6)0.022 (4)0.022 (7)0.000 (3)−0.004 (4)0.007 (3)
C9'0.025 (5)0.013 (4)0.011 (6)−0.001 (4)0.008 (4)0.005 (4)
C10'0.018 (6)0.022 (4)0.022 (7)0.000 (3)−0.004 (4)0.007 (3)
C110.010 (3)0.021 (3)0.013 (3)−0.002 (3)−0.001 (3)−0.001 (2)
C120.015 (4)0.017 (3)0.017 (6)−0.002 (3)0.009 (4)−0.006 (4)
C130.008 (5)0.018 (3)0.015 (7)0.001 (3)0.000 (4)−0.002 (3)
C12'0.015 (4)0.017 (3)0.017 (6)−0.002 (3)0.009 (4)−0.006 (4)
C13'0.008 (5)0.018 (3)0.015 (7)0.001 (3)0.000 (4)−0.002 (3)

Geometric parameters (Å, °)

Zn1—O12.044 (4)C4—H4B0.9900
Zn1—O2i2.045 (4)C5—C61.519 (8)
Zn1—O3ii2.034 (4)C5—H5A0.9900
Zn1—O4iii2.044 (4)C5—H5B0.9900
Zn1—N12.031 (5)C6—C81.532 (8)
Zn1—Zn1i2.8517 (13)C6—C71.533 (7)
O1—C11.246 (7)C6—H61.0000
O2—C11.267 (7)C7—H7A0.9900
O2—Zn1i2.045 (4)C7—H7B0.9900
O3—C81.257 (7)C9—C101.384 (10)
O3—Zn1iv2.034 (4)C9—H90.9500
O4—C81.252 (7)C10—C111.392 (10)
O4—Zn1v2.044 (4)C10—H100.9500
N1—C13'1.338 (9)C9'—C10'1.385 (10)
N1—C131.338 (9)C9'—H9'0.9500
N1—C9'1.351 (9)C10'—C111.393 (10)
N1—C91.351 (9)C10'—H10'0.9500
C1—C21.522 (8)C11—C12'1.390 (10)
C2—C71.526 (7)C11—C121.391 (10)
C2—C31.537 (8)C11—C11vi1.478 (11)
C2—H21.0000C12—C131.380 (10)
C3—C41.526 (8)C12—H120.9500
C3—H3A0.9900C13—H130.9500
C3—H3B0.9900C12'—C13'1.380 (10)
C4—C51.526 (8)C12'—H12'0.9500
C4—H4A0.9900C13'—H13'0.9500
N1—Zn1—O3ii99.06 (17)C6—C5—H5B109.2
N1—Zn1—O2i95.55 (16)C4—C5—H5B109.2
O3ii—Zn1—O2i88.19 (16)H5A—C5—H5B107.9
N1—Zn1—O1102.59 (16)C5—C6—C8112.8 (5)
O3ii—Zn1—O189.70 (15)C5—C6—C7111.8 (5)
O2i—Zn1—O1161.85 (15)C8—C6—C7112.9 (5)
N1—Zn1—O4iii98.71 (17)C5—C6—H6106.3
O3ii—Zn1—O4iii162.21 (15)C8—C6—H6106.3
O2i—Zn1—O4iii89.29 (16)C7—C6—H6106.3
O1—Zn1—O4iii87.23 (15)C2—C7—C6111.4 (5)
N1—Zn1—Zn1i169.00 (12)C2—C7—H7A109.3
O3ii—Zn1—Zn1i82.66 (11)C6—C7—H7A109.3
O2i—Zn1—Zn1i73.59 (11)C2—C7—H7B109.3
O1—Zn1—Zn1i88.25 (12)C6—C7—H7B109.3
O4iii—Zn1—Zn1i79.73 (11)H7A—C7—H7B108.0
C1—O1—Zn1117.5 (4)O4—C8—O3125.4 (5)
C1—O2—Zn1i135.7 (4)O4—C8—C6117.8 (5)
C8—O3—Zn1iv124.3 (4)O3—C8—C6116.7 (5)
C8—O4—Zn1v127.7 (4)N1—C9—C10123 (2)
C13'—N1—C9'118.7 (15)N1—C9—H9118.4
C13—N1—C9'115.4 (14)C10—C9—H9118.4
C13'—N1—C9115.0 (15)C9—C10—C11119 (2)
C13—N1—C9117.4 (15)C9—C10—H10120.6
C13'—N1—Zn1120.0 (11)C11—C10—H10120.6
C13—N1—Zn1121.4 (11)N1—C9'—C10'122 (2)
C9'—N1—Zn1121.2 (11)N1—C9'—H9'119.2
C9—N1—Zn1121.2 (11)C10'—C9'—H9'119.2
O1—C1—O2123.4 (5)C9'—C10'—C11120 (2)
O1—C1—C2119.6 (5)C9'—C10'—H10'119.8
O2—C1—C2116.9 (5)C11—C10'—H10'119.8
C7—C2—C1112.3 (5)C12'—C11—C10115.0 (14)
C7—C2—C3109.8 (5)C12—C11—C10118.1 (14)
C1—C2—C3111.1 (5)C12'—C11—C10'116.8 (14)
C7—C2—H2107.8C12—C11—C10'114.3 (14)
C1—C2—H2107.8C12'—C11—C11vi120.7 (12)
C3—C2—H2107.8C12—C11—C11vi121.1 (12)
C4—C3—C2110.7 (5)C10—C11—C11vi120.7 (12)
C4—C3—H3A109.5C10'—C11—C11vi122.5 (11)
C2—C3—H3A109.5C13—C12—C11120 (2)
C4—C3—H3B109.5C13—C12—H12120.2
C2—C3—H3B109.5C11—C12—H12120.2
H3A—C3—H3B108.1N1—C13—C12123 (2)
C5—C4—C3111.0 (5)N1—C13—H13118.5
C5—C4—H4A109.4C12—C13—H13118.5
C3—C4—H4A109.4C13'—C12'—C11120 (2)
C5—C4—H4B109.4C13'—C12'—H12'119.8
C3—C4—H4B109.4C11—C12'—H12'119.8
H4A—C4—H4B108.0N1—C13'—C12'122 (2)
C6—C5—C4111.9 (5)N1—C13'—H13'118.9
C6—C5—H5A109.2C12'—C13'—H13'118.9
C4—C5—H5A109.2
N1—Zn1—O1—C1171.8 (4)C3—C2—C7—C656.6 (6)
O3ii—Zn1—O1—C1−89.0 (4)C5—C6—C7—C2−54.5 (6)
O2i—Zn1—O1—C1−5.7 (7)C8—C6—C7—C2177.0 (5)
O4iii—Zn1—O1—C173.5 (4)Zn1v—O4—C8—O3−3.1 (8)
Zn1i—Zn1—O1—C1−6.3 (4)Zn1v—O4—C8—C6173.7 (3)
O3ii—Zn1—N1—C13'−0.6 (6)Zn1iv—O3—C8—O4−0.9 (8)
O2i—Zn1—N1—C13'−89.7 (6)Zn1iv—O3—C8—C6−177.8 (3)
O1—Zn1—N1—C13'91.1 (6)C5—C6—C8—O416.7 (7)
O4iii—Zn1—N1—C13'−179.8 (6)C7—C6—C8—O4144.6 (5)
Zn1i—Zn1—N1—C13'−98.8 (9)C5—C6—C8—O3−166.2 (5)
O3ii—Zn1—N1—C1319.4 (6)C7—C6—C8—O3−38.3 (7)
O2i—Zn1—N1—C13−69.6 (6)C13'—N1—C9—C1019.0 (10)
O1—Zn1—N1—C13111.2 (6)C13—N1—C9—C10−0.1 (3)
O4iii—Zn1—N1—C13−159.8 (6)Zn1—N1—C9—C10177.0 (3)
Zn1i—Zn1—N1—C13−78.8 (10)N1—C9—C10—C11−0.2 (3)
O3ii—Zn1—N1—C9'−177.8 (6)C13'—N1—C9'—C10'−0.1 (3)
O2i—Zn1—N1—C9'93.2 (6)Zn1—N1—C9'—C10'177.1 (3)
O1—Zn1—N1—C9'−86.0 (6)N1—C9'—C10'—C11−0.3 (3)
O4iii—Zn1—N1—C9'3.0 (6)C9—C10—C11—C12'−18.2 (11)
Zn1i—Zn1—N1—C9'84.0 (9)C9—C10—C11—C120.6 (6)
O3ii—Zn1—N1—C9−157.6 (6)C9—C10—C11—C10'82 (6)
O2i—Zn1—N1—C9113.4 (6)C9—C10—C11—C11vi−176.8 (5)
O1—Zn1—N1—C9−65.9 (6)C9'—C10'—C11—C12'0.7 (6)
O4iii—Zn1—N1—C923.2 (6)C9'—C10'—C11—C1219.4 (10)
Zn1i—Zn1—N1—C9104.2 (9)C9'—C10'—C11—C10−87 (6)
Zn1—O1—C1—O213.7 (8)C9'—C10'—C11—C11vi−177.0 (6)
Zn1—O1—C1—C2−167.4 (4)C10—C11—C12—C13−0.6 (8)
Zn1i—O2—C1—O1−16.9 (9)C10'—C11—C12—C13−19.4 (12)
Zn1i—O2—C1—C2164.2 (4)C11vi—C11—C12—C13176.7 (7)
O1—C1—C2—C7152.2 (5)C13'—N1—C13—C12−86 (7)
O2—C1—C2—C7−28.9 (7)C9'—N1—C13—C1219.2 (12)
O1—C1—C2—C328.7 (7)C9—N1—C13—C120.1 (7)
O2—C1—C2—C3−152.3 (5)Zn1—N1—C13—C12−177.0 (5)
C7—C2—C3—C4−58.1 (6)C11—C12—C13—N10.3 (9)
C1—C2—C3—C466.7 (6)C10'—C11—C12'—C13'−0.8 (8)
C2—C3—C4—C557.2 (6)C11vi—C11—C12'—C13'176.9 (6)
C3—C4—C5—C6−54.6 (7)C9'—N1—C13'—C12'0.0 (7)
C4—C5—C6—C8−178.4 (5)Zn1—N1—C13'—C12'−177.3 (5)
C4—C5—C6—C753.2 (6)C11—C12'—C13'—N10.5 (9)
C1—C2—C7—C6−67.6 (6)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2535).

References

  • Bailey, A. J., Lee, C., Feller, R. K., Orton, J. B., Mellot-Draznieks, C., Slater, B., Harrison, W. T. A., Simoncic, P., Navrotsky, A., Grossel, M. C. & Cheetham, A. K. (2008). Angew. Chem. Int. Ed.47, 8634–8637. [PubMed]
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography