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Acta Cryst. (2009). E65, m1179    [ doi:10.1107/S1600536809035168 ]

Poly[([mu]2-4,4'-bipyridine-[kappa]2N:N')bis([mu]4-cyclohexane-1,3-dicarboxylato-[kappa]4O:O':O'':O''')dizinc(II)]

M. R. Rizal and S. W. Ng

Abstract top

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 top

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

Experimental top

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 top

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.

Computing details top

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

Figures top
[Figure 1] 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. Symmetry operations i: 0.5-x, 1.5-y, 1-z; ii: 0.5-x, 0.5+y, 0.5-z; iii: x, 1-y, 0.5+z.
Poly[(µ2-4,4'-bipyridine-κ2N:N')bis(µ4-cyclohexane- 1,3-dicarboxylato-κ4O:O':O'':O''')dizinc(II)] top
Crystal data top
[Zn2(C8H10O4)2(C10H8N2)]F(000) = 1288
Mr = 313.64Dx = 1.683 Mg m−3
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 mm−1
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 top
Bruker SMART APEX
diffractometer		2175 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 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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0478P)2]
where P = (Fo2 + 2Fc2)/3
2175 reflections(Δ/σ)max = 0.001
184 parametersΔρmax = 0.77 e Å−3
36 restraintsΔρmin = −0.65 e Å−3
Crystal data top
[Zn2(C8H10O4)2(C10H8N2)]V = 2475.8 (3) Å3
Mr = 313.64Z = 8
Monoclinic, C2/cMo Kα radiation
a = 22.251 (2) ŵ = 1.99 mm−1
b = 13.436 (1) ÅT = 100 K
c = 8.552 (1) Å0.12 × 0.02 × 0.02 mm
β = 104.446 (5)°
Data collection top
Bruker SMART APEX
diffractometer		2175 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1407 reflections with I > 2σ(I)
Tmin = 0.557, Tmax = 1.000Rint = 0.116
8536 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.123Δρmax = 0.77 e Å−3
S = 0.99Δρmin = −0.65 e Å−3
2175 reflectionsAbsolute structure: ?
184 parametersFlack parameter: ?
36 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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.
Acknowledgements top

We thank the University of Malaya for supporting this study.

references
References top

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.

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.

Westrip, S. P. (2009). publCIF. In preparation.