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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): m1178.
Published online 2009 September 9. doi:  10.1107/S1600536809035144
PMCID: PMC2970336

Bis(μ-cyclo­hexane-1,3-dicarboxyl­ato)-κ3 O 1:O 4,O 4′3 O 1,O 1′:O 4-bis­[aqua­(1,10-phenanthroline-κ2 N,N′)zinc(II)]

Abstract

The cyclo­hexane-1,3-dicarboxyl­ate dianion in the dinuclear centrosymmetric title compound, [Zn2(C8H10O4)2(C12H8N2)2(H2O)2], has a chair conformation with both carboxyl­ate groups in equatorial positions. One carboxyl­ate group chelates a ZnII atom, whereas the other binds through one O atom only to confer a six-coordinate status to the N-heterocycle-chelated water-coordinated ZnII atom. Adjacent dinuclear mol­ecules are linked by O—H(...)O hydrogen bonds into a linear chain.

Related literature

For the isostructural manganese(II) analog, see: Thirumurugan et al. (2006 [triangle]). For a review of the mol­ecular architectures of metal carboxyl­ate adducts of 2,2′-bipyridine-like ligands, see: Ye et al. (2003 [triangle]).

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Object name is e-65-m1178-scheme1.jpg

Experimental

Crystal data

  • [Zn2(C8H10O4)2(C12H8N2)2(H2O)2]
  • M r = 867.50
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1178-efi1.jpg
  • a = 9.6172 (2) Å
  • b = 17.4722 (5) Å
  • c = 11.4822 (3) Å
  • β = 104.393 (2)°
  • V = 1868.84 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.35 mm−1
  • T = 100 K
  • 0.20 × 0.16 × 0.15 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.774, T max = 0.823
  • 9952 measured reflections
  • 3289 independent reflections
  • 2706 reflections with I > 2σ(I)
  • R int = 0.032

Refinement

  • R[F 2 > 2σ(F 2)] = 0.069
  • wR(F 2) = 0.177
  • S = 1.09
  • 3289 reflections
  • 261 parameters
  • 74 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 1.17 e Å−3
  • Δρmin = −0.51 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]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035144/tk2534sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035144/tk2534Isup2.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 (0.10 g, 0.46 mmol), cyclohexane-1,3-dicarboxylic acid (mixture of cis- and trans-isomers) (0.08 g, 0.46 mmol) and 1,10-phenanthroline (0.09 g, 0.46 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 water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H 0.84±0.01 Å; their displacement factors were refined.

The carbon atoms of the 1,10-phenanthroline molecule displayed somewhat elongated thermal elliposoids. As such, their anisotropic displacement factors were restrained to be nearly isotropic.

The final difference Fourier map had a peak in the vicinity of the C1 and C6 atoms.

Figures

Fig. 1.
50% Probability displacement ellipsoid plot of Zn2(H2O)2(C12H8N2)2(C8H10O4)2. Hydrogen atoms are drawn as spheres of arbitrary radius. Symmetry code (i): 2-x, 1-y, 1-z.

Crystal data

[Zn2(C8H10O4)2(C12H8N2)2(H2O)2]F(000) = 896
Mr = 867.50Dx = 1.542 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2661 reflections
a = 9.6172 (2) Åθ = 2.2–26.3°
b = 17.4722 (5) ŵ = 1.35 mm1
c = 11.4822 (3) ÅT = 100 K
β = 104.393 (2)°Block, colorless
V = 1868.84 (8) Å30.20 × 0.16 × 0.15 mm
Z = 2

Data collection

Bruker SMART APEX diffractometer3289 independent reflections
Radiation source: fine-focus sealed tube2706 reflections with I > 2σ(I)
graphiteRint = 0.032
ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −11→11
Tmin = 0.774, Tmax = 0.823k = −20→20
9952 measured reflectionsl = −10→13

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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177H atoms treated by a mixture of independent and constrained refinement
S = 1.09w = 1/[σ2(Fo2) + (0.0653P)2 + 9.3251P] where P = (Fo2 + 2Fc2)/3
3289 reflections(Δ/σ)max = 0.001
261 parametersΔρmax = 1.17 e Å3
74 restraintsΔρmin = −0.51 e Å3

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

xyzUiso*/Ueq
Zn10.70076 (7)0.51170 (4)0.71412 (7)0.0348 (3)
O10.8609 (5)0.5855 (3)0.7036 (5)0.0516 (13)
O20.7359 (6)0.6719 (3)0.5775 (5)0.0541 (14)
O31.1660 (5)0.5852 (3)0.3118 (4)0.0461 (12)
O41.3286 (4)0.5440 (3)0.4667 (4)0.0414 (11)
O1w0.5440 (5)0.5921 (3)0.6510 (4)0.0367 (10)
H110.593 (7)0.626 (3)0.627 (7)0.06 (3)*
H120.471 (5)0.572 (4)0.606 (6)0.05 (2)*
N10.5460 (6)0.4333 (3)0.7566 (5)0.0394 (13)
N20.7539 (6)0.5156 (4)0.9034 (5)0.0495 (16)
C11.1790 (11)0.7240 (5)0.4694 (11)0.085 (3)
H1A1.10880.73180.39120.102*
H1B1.27500.73860.45980.102*
C21.1393 (10)0.7760 (5)0.5650 (11)0.090 (4)
H2A1.21520.77300.64100.108*
H2B1.13220.82980.53710.108*
C30.9953 (11)0.7504 (5)0.5869 (12)0.096 (4)
H3A0.97540.78090.65360.116*
H3B0.91790.76090.51390.116*
C40.9932 (9)0.6721 (5)0.6155 (10)0.070 (3)
H41.06520.66530.69430.084*
C51.0389 (7)0.6182 (4)0.5277 (7)0.0426 (16)
H5A0.96300.61620.45160.051*
H5B1.05170.56590.56200.051*
C61.1801 (9)0.6455 (5)0.5022 (9)0.064 (2)
H61.25340.64150.58080.077*
C71.2268 (6)0.5891 (4)0.4205 (6)0.0369 (15)
C80.8505 (7)0.6411 (4)0.6334 (8)0.0499 (19)
C90.4467 (8)0.3928 (4)0.6845 (8)0.0502 (18)
H90.43020.40130.60040.060*
C100.3633 (9)0.3378 (5)0.7238 (10)0.066 (2)
H100.29320.30940.66750.079*
C110.3834 (10)0.3256 (5)0.8412 (11)0.074 (3)
H11A0.32700.28840.86890.089*
C120.4866 (10)0.3671 (5)0.9239 (8)0.068 (3)
C130.5188 (13)0.3622 (6)1.0544 (11)0.089 (3)
H130.46550.32741.08990.107*
C140.6173 (15)0.4034 (7)1.1242 (10)0.094 (4)
H140.63210.39761.20860.113*
C150.7051 (12)0.4574 (6)1.0810 (8)0.079 (3)
C160.8171 (14)0.5024 (7)1.1488 (10)0.096 (4)
H160.84100.49751.23380.115*
C170.8914 (12)0.5518 (7)1.0997 (10)0.092 (4)
H170.96540.58221.14840.110*
C180.8568 (8)0.5576 (5)0.9736 (7)0.065 (2)
H180.90870.59270.93730.078*
C190.6786 (9)0.4657 (5)0.9548 (6)0.053 (2)
C200.5701 (8)0.4215 (4)0.8787 (7)0.0470 (18)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0269 (4)0.0414 (4)0.0374 (4)−0.0027 (3)0.0104 (3)−0.0022 (3)
O10.031 (2)0.049 (3)0.076 (4)−0.009 (2)0.014 (2)−0.004 (3)
O20.056 (3)0.037 (3)0.078 (4)−0.011 (2)0.033 (3)−0.001 (2)
O30.032 (2)0.060 (3)0.044 (3)0.002 (2)0.004 (2)0.001 (2)
O40.028 (2)0.059 (3)0.037 (3)−0.005 (2)0.0079 (19)0.004 (2)
O1w0.026 (2)0.049 (3)0.035 (3)−0.002 (2)0.008 (2)0.002 (2)
N10.037 (3)0.040 (3)0.046 (3)0.005 (2)0.021 (3)0.007 (3)
N20.040 (3)0.067 (4)0.034 (3)0.026 (3)−0.005 (3)−0.017 (3)
C10.082 (6)0.062 (6)0.138 (10)−0.014 (5)0.079 (7)−0.008 (6)
C20.080 (6)0.057 (5)0.164 (11)−0.035 (5)0.087 (7)−0.049 (6)
C30.086 (7)0.068 (6)0.166 (11)−0.039 (5)0.090 (8)−0.057 (7)
C40.057 (5)0.051 (5)0.120 (8)−0.012 (4)0.057 (5)−0.016 (5)
C50.038 (4)0.040 (4)0.055 (5)−0.008 (3)0.019 (3)−0.001 (3)
C60.055 (5)0.056 (5)0.098 (7)−0.016 (4)0.049 (5)−0.025 (5)
C70.028 (3)0.046 (4)0.040 (4)−0.011 (3)0.015 (3)−0.005 (3)
C80.036 (4)0.047 (4)0.075 (5)−0.006 (3)0.028 (4)−0.022 (4)
C90.044 (4)0.045 (4)0.069 (5)−0.008 (3)0.028 (4)−0.001 (3)
C100.054 (4)0.049 (4)0.109 (7)−0.001 (3)0.047 (5)0.004 (4)
C110.065 (5)0.050 (4)0.126 (7)0.019 (4)0.059 (5)0.028 (5)
C120.085 (5)0.065 (5)0.079 (5)0.053 (4)0.064 (5)0.043 (4)
C130.107 (7)0.086 (6)0.100 (7)0.064 (5)0.073 (6)0.056 (5)
C140.122 (7)0.112 (7)0.062 (6)0.084 (6)0.050 (6)0.036 (5)
C150.091 (6)0.090 (6)0.055 (5)0.067 (5)0.020 (5)0.009 (5)
C160.112 (7)0.108 (7)0.056 (5)0.080 (6)−0.003 (5)−0.018 (5)
C170.077 (6)0.102 (7)0.071 (6)0.055 (5)−0.029 (5)−0.044 (5)
C180.049 (4)0.078 (5)0.053 (4)0.035 (4)−0.015 (4)−0.028 (4)
C190.062 (4)0.067 (5)0.035 (4)0.046 (4)0.019 (3)0.012 (3)
C200.056 (4)0.050 (4)0.045 (4)0.029 (3)0.031 (3)0.018 (3)

Geometric parameters (Å, °)

Zn1—O12.035 (5)C4—C51.521 (10)
Zn1—O3i2.188 (5)C4—C81.536 (9)
Zn1—O4i2.247 (5)C4—H41.0000
Zn1—O1w2.056 (5)C5—C61.536 (9)
Zn1—N12.166 (5)C5—H5A0.9900
Zn1—N22.107 (6)C5—H5B0.9900
O1—C81.250 (10)C6—C71.504 (10)
O2—C81.251 (9)C6—H61.0000
O3—C71.241 (8)C9—C101.397 (10)
O3—Zn1i2.188 (5)C9—H90.9500
O4—C71.266 (8)C10—C111.331 (14)
O4—Zn1i2.247 (5)C10—H100.9500
O1w—H110.84 (6)C11—C121.394 (14)
O1w—H120.84 (6)C11—H11A0.9500
N1—C91.306 (9)C12—C201.423 (11)
N1—C201.378 (9)C12—C131.456 (15)
N2—C181.331 (10)C13—C141.297 (16)
N2—C191.358 (11)C13—H130.9500
C1—C61.422 (12)C14—C151.434 (17)
C1—C21.544 (12)C14—H140.9500
C1—H1A0.9900C15—C191.416 (11)
C1—H1B0.9900C15—C161.403 (16)
C2—C31.535 (10)C16—C171.331 (17)
C2—H2A0.9900C16—H160.9500
C2—H2B0.9900C17—C181.407 (14)
C3—C41.408 (13)C17—H170.9500
C3—H3A0.9900C18—H180.9500
C3—H3B0.9900C19—C201.412 (12)
O1—Zn1—O3i90.3 (2)C6—C5—H5A109.6
O1—Zn1—O4i98.2 (2)C4—C5—H5B109.6
O1—Zn1—O1w92.6 (2)C6—C5—H5B109.6
O1—Zn1—N292.7 (2)H5A—C5—H5B108.1
O1—Zn1—N1170.6 (2)C1—C6—C7116.8 (8)
O3i—Zn1—O4i58.8 (2)C1—C6—C5113.7 (7)
O3i—Zn1—O1w152.1 (2)C7—C6—C5109.3 (6)
O3i—Zn1—N190.0 (2)C1—C6—H6105.3
O3i—Zn1—N299.5 (2)C7—C6—H6105.3
O4i—Zn1—O1w93.3 (2)C5—C6—H6105.3
O4i—Zn1—N189.9 (2)O3—C7—O4120.6 (6)
O4i—Zn1—N2155.5 (2)O3—C7—C6121.6 (7)
O1w—Zn1—N191.6 (2)O4—C7—C6117.8 (7)
O1w—Zn1—N2108.1 (2)O2—C8—O1125.7 (6)
N1—Zn1—N278.0 (2)O2—C8—C4118.9 (8)
C8—O1—Zn1126.2 (5)O1—C8—C4115.4 (7)
C7—O3—Zn1i91.9 (4)N1—C9—C10123.7 (8)
C7—O4—Zn1i88.6 (4)N1—C9—H9118.1
Zn1—O1w—H11100 (6)C10—C9—H9118.1
Zn1—O1w—H12111 (5)C11—C10—C9119.2 (9)
H11—O1w—H12123 (8)C11—C10—H10120.4
C9—N1—C20118.4 (6)C9—C10—H10120.4
C9—N1—Zn1129.4 (5)C10—C11—C12120.3 (8)
C20—N1—Zn1111.9 (5)C10—C11—H11A119.8
C18—N2—C19119.2 (7)C12—C11—H11A119.8
C18—N2—Zn1126.6 (6)C11—C12—C20118.1 (8)
C19—N2—Zn1114.1 (5)C11—C12—C13127.1 (9)
C6—C1—C2111.5 (8)C20—C12—C13114.9 (10)
C6—C1—H1A109.3C14—C13—C12122.6 (10)
C2—C1—H1A109.3C14—C13—H13118.7
C6—C1—H1B109.3C12—C13—H13118.7
C2—C1—H1B109.3C13—C14—C15123.7 (10)
H1A—C1—H1B108.0C13—C14—H14118.2
C3—C2—C1109.7 (7)C15—C14—H14118.2
C3—C2—H2A109.7C14—C15—C19116.7 (11)
C1—C2—H2A109.7C14—C15—C16127.9 (11)
C3—C2—H2B109.7C19—C15—C16115.4 (11)
C1—C2—H2B109.7C17—C16—C15123.2 (10)
H2A—C2—H2B108.2C17—C16—H16118.4
C4—C3—C2112.8 (8)C15—C16—H16118.4
C4—C3—H3A109.0C16—C17—C18117.9 (11)
C2—C3—H3A109.0C16—C17—H17121.1
C4—C3—H3B109.0C18—C17—H17121.1
C2—C3—H3B109.0N2—C18—C17122.2 (11)
H3A—C3—H3B107.8N2—C18—H18118.9
C3—C4—C5115.1 (8)C17—C18—H18118.9
C3—C4—C8116.0 (7)N2—C19—C20118.3 (6)
C5—C4—C8106.6 (6)N2—C19—C15122.0 (9)
C3—C4—H4106.1C20—C19—C15119.6 (9)
C5—C4—H4106.1N1—C20—C19117.3 (6)
C8—C4—H4106.1N1—C20—C12120.2 (8)
C4—C5—C6110.4 (6)C19—C20—C12122.5 (8)
C4—C5—H5A109.6
O1w—Zn1—O1—C8−26.9 (6)C3—C4—C8—O229.2 (13)
N2—Zn1—O1—C8−135.2 (6)C5—C4—C8—O2−100.4 (8)
O3i—Zn1—O1—C8125.3 (6)C3—C4—C8—O1−151.5 (9)
O4i—Zn1—O1—C866.8 (6)C5—C4—C8—O178.9 (9)
O1w—Zn1—N1—C972.9 (6)C20—N1—C9—C10−0.2 (10)
N2—Zn1—N1—C9−178.9 (6)Zn1—N1—C9—C10172.7 (5)
O3i—Zn1—N1—C9−79.2 (6)N1—C9—C10—C110.8 (12)
O4i—Zn1—N1—C9−20.4 (6)C9—C10—C11—C12−0.2 (12)
O1w—Zn1—N1—C20−113.8 (4)C10—C11—C12—C20−0.9 (11)
N2—Zn1—N1—C20−5.6 (4)C10—C11—C12—C13178.2 (7)
O3i—Zn1—N1—C2094.1 (4)C11—C12—C13—C14−180.0 (9)
O4i—Zn1—N1—C20152.9 (4)C20—C12—C13—C14−0.9 (12)
O1—Zn1—N2—C182.1 (6)C12—C13—C14—C15−0.5 (14)
O1w—Zn1—N2—C18−91.6 (5)C13—C14—C15—C191.1 (13)
N1—Zn1—N2—C18−179.3 (6)C13—C14—C15—C16−177.6 (9)
O3i—Zn1—N2—C1892.8 (6)C14—C15—C16—C17−179.2 (9)
O4i—Zn1—N2—C18118.8 (6)C19—C15—C16—C172.2 (12)
O1—Zn1—N2—C19−173.6 (4)C15—C16—C17—C18−1.2 (14)
O1w—Zn1—N2—C1992.7 (5)C19—N2—C18—C170.5 (10)
N1—Zn1—N2—C195.0 (4)Zn1—N2—C18—C17−175.0 (5)
O3i—Zn1—N2—C19−82.9 (4)C16—C17—C18—N2−0.2 (12)
O4i—Zn1—N2—C19−56.9 (7)C18—N2—C19—C20−179.8 (6)
C6—C1—C2—C3−55.1 (14)Zn1—N2—C19—C20−3.8 (7)
C1—C2—C3—C453.5 (14)C18—N2—C19—C150.6 (9)
C2—C3—C4—C5−52.1 (13)Zn1—N2—C19—C15176.6 (5)
C2—C3—C4—C8−177.5 (9)C14—C15—C19—N2179.3 (6)
C3—C4—C5—C648.8 (11)C16—C15—C19—N2−1.8 (10)
C8—C4—C5—C6178.9 (8)C14—C15—C19—C20−0.2 (10)
C2—C1—C6—C7−176.1 (8)C16—C15—C19—C20178.6 (6)
C2—C1—C6—C555.2 (12)C9—N1—C20—C19179.7 (6)
C4—C5—C6—C1−50.4 (11)Zn1—N1—C20—C195.5 (7)
C4—C5—C6—C7177.0 (8)C9—N1—C20—C12−0.9 (9)
Zn1i—O3—C7—O41.5 (6)Zn1—N1—C20—C12−175.0 (5)
Zn1i—O3—C7—C6−176.8 (5)N2—C19—C20—N1−1.3 (9)
Zn1i—O4—C7—O3−1.4 (6)C15—C19—C20—N1178.3 (6)
Zn1i—O4—C7—C6176.9 (5)N2—C19—C20—C12179.3 (6)
C1—C6—C7—O3−56.5 (10)C15—C19—C20—C12−1.2 (10)
C5—C6—C7—O374.4 (9)C11—C12—C20—N11.4 (9)
C1—C6—C7—O4125.2 (9)C13—C12—C20—N1−177.7 (6)
C5—C6—C7—O4−103.9 (8)C11—C12—C20—C19−179.1 (6)
Zn1—O1—C8—O217.5 (11)C13—C12—C20—C191.7 (9)
Zn1—O1—C8—C4−161.7 (5)

Symmetry codes: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1w—H11···O20.84 (6)1.80 (7)2.614 (6)162 (8)
O1w—H12···O4ii0.84 (6)1.89 (3)2.701 (6)161 (8)

Symmetry codes: (ii) x−1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2534).

References

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  • Westrip, S. P. (2009). publCIF In preparation.
  • Ye, B.-H., Tong, M.-L. & Chen, X.-M. (2003). Coord. Chem. Rev.246, 185–202.

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