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Acta Cryst. (2009). E65, m1178    [ doi:10.1107/S1600536809035144 ]

Bis([mu]-cyclohexane-1,3-dicarboxylato)-[kappa]3O1:O4,O4';[kappa]3O1,O1':O4-bis[aqua(1,10-phenanthroline-[kappa]2N,N')zinc(II)]

M. R. Rizal and S. W. Ng

Abstract top

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 top

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

Experimental top

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 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 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.

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 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.
Bis(µ-cyclohexane-1,3-dicarboxylato)-κ3O1: O4,O4';κ3O1,O1':O4- bis[aqua(1,10-phenanthroline-κ2N,N')zinc(II)] top
Crystal data top
[Zn2(C8H10O4)2(C12H8N2)2(H2O)2]F(000) = 896
Mr = 867.50Dx = 1.542 Mg m−3
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 mm−1
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 top
Bruker SMART APEX
diffractometer		3289 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 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)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177H atoms treated by a mixture of independent and constrained refinement
S = 1.09 w = 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 Å−3
74 restraintsΔρmin = −0.51 e Å−3
Crystal data top
[Zn2(C8H10O4)2(C12H8N2)2(H2O)2]V = 1868.84 (8) Å3
Mr = 867.50Z = 2
Monoclinic, P21/cMo Kα radiation
a = 9.6172 (2) ŵ = 1.35 mm−1
b = 17.4722 (5) ÅT = 100 K
c = 11.4822 (3) Å0.20 × 0.16 × 0.15 mm
β = 104.393 (2)°
Data collection top
Bruker SMART APEX
diffractometer		3289 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2706 reflections with I > 2σ(I)
Tmin = 0.774, Tmax = 0.823Rint = 0.032
9952 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.069H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.177Δρmax = 1.17 e Å−3
S = 1.09Δρmin = −0.51 e Å−3
3289 reflectionsAbsolute structure: ?
261 parametersFlack parameter: ?
74 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H11···O20.84 (6)1.80 (7)2.614 (6)162 (8)
O1w—H12···O4i0.84 (6)1.89 (3)2.701 (6)161 (8)
Symmetry codes: (i) x−1, y, z.
Acknowledgements top

We thank the University of Malaya for supporting this study.

references
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