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Acta Cryst. (2008). E64, m855    [ doi:10.1107/S1600536808015742 ]

(5,5'-Dicarboxybiphenyl-2,2'-dicarboxylato-[kappa]2O2,O2')bis(1,10-phenanthroline-[kappa]2N,N')zinc(II) dihydrate

R.-Z. Chen, F.-J. Guo and F.-L. Meng

Abstract top

In the title compound, [Zn(C16H8O8)(C12H8N2)2]·2H2O, the ZnII atom is located on a twofold rotation axis and is six-coordinated by two O atoms from a 5,5'-dicarboxybiphenyl-2,2'-dicarboxylate ligand and four N atoms from two 1,10-phenanthroline molecules in a distorted octahedral geometry. The crystal structure involves O-H...O hydrogen bonds.

Comment top

In the construction of new coordination polymers, multi-carboxylates act as multifunctional organic ligands not only due to their various coordination modes, resulting from fully or partially deprotonated sites, to allow for the large diversity in topologies, but also due to the ability to act as hydrogen-bond acceptors and donors to assemble supramolecular structures (Che et al., 2006; Chen et al., 2008; Lehn, 1990). We chose biphenyl-2,5,2',5'-tetracarboxylic acid (H4bptc) as a bridging ligand, 1,10-phenanthroline (phen) as a neutral ligand, and zinc(II) as a metal center, generating the title compound. We report here its crystal structure.

In the title compound, the ZnII atom, lying on a twofold rotation axis, is six-coordinated by two O atoms from one H2bptc ligand and four N atoms from two phen molecules in a distorted octahedral geometry (Fig. 1). The twofold rotation axis passes through the midpoint of the bond connecting two benzene rings of the H2bptc ligand. The bond lengths are within the normal ranges (Table 1) (Zang et al., 2006). The crystal structure involves O—H···O hydrogen bonds between the carboxylate O atoms and water molecules (Table 2).

Related literature top

For related literature, see: Che et al. (2006); Chen et al. (2008); Lehn (1990); Zang et al. (2006).

Experimental top

A mixture of ZnCl2.2H2O (0.017 g, 0.1 mmol), H4bptc (0.066 g, 0.2 mmol), phen (0.040 g, 0.2 mmol) and H2O(15 ml) in a 25 ml Teflon-lined stainless steel reactor was heated from 298 to 443 K in 2 h and a constant temperature was maintained at 443 K for 72 h. After cooling to 298 K, colorless crystals of the title compound were obtained from the reaction.

Refinement top

H atoms bonded to C atoms and carboxylate O atom were positioned geometrically and refined as riding atoms, with C—H = 0.93 and O—H = 0.82 Å and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O). The water H-atoms were located from a difference Fourier map and refined with a distance restraint of O—H = 0.85 (1) Å and Uiso(H) = 0.064 Å2.

Computing details top

Data collection: SMART (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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) 1-x, y, 1.5-z.]
(5,5'-Dicarboxybiphenyl-2,2'-dicarboxylato-κ2O2,O2')bis(1,10- phenanthroline-κ2N,N')zinc(II) dihydrate top
Crystal data top
[Zn(C16H8O8)(C12H8N2)2]·2H2OF000 = 1624
Mr = 790.03Dx = 1.491 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3487 reflections
a = 16.901 (5) Åθ = 2.0–26.0º
b = 9.473 (3) ŵ = 0.77 mm−1
c = 22.126 (7) ÅT = 293 (2) K
β = 96.429 (5)ºBlock, colorless
V = 3520.4 (19) Å30.26 × 0.22 × 0.20 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3487 independent reflections
Radiation source: fine-focus sealed tube2437 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.049
T = 293(2) Kθmax = 26.2º
φ and ω scansθmin = 1.9º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −20→18
Tmin = 0.817, Tmax = 0.853k = −11→11
9664 measured reflectionsl = −21→27
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)] = 0.057H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.125  w = 1/[σ2(Fo2) + (0.0505P)2 + 0.8309P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3487 reflectionsΔρmax = 0.31 e Å−3
255 parametersΔρmin = −0.22 e Å−3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Zn(C16H8O8)(C12H8N2)2]·2H2OV = 3520.4 (19) Å3
Mr = 790.03Z = 4
Monoclinic, C2/cMo Kα
a = 16.901 (5) ŵ = 0.77 mm−1
b = 9.473 (3) ÅT = 293 (2) K
c = 22.126 (7) Å0.26 × 0.22 × 0.20 mm
β = 96.429 (5)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3487 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2437 reflections with I > 2σ(I)
Tmin = 0.817, Tmax = 0.853Rint = 0.049
9664 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0572 restraints
wR(F2) = 0.125H atoms treated by a mixture of
independent and constrained refinement
S = 1.04Δρmax = 0.31 e Å−3
3487 reflectionsΔρmin = −0.22 e Å−3
255 parameters
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3739 (2)0.3651 (5)0.63923 (18)0.0637 (11)
H10.35430.29580.66340.076*
C20.3354 (3)0.3873 (6)0.5804 (2)0.0880 (16)
H20.29130.33370.56560.106*
C30.3645 (3)0.4896 (6)0.5454 (2)0.0926 (17)
H30.33900.50770.50670.111*
C40.4311 (3)0.5664 (5)0.5667 (2)0.0762 (14)
C50.4663 (4)0.6727 (6)0.5317 (2)0.0988 (19)
H50.44240.69480.49290.119*
C60.5326 (4)0.7401 (6)0.5538 (3)0.106 (2)
H60.55420.80740.52980.127*
C70.5713 (3)0.7116 (4)0.6134 (2)0.0776 (14)
C80.6414 (4)0.7740 (5)0.6377 (3)0.098 (2)
H80.66590.84080.61520.117*
C90.6744 (3)0.7386 (5)0.6936 (3)0.0906 (17)
H90.72220.77930.70980.109*
C100.6361 (3)0.6400 (4)0.7274 (2)0.0722 (13)
H100.65930.61640.76610.087*
C110.5368 (3)0.6116 (4)0.6493 (2)0.0600 (11)
C120.4662 (3)0.5378 (4)0.62567 (18)0.0588 (11)
C130.40756 (18)0.1983 (3)0.81456 (14)0.0328 (7)
C140.47901 (16)0.1060 (3)0.82887 (12)0.0264 (7)
C150.51756 (16)0.0460 (3)0.78249 (12)0.0240 (6)
C160.58975 (17)−0.0230 (3)0.79802 (13)0.0299 (7)
H160.6169−0.06130.76760.036*
C170.62178 (18)−0.0353 (3)0.85843 (14)0.0335 (7)
C180.58141 (19)0.0192 (4)0.90393 (14)0.0421 (9)
H180.60210.00940.94450.051*
C190.51007 (18)0.0882 (3)0.88893 (13)0.0383 (8)
H190.48240.12350.91970.046*
C200.6999 (2)−0.1096 (4)0.87475 (16)0.0460 (9)
N10.43688 (18)0.4390 (3)0.66158 (13)0.0510 (8)
N20.5682 (2)0.5791 (3)0.70633 (15)0.0563 (8)
O10.40798 (12)0.2849 (2)0.77191 (9)0.0370 (5)
O20.35134 (14)0.1861 (3)0.84667 (11)0.0646 (8)
O1W0.33466 (18)0.0544 (3)0.95823 (12)0.0704 (8)
O30.73266 (15)−0.1494 (3)0.82746 (11)0.0707 (9)
H3A0.7749−0.18930.83840.106*
O40.72855 (15)−0.1289 (3)0.92612 (11)0.0786 (10)
Zn10.50000.41820 (6)0.75000.0430 (2)
H1B0.315 (2)0.112 (3)0.9823 (14)0.064*
H1A0.333 (2)0.110 (3)0.9282 (12)0.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.053 (3)0.081 (3)0.058 (3)0.011 (2)0.009 (2)0.017 (2)
C20.054 (3)0.135 (5)0.074 (3)0.021 (3)0.002 (2)0.021 (3)
C30.085 (4)0.133 (5)0.061 (3)0.046 (4)0.016 (3)0.038 (3)
C40.092 (4)0.076 (3)0.065 (3)0.033 (3)0.030 (3)0.029 (3)
C50.145 (6)0.088 (4)0.072 (4)0.041 (4)0.049 (4)0.042 (3)
C60.168 (6)0.065 (4)0.097 (5)0.018 (4)0.071 (4)0.030 (3)
C70.116 (4)0.045 (3)0.084 (4)0.007 (3)0.065 (3)0.006 (2)
C80.151 (6)0.051 (3)0.109 (5)−0.032 (3)0.093 (4)−0.018 (3)
C90.113 (4)0.068 (3)0.104 (4)−0.040 (3)0.071 (4)−0.032 (3)
C100.093 (4)0.052 (2)0.081 (3)−0.023 (2)0.047 (3)−0.020 (2)
C110.083 (3)0.035 (2)0.070 (3)0.007 (2)0.044 (2)−0.0001 (19)
C120.076 (3)0.051 (2)0.056 (3)0.027 (2)0.033 (2)0.0180 (19)
C130.0281 (18)0.0396 (18)0.0312 (18)0.0106 (14)0.0054 (14)0.0015 (15)
C140.0225 (16)0.0314 (17)0.0255 (16)0.0040 (12)0.0037 (12)−0.0001 (12)
C150.0231 (16)0.0238 (15)0.0253 (16)0.0002 (11)0.0036 (12)0.0000 (11)
C160.0247 (17)0.0352 (17)0.0304 (18)0.0077 (13)0.0056 (13)−0.0018 (13)
C170.0262 (18)0.0431 (18)0.0310 (18)0.0093 (14)0.0018 (13)0.0017 (14)
C180.039 (2)0.063 (2)0.0236 (18)0.0165 (17)0.0000 (14)−0.0008 (16)
C190.0358 (19)0.054 (2)0.0266 (17)0.0185 (16)0.0097 (14)−0.0025 (15)
C200.033 (2)0.070 (3)0.035 (2)0.0191 (17)0.0034 (16)0.0049 (17)
N10.051 (2)0.0519 (19)0.052 (2)0.0120 (16)0.0165 (15)0.0146 (15)
N20.072 (2)0.0382 (17)0.066 (2)−0.0056 (17)0.0362 (18)−0.0067 (16)
O10.0319 (13)0.0374 (12)0.0422 (13)0.0101 (10)0.0063 (10)0.0116 (10)
O20.0449 (16)0.098 (2)0.0564 (17)0.0427 (15)0.0294 (12)0.0411 (15)
O1W0.079 (2)0.088 (2)0.0457 (19)0.0195 (17)0.0126 (15)0.0143 (15)
O30.0530 (17)0.121 (2)0.0388 (15)0.0559 (17)0.0072 (12)0.0098 (15)
O40.0610 (19)0.133 (3)0.0394 (16)0.0561 (18)−0.0040 (13)0.0029 (16)
Zn10.0470 (4)0.0373 (3)0.0467 (4)0.0000.0144 (3)0.000
Geometric parameters (Å, °) top
C1—N11.323 (5)C13—O21.254 (4)
C1—C21.405 (6)C13—C141.496 (4)
C1—H10.9300C14—C191.383 (4)
C2—C31.366 (7)C14—C151.396 (4)
C2—H20.9300C15—C161.393 (4)
C3—C41.378 (7)C15—C15i1.493 (5)
C3—H30.9300C16—C171.390 (4)
C4—C121.399 (6)C16—H160.9300
C4—C51.439 (7)C17—C181.378 (4)
C5—C61.334 (7)C17—C201.504 (4)
C5—H50.9300C18—C191.379 (4)
C6—C71.431 (7)C18—H180.9300
C6—H60.9300C19—H190.9300
C7—C81.378 (7)C20—O41.198 (4)
C7—C111.404 (5)C20—O31.294 (4)
C8—C91.341 (7)N1—Zn12.130 (3)
C8—H80.9300N2—Zn12.199 (3)
C9—C101.399 (6)O1—Zn12.102 (2)
C9—H90.9300O1W—H1B0.86 (3)
C10—N21.321 (5)O1W—H1A0.85 (3)
C10—H100.9300O3—H3A0.8200
C11—N21.348 (5)Zn1—O12.102 (2)
C11—C121.431 (6)Zn1—N12.130 (3)
C12—N11.357 (4)Zn1—N22.199 (3)
C13—O11.251 (3)
N1—C1—C2122.5 (4)C16—C15—C14118.5 (3)
N1—C1—H1118.8C16—C15—C15i118.7 (3)
C2—C1—H1118.8C14—C15—C15i122.7 (3)
C3—C2—C1118.2 (5)C17—C16—C15120.9 (3)
C3—C2—H2120.9C17—C16—H16119.6
C1—C2—H2120.9C15—C16—H16119.6
C2—C3—C4120.8 (5)C18—C17—C16120.0 (3)
C2—C3—H3119.6C18—C17—C20119.5 (3)
C4—C3—H3119.6C16—C17—C20120.5 (3)
C3—C4—C12117.5 (4)C17—C18—C19119.5 (3)
C3—C4—C5123.8 (5)C17—C18—H18120.2
C12—C4—C5118.7 (5)C19—C18—H18120.2
C6—C5—C4121.3 (5)C18—C19—C14121.1 (3)
C6—C5—H5119.4C18—C19—H19119.5
C4—C5—H5119.4C14—C19—H19119.5
C5—C6—C7121.7 (5)O4—C20—O3124.0 (3)
C5—C6—H6119.1O4—C20—C17123.3 (3)
C7—C6—H6119.1O3—C20—C17112.7 (3)
C8—C7—C11117.4 (5)C1—N1—C12118.5 (4)
C8—C7—C6124.2 (5)C1—N1—Zn1126.4 (3)
C11—C7—C6118.3 (5)C12—N1—Zn1115.1 (3)
C9—C8—C7120.2 (5)C10—N2—C11117.7 (4)
C9—C8—H8119.9C10—N2—Zn1128.7 (3)
C7—C8—H8119.9C11—N2—Zn1113.5 (3)
C8—C9—C10119.3 (5)C13—O1—Zn1129.41 (19)
C8—C9—H9120.3H1B—O1W—H1A96 (4)
C10—C9—H9120.3C20—O3—H3A109.5
N2—C10—C9122.6 (5)O1—Zn1—O1i106.16 (11)
N2—C10—H10118.7O1—Zn1—N1i98.70 (10)
C9—C10—H10118.7O1i—Zn1—N1i87.72 (10)
N2—C11—C7122.7 (5)O1—Zn1—N187.72 (10)
N2—C11—C12117.1 (3)O1i—Zn1—N198.70 (10)
C7—C11—C12120.2 (5)N1i—Zn1—N1169.36 (16)
N1—C12—C4122.4 (4)O1—Zn1—N2162.88 (11)
N1—C12—C11117.8 (4)O1i—Zn1—N282.94 (10)
C4—C12—C11119.7 (4)N1i—Zn1—N296.08 (12)
O1—C13—O2123.8 (3)N1—Zn1—N276.44 (13)
O1—C13—C14118.1 (3)O1—Zn1—N2i82.94 (10)
O2—C13—C14118.1 (3)O1i—Zn1—N2i162.88 (11)
C19—C14—C15119.9 (3)N1i—Zn1—N2i76.44 (13)
C19—C14—C13119.0 (3)N1—Zn1—N2i96.08 (12)
C15—C14—C13121.0 (2)N2—Zn1—N2i92.23 (15)
N1—C1—C2—C3−0.2 (7)C16—C17—C20—O4−176.6 (4)
C1—C2—C3—C41.7 (8)C18—C17—C20—O3−177.0 (3)
C2—C3—C4—C12−1.5 (7)C16—C17—C20—O33.8 (5)
C2—C3—C4—C5178.1 (4)C2—C1—N1—C12−1.4 (6)
C3—C4—C5—C6−177.5 (5)C2—C1—N1—Zn1179.3 (3)
C12—C4—C5—C62.2 (8)C4—C12—N1—C11.6 (5)
C4—C5—C6—C7−0.8 (9)C11—C12—N1—C1−176.8 (3)
C5—C6—C7—C8177.4 (5)C4—C12—N1—Zn1−179.0 (3)
C5—C6—C7—C11−1.3 (8)C11—C12—N1—Zn12.6 (4)
C11—C7—C8—C90.1 (7)C9—C10—N2—C112.0 (6)
C6—C7—C8—C9−178.6 (5)C9—C10—N2—Zn1178.0 (3)
C7—C8—C9—C10−1.2 (7)C7—C11—N2—C10−3.2 (5)
C8—C9—C10—N20.2 (7)C12—C11—N2—C10175.9 (3)
C8—C7—C11—N22.2 (6)C7—C11—N2—Zn1−179.8 (3)
C6—C7—C11—N2−179.1 (4)C12—C11—N2—Zn1−0.8 (4)
C8—C7—C11—C12−176.9 (4)O2—C13—O1—Zn1135.8 (3)
C6—C7—C11—C121.9 (6)C14—C13—O1—Zn1−42.9 (4)
C3—C4—C12—N1−0.2 (6)C13—O1—Zn1—O1i63.6 (2)
C5—C4—C12—N1−179.8 (4)C13—O1—Zn1—N1i−26.5 (3)
C3—C4—C12—C11178.2 (4)C13—O1—Zn1—N1162.0 (3)
C5—C4—C12—C11−1.5 (6)C13—O1—Zn1—N2−176.0 (3)
N2—C11—C12—N1−1.2 (5)C13—O1—Zn1—N2i−101.6 (3)
C7—C11—C12—N1177.9 (3)C1—N1—Zn1—O1−9.4 (3)
N2—C11—C12—C4−179.6 (3)C12—N1—Zn1—O1171.3 (2)
C7—C11—C12—C4−0.5 (6)C1—N1—Zn1—O1i96.6 (3)
O1—C13—C14—C19134.7 (3)C12—N1—Zn1—O1i−82.7 (2)
O2—C13—C14—C19−44.2 (4)C1—N1—Zn1—N1i−136.8 (3)
O1—C13—C14—C15−40.9 (4)C12—N1—Zn1—N1i43.9 (2)
O2—C13—C14—C15140.3 (3)C1—N1—Zn1—N2177.1 (3)
C19—C14—C15—C16−4.1 (4)C12—N1—Zn1—N2−2.2 (2)
C13—C14—C15—C16171.4 (3)C1—N1—Zn1—N2i−92.1 (3)
C19—C14—C15—C15i172.4 (2)C12—N1—Zn1—N2i88.6 (2)
C13—C14—C15—C15i−12.1 (4)C10—N2—Zn1—O1162.7 (3)
C14—C15—C16—C171.7 (4)C11—N2—Zn1—O1−21.1 (5)
C15i—C15—C16—C17−175.0 (2)C10—N2—Zn1—O1i−73.9 (3)
C15—C16—C17—C181.1 (5)C11—N2—Zn1—O1i102.3 (2)
C15—C16—C17—C20−179.8 (3)C10—N2—Zn1—N1i13.1 (3)
C16—C17—C18—C19−1.3 (5)C11—N2—Zn1—N1i−170.7 (2)
C20—C17—C18—C19179.5 (3)C10—N2—Zn1—N1−174.6 (3)
C17—C18—C19—C14−1.1 (5)C11—N2—Zn1—N11.6 (2)
C15—C14—C19—C183.9 (5)C10—N2—Zn1—N2i89.7 (3)
C13—C14—C19—C18−171.7 (3)C11—N2—Zn1—N2i−94.1 (3)
C18—C17—C20—O42.6 (6)
Symmetry codes: (i) −x+1, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O2ii0.821.742.538 (3)162
O1W—H1B···O4iii0.86 (3)2.24 (2)2.966 (4)143 (3)
O1W—H1A···O20.85 (3)2.00 (2)2.808 (4)159 (4)
Symmetry codes: (ii) x+1/2, y−1/2, z; (iii) −x+1, −y, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Zn1—O12.102 (2)Zn1—N22.199 (3)
Zn1—N12.130 (3)
O1—Zn1—O1i106.16 (11)N1—Zn1—N276.44 (13)
O1—Zn1—N1i98.70 (10)O1—Zn1—N2i82.94 (10)
O1—Zn1—N187.72 (10)N1—Zn1—N2i96.08 (12)
N1i—Zn1—N1169.36 (16)N2—Zn1—N2i92.23 (15)
O1—Zn1—N2162.88 (11)
Symmetry codes: (i) −x+1, y, −z+3/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O2ii0.821.742.538 (3)162
O1W—H1B···O4iii0.86 (3)2.24 (2)2.966 (4)143 (3)
O1W—H1A···O20.85 (3)2.00 (2)2.808 (4)159 (4)
Symmetry codes: (ii) x+1/2, y−1/2, z; (iii) −x+1, −y, −z+2.
Acknowledgements top

The authors thank Changchun Normal University for supporting this work.

references
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