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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): m855.
Published online 2008 June 7. doi:  10.1107/S1600536808015742
PMCID: PMC2961799

(5,5′-Dicarboxy­biphenyl-2,2′-dicarboxyl­ato-κ2 O 2,O 2′)bis­(1,10-phenanthroline-κ2 N,N′)zinc(II) dihydrate

Abstract

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.

Related literature

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

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Object name is e-64-0m855-scheme1.jpg

Experimental

Crystal data

  • [Zn(C16H8O8)(C12H8N2)2]·2H2O
  • M r = 790.03
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m855-efi1.jpg
  • a = 16.901 (5) Å
  • b = 9.473 (3) Å
  • c = 22.126 (7) Å
  • β = 96.429 (5)°
  • V = 3520.4 (19) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.77 mm−1
  • T = 293 (2) K
  • 0.26 × 0.22 × 0.20 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.817, T max = 0.853
  • 9664 measured reflections
  • 3487 independent reflections
  • 2437 reflections with I > 2σ(I)
  • R int = 0.049

Refinement

  • R[F 2 > 2σ(F 2)] = 0.057
  • wR(F 2) = 0.124
  • S = 1.04
  • 3487 reflections
  • 255 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.22 e Å−3

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

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015742/hy2133sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015742/hy2133Isup2.hkl

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

Acknowledgments

The authors thank Changchun Normal University for supporting this work.

supplementary crystallographic information

Comment

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).

Experimental

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

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.

Figures

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.]

Crystal data

[Zn(C16H8O8)(C12H8N2)2]·2H2OF000 = 1624
Mr = 790.03Dx = 1.491 Mg m3
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 mm1
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

Bruker SMART APEX CCD area-detector diffractometer3487 independent reflections
Radiation source: fine-focus sealed tube2437 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.049
T = 293(2) Kθmax = 26.2º
[var phi] 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

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 Å3
255 parametersΔρmin = −0.22 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

Special details

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)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2133).

References

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