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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 10| October 2012| Page m1276
https://doi.org/10.1107/S1600536812038901

Poly[(μ4-bi­phenyl-2,4′-di­carboxyl­ato-κ5O2:O2′:O4:O4,O4′)zinc]

Yu-Guang Tiana*

aCollege of Pharmaceutical Engineering, Guangdong Food and Drug Vocational College, Guangzhou 510520, People's Republic of China
*Correspondence e-mail: tianyg1980@yahoo.cn

(Received 17 August 2012; accepted 11 September 2012; online 19 September 2012)

The crystal structure of the polymeric title complex, [Zn(C14H8O4)]n, is composed of layers parallel to (110) formed by linking of Zn–carboxyl­ate chains with biphenyl units of the biphenyl-2,4′-dicarboxyl­ate (bpdc) ligands. The ZnII atom is five-coordinated in a distorted square-pyramidal geometry by five O atoms from four bpdc ligands. The dihedral angle between the benzene rings is 52.32 (12)°.

Related literature

For related structures, see: Guo et al. (2010[Guo, F., Zhang, X.-L., Zhu, B.-Y. & Qiu, J.-C. (2010). J. Mol. Evol. 20, 38-41.]); Jia et al. (2011[Jia, W.-W., Luo, J.-H. & Zhu, M.-L. (2011). Cryst. Growth Des. 11, 2386-2390.]); Zhang et al. (2011[Zhang, X.-L., Jin, M.-F., Qiu, Y.-E. & Guo, F. (2011). Inorg. Chem. Commun. 14, 952-956.]).

[Scheme 1]

Experimental

Crystal data

  • [Zn(C14H8O4)]

  • Mr = 305.59

  • Orthorhombic, P b c a

  • a = 12.702 (8) Å

  • b = 7.178 (4) Å

  • c = 25.368 (15) Å

  • V = 2313 (2) Å3

  • Z = 8

  • Mo Kα radiation

  • μ = 2.13 mm−1

  • T = 296 K

  • 0.25 × 0.20 × 0.18 mm
Data collection

  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.606, Tmax = 0.682

  • 10978 measured reflections

  • 2080 independent reflections

  • 1453 reflections with I > 2σ(I)

  • Rint = 0.060
Refinement

  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.086

  • S = 1.06

  • 2080 reflections

  • 172 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.43 e Å−3

  • Δρmin = −0.44 e Å−3

Table 1
Selected bond lengths (Å)

Zn1—O1i 1.971 (3)
Zn1—O2ii 1.937 (3)
Zn1—O3 2.130 (3)
Zn1—O3iii 2.003 (3)
Zn1—O4 2.204 (3)
Symmetry codes: (i) [x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]; (ii) -x+2, -y+1, -z+1; (iii) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812038901/hy2581sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812038901/hy2581Isup2.hkl

checkCIF report


Comment top

In recent years, the design and synthesis of metal-oganic frameworks (MOFs) are of great interest in the view of their fascinating structural diversity and significance of discovering new materials in the field of catalysis, gas storage, fluorescence, magnetism and so on. However, how to choose the metal centers and multidentate ligands is still a challedge. Biphenyl-2,4'-dicarboxylic acid (H2bpdc) can be utilized as a multifunctional bridging ligand because it can bridge metal centers to form chains, layers or three-dimensional networks. The rotation of the C—C single bond between the two phenyl rings gives rise to a skew coordination orientation of the carboxylate groups, which is favorable for the formation of various new complexes with intriguing architectures and topologies (Guo et al., 2010; Jia et al., 2011; Zhang et al., 2011). Recently, we synthesized the title coordination polymer under hydrothermal conditions.

In the title compound (Fig. 1), the bpdc ligand is fully deprotonated. The ZnII atom is five-coordinated by five O atoms from four different bpdc ligands in a distorted square-pyramidal geometry, with Zn—O distances and O—Zn—O angles ranging from 1.937 (2) to 2.204 (2) Å (Table 1) and 92.02 (11) to 108.20 (13)°, respectively. Adjacent ZnII atoms are bridged by a bidentate carboxylate group and a tridentate carboxylate group, which come from two different bpdc ligands, forming a Zn-carboxylate chain. These chains are further linked by the bpdc ligands into a layer structure (Fig. 2).

Related literature top

For related structures, see: Guo et al. (2010); Jia et al. (2011); Zhang et al. (2011).

Experimental top

A mixture of ZnCl2 (0.068 g, 0.5 mmol), biphenyl-2,4'-dicarboxylic acid (0.121 g, 0.5 mmol) and water (8 ml) in the presence of CH3COOH (2 ml) was stirred vigorously for 30 min and then sealed in a 20 ml Teflon-lined stainless-steel autoclave. The autoclave was heated and maintained at 393 K for 3 days, and then cooled to room temperature at 5 K h-1 to yield colorless block crystals.

Refinement top

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C).

Structure description top

In recent years, the design and synthesis of metal-oganic frameworks (MOFs) are of great interest in the view of their fascinating structural diversity and significance of discovering new materials in the field of catalysis, gas storage, fluorescence, magnetism and so on. However, how to choose the metal centers and multidentate ligands is still a challedge. Biphenyl-2,4'-dicarboxylic acid (H2bpdc) can be utilized as a multifunctional bridging ligand because it can bridge metal centers to form chains, layers or three-dimensional networks. The rotation of the C—C single bond between the two phenyl rings gives rise to a skew coordination orientation of the carboxylate groups, which is favorable for the formation of various new complexes with intriguing architectures and topologies (Guo et al., 2010; Jia et al., 2011; Zhang et al., 2011). Recently, we synthesized the title coordination polymer under hydrothermal conditions.

In the title compound (Fig. 1), the bpdc ligand is fully deprotonated. The ZnII atom is five-coordinated by five O atoms from four different bpdc ligands in a distorted square-pyramidal geometry, with Zn—O distances and O—Zn—O angles ranging from 1.937 (2) to 2.204 (2) Å (Table 1) and 92.02 (11) to 108.20 (13)°, respectively. Adjacent ZnII atoms are bridged by a bidentate carboxylate group and a tridentate carboxylate group, which come from two different bpdc ligands, forming a Zn-carboxylate chain. These chains are further linked by the bpdc ligands into a layer structure (Fig. 2).

For related structures, see: Guo et al. (2010); Jia et al. (2011); Zhang et al. (2011).

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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 2-x, 1-y, 1-z; (ii) 3/2-x, -1/2+y, z; (iii) -1/2+x, 3/2-y, 1-z.]
[Figure 2] Fig. 2. A view of the layer structure in the title compound.
Poly[(µ4-biphenyl-2,4'-dicarboxylato-κ5O2:O2':O4:O4,O4')zinc] top
Crystal data top
[Zn(C14H8O4)]F(000) = 1232.0
Mr = 305.59Dx = 1.755 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1609 reflections
a = 12.702 (8) Åθ = 2.3–21.7°
b = 7.178 (4) ŵ = 2.13 mm−1
c = 25.368 (15) ÅT = 296 K
V = 2313 (2) Å3Block, colourless
Z = 80.25 × 0.20 × 0.18 mm
Data collection top
Bruker APEXII CCD
diffractometer		2080 independent reflections
Radiation source: fine-focus sealed tube1453 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.060
φ and ω scansθmax = 25.2°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→15
Tmin = 0.606, Tmax = 0.682k = −8→8
10978 measured reflectionsl = −24→30
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)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.031P)2 + 1.2131P]
where P = (Fo2 + 2Fc2)/3
2080 reflections(Δ/σ)max = 0.001
172 parametersΔρmax = 0.43 e Å−3
1 restraintΔρmin = −0.44 e Å−3
Crystal data top
[Zn(C14H8O4)]V = 2313 (2) Å3
Mr = 305.59Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.702 (8) ŵ = 2.13 mm−1
b = 7.178 (4) ÅT = 296 K
c = 25.368 (15) Å0.25 × 0.20 × 0.18 mm
Data collection top
Bruker APEXII CCD
diffractometer		2080 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1453 reflections with I > 2σ(I)
Tmin = 0.606, Tmax = 0.682Rint = 0.060
10978 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0361 restraint
wR(F2) = 0.086H-atom parameters constrained
S = 1.06Δρmax = 0.43 e Å−3
2080 reflectionsΔρmin = −0.44 e Å−3
172 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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Zn10.75928 (3)0.20620 (6)0.422620 (17)0.03431 (17)
C11.0994 (3)1.0497 (6)0.63381 (14)0.0321 (9)
C21.0009 (3)1.0593 (5)0.66637 (13)0.0296 (9)
C30.9958 (3)1.1891 (6)0.70684 (16)0.0443 (11)
H31.04841.27870.70970.053*
C40.9143 (3)1.1879 (6)0.74286 (16)0.0499 (12)
H40.91341.27340.77040.060*
C50.8346 (3)1.0598 (6)0.73783 (15)0.0472 (11)
H50.77931.05810.76190.057*
C60.8373 (3)0.9341 (5)0.69682 (15)0.0371 (10)
H60.78230.84970.69320.044*
C70.9202 (3)0.9289 (5)0.66038 (13)0.0289 (9)
C80.9135 (3)0.7914 (5)0.61639 (14)0.0296 (8)
C90.8928 (3)0.6051 (6)0.62683 (15)0.0381 (10)
H90.89070.56330.66150.046*
C100.8751 (3)0.4808 (6)0.58591 (15)0.0412 (10)
H100.86180.35610.59340.049*
C110.8772 (3)0.5406 (5)0.53420 (14)0.0319 (9)
C120.9020 (3)0.7254 (5)0.52361 (14)0.0330 (9)
H120.90660.76580.48890.040*
C130.9201 (3)0.8498 (5)0.56432 (14)0.0333 (9)
H130.93670.97310.55670.040*
C140.8443 (3)0.4097 (6)0.49200 (15)0.0337 (9)
O11.1384 (2)1.2024 (4)0.61869 (12)0.0545 (8)
O21.13685 (19)0.8913 (4)0.62598 (10)0.0400 (7)
O30.8129 (2)0.4737 (3)0.44709 (10)0.0398 (6)
O40.8418 (2)0.2388 (4)0.49848 (11)0.0462 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0357 (3)0.0219 (3)0.0453 (3)−0.0005 (2)0.0018 (2)−0.0084 (2)
C10.031 (2)0.031 (2)0.035 (2)−0.0027 (19)−0.0082 (17)−0.0021 (18)
C20.030 (2)0.027 (2)0.032 (2)0.0031 (16)−0.0043 (16)−0.0039 (18)
C30.041 (2)0.040 (3)0.051 (3)0.003 (2)−0.008 (2)−0.013 (2)
C40.055 (3)0.054 (3)0.041 (3)0.012 (2)−0.005 (2)−0.021 (2)
C50.048 (3)0.055 (3)0.039 (3)0.017 (2)0.005 (2)−0.003 (2)
C60.036 (2)0.034 (3)0.041 (2)−0.0001 (18)−0.0007 (18)0.0013 (19)
C70.032 (2)0.028 (2)0.027 (2)0.0044 (16)−0.0030 (16)0.0012 (16)
C80.0271 (19)0.031 (2)0.031 (2)−0.0021 (17)−0.0023 (16)−0.0023 (18)
C90.047 (3)0.037 (2)0.031 (2)−0.009 (2)−0.0028 (18)0.0033 (19)
C100.051 (3)0.027 (2)0.046 (3)−0.0061 (19)−0.007 (2)0.001 (2)
C110.026 (2)0.034 (2)0.035 (2)−0.0012 (17)−0.0001 (16)−0.0038 (19)
C120.037 (2)0.035 (2)0.028 (2)−0.0041 (18)−0.0029 (17)0.0002 (18)
C130.037 (2)0.024 (2)0.040 (2)−0.0066 (17)−0.0041 (17)0.0019 (18)
C140.026 (2)0.040 (3)0.034 (2)0.0002 (18)0.0010 (17)−0.007 (2)
O10.0431 (17)0.0318 (18)0.088 (2)−0.0026 (14)0.0184 (15)−0.0057 (16)
O20.0440 (16)0.0259 (15)0.0502 (17)0.0058 (13)0.0097 (13)−0.0021 (13)
O30.0527 (17)0.0279 (12)0.0388 (16)0.0081 (12)−0.0096 (14)−0.0153 (13)
O40.0600 (19)0.0300 (17)0.0486 (18)−0.0129 (14)−0.0018 (14)−0.0046 (13)
Geometric parameters (Å, º) top
Zn1—O1i1.971 (3)C6—C71.401 (5)
Zn1—O2ii1.937 (3)C6—H60.9300
Zn1—O32.130 (3)C7—C81.493 (5)
Zn1—O3iii2.003 (3)C8—C131.388 (5)
Zn1—O42.204 (3)C8—C91.389 (5)
C1—O21.249 (4)C9—C101.387 (5)
C1—O11.263 (4)C9—H90.9300
C1—C21.501 (5)C10—C111.381 (5)
C2—C31.388 (5)C10—H100.9300
C2—C71.396 (5)C11—C121.390 (5)
C3—C41.380 (6)C11—C141.484 (5)
C3—H30.9300C12—C131.384 (5)
C4—C51.374 (6)C12—H120.9300
C4—H40.9300C13—H130.9300
C5—C61.378 (5)C14—O41.238 (5)
C5—H50.9300C14—O31.292 (4)
O2ii—Zn1—O1i108.20 (13)C2—C7—C8124.5 (3)
O2ii—Zn1—O3iii102.00 (11)C6—C7—C8117.9 (3)
O1i—Zn1—O3iii94.92 (12)C13—C8—C9118.9 (3)
O2ii—Zn1—O3107.08 (11)C13—C8—C7120.6 (3)
O1i—Zn1—O395.97 (11)C9—C8—C7120.3 (3)
O3iii—Zn1—O3143.83 (14)C10—C9—C8120.5 (4)
O2ii—Zn1—O4105.69 (11)C10—C9—H9119.8
O1i—Zn1—O4143.07 (12)C8—C9—H9119.8
O3iii—Zn1—O492.02 (11)C11—C10—C9120.5 (4)
O3—Zn1—O459.85 (10)C11—C10—H10119.7
O2—C1—O1126.3 (4)C9—C10—H10119.7
O2—C1—C2116.6 (3)C10—C11—C12119.0 (3)
O1—C1—C2117.0 (3)C10—C11—C14118.9 (4)
C3—C2—C7119.7 (4)C12—C11—C14121.9 (3)
C3—C2—C1118.5 (3)C13—C12—C11120.6 (3)
C7—C2—C1121.4 (3)C13—C12—H12119.7
C4—C3—C2121.4 (4)C11—C12—H12119.7
C4—C3—H3119.3C12—C13—C8120.3 (4)
C2—C3—H3119.3C12—C13—H13119.8
C5—C4—C3119.7 (4)C8—C13—H13119.8
C5—C4—H4120.2O4—C14—O3117.5 (3)
C3—C4—H4120.2O4—C14—C11122.6 (4)
C4—C5—C6119.3 (4)O3—C14—C11119.9 (4)
C4—C5—H5120.3C1—O1—Zn1iv139.1 (3)
C6—C5—H5120.3C1—O2—Zn1ii133.6 (3)
C5—C6—C7122.3 (4)C14—O3—Zn1v135.3 (2)
C5—C6—H6118.9C14—O3—Zn192.0 (2)
C7—C6—H6118.9Zn1v—O3—Zn1120.98 (13)
C2—C7—C6117.5 (3)C14—O4—Zn190.1 (2)
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y−1/2, z; (iv) x+1/2, −y+3/2, −z+1; (v) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula[Zn(C14H8O4)]
Mr305.59
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)12.702 (8), 7.178 (4), 25.368 (15)
V (Å3)2313 (2)
Z8
Radiation typeMo Kα
µ (mm−1)2.13
Crystal size (mm)0.25 × 0.20 × 0.18
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.606, 0.682
No. of measured, independent and
observed [I > 2σ(I)] reflections		10978, 2080, 1453
Rint0.060
(sin θ/λ)max (Å−1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.086, 1.06
No. of reflections2080
No. of parameters172
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.43, −0.44

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Zn1—O1i1.971 (3)Zn1—O3iii2.003 (3)
Zn1—O2ii1.937 (3)Zn1—O42.204 (3)
Zn1—O32.130 (3)
Symmetry codes: (i) x−1/2, −y+3/2, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+3/2, y−1/2, z.
 

Acknowledgements

The author acknowledges Guangdong Food and Drug Vocational College for supporting this work.

References

First citationBrandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
 First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationGuo, F., Zhang, X.-L., Zhu, B.-Y. & Qiu, J.-C. (2010). J. Mol. Evol. 20, 38–41.  CAS Google Scholar
 First citationJia, W.-W., Luo, J.-H. & Zhu, M.-L. (2011). Cryst. Growth Des. 11, 2386–2390.  Web of Science CSD CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationZhang, X.-L., Jin, M.-F., Qiu, Y.-E. & Guo, F. (2011). Inorg. Chem. Commun. 14, 952–956.  Web of Science CSD CrossRef Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 10| October 2012| Page m1276
https://doi.org/10.1107/S1600536812038901
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