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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m880.
Published online 2009 July 8. doi:  10.1107/S1600536809025525
PMCID: PMC2977467

Aqua­(2,2′-bipyridine)bis­(4-hydroxy­benzoato)zinc(II)

Abstract

In the title complex, [Zn(C7H5O3)2(C10H8N2)(H2O)], the ZnII ion is coordinated by two 4-hydroxy­benzoate anions, one 2,2′-bipyridine mol­ecule and one water mol­ecule and displays a distorted octa­hedral geometry. One Zn—O bond [2.5300 (15) Å] is much longer than the others in the mol­ecule. In the crystal structure, the face-to-face separation of 3.547 (9) Å suggests no π–π stacking between parallel bipyridine ring systems, and an extensive O—H(...)O hydrogen-bonding network between the coordinated water molecule, the phenol group and carboxylate O atoms is present.

Related literature

For general background, see: Xu et al. (2007a [triangle],b [triangle]); Li et al. (2005 [triangle]). For a related structure, see: Kong et al. (2008 [triangle]). For the smaller metal—O—C bond angle corresponding to the longer coordination bond, see: Li et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m880-scheme1.jpg

Experimental

Crystal data

  • [Zn(C7H5O3)2(C10H8N2)(H2O)]
  • M r = 513.79
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m880-efi1.jpg
  • a = 10.3549 (12) Å
  • b = 19.524 (3) Å
  • c = 11.5544 (18) Å
  • β = 107.97 (2)°
  • V = 2221.9 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.16 mm−1
  • T = 294 K
  • 0.40 × 0.32 × 0.28 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.659, T max = 0.724
  • 13723 measured reflections
  • 5092 independent reflections
  • 3794 reflections with I > 2σ(I)
  • R int = 0.028

Refinement

  • R[F 2 > 2σ(F 2)] = 0.033
  • wR(F 2) = 0.084
  • S = 1.07
  • 5092 reflections
  • 307 parameters
  • H-atom parameters constrained
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.31 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 [triangle]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SIR92 (Altomare et al., 1993 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025525/hk2727sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025525/hk2727Isup2.hkl

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

Acknowledgments

The project was supported by the ZIJIN project of Zhejiang University, China.

supplementary crystallographic information

Comment

As a part of our ongoing investigation on the nature of π-π stacking (Xu et al., 2007a, 2007b; Li et al., 2005), the title complex was prepared in the laboratory and its crystal structure is reported herein.

The molecular structure of the title complex is shown in Fig. 1. The ZnII cation is coordinated by two 4-hydroxybenzoate anions, one 2,2-bipyridine and one water molecules with a distorted octahedral geometry. The Zn—O1 [2.5300 (15) Å] bond is much longer than the other Zn—O bonds in the molecule (Table 1), but the smaller Zn–O2–C1 [103.38 (13)°] bond angle suggests the existence of a genuine bonding between O1 and Zn atoms (Li et al. 2005). This is similar to that in aqua-(4-hydroxybenzoato)(4-hydroxybenzoato) (1,10-phenanthroline)zinc monohydrate (Kong et al., 2008).

In the crystal structure, extensive O—H···O hydrogen bonding occurs (Table 2) and the longer face-to-face separation of 3.547 (9) Å between parallel bipyridine ligands, related by an inversion center, suggests no π-π stacking.

Experimental

ZnCl2 (0.136 g, 1 mmol), 4-hydroxybenzoic acid (0.14 g, 1 mmol), Na2CO3 (0.053 g, 0.5 mmol) and 2,2-bipyridine (0.156 g, 1 mmol) were dissolved in a water/ethanol solution (20 ml, 2:3). The mixture was refluxed for 4 h, and then cooled to room temperature and filtered. Colorless single crystals were obtained from the filtrate after 10 d.

Refinement

H atoms of hydroxy groups and water molecules were located in a difference Fourier map and refined as riding in their as-found relative positions, Uiso(H) = 1.5Ueq(O). Other H atoms were placed in calculated positions with C—H = 0.93 Å, and refined in riding mode with Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of the title complex with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). The dashed line indicates the intramolecular hydrogen bonding.

Crystal data

[Zn(C7H5O3)2(C10H8N2)(H2O)]F(000) = 1056
Mr = 513.79Dx = 1.536 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8786 reflections
a = 10.3549 (12) Åθ = 2.8–25.0°
b = 19.524 (3) ŵ = 1.16 mm1
c = 11.5544 (18) ÅT = 294 K
β = 107.97 (2)°Prism, colorless
V = 2221.9 (6) Å30.40 × 0.32 × 0.28 mm
Z = 4

Data collection

Rigaku R-AXIS RAPID IP diffractometer5092 independent reflections
Radiation source: fine-focus sealed tube3794 reflections with I > 2σ(I)
graphiteRint = 0.028
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 2.1°
ω scansh = −13→12
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −16→25
Tmin = 0.659, Tmax = 0.724l = −15→14
13723 measured reflections

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)] = 0.033Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.07w = 1/[σ2(Fo2) + (0.0381P)2 + 0.2291P] where P = (Fo2 + 2Fc2)/3
5092 reflections(Δ/σ)max = 0.001
307 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.30 e Å3

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.
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)

xyzUiso*/Ueq
Zn0.72142 (2)0.523813 (12)0.76441 (2)0.03203 (9)
N10.71413 (18)0.55972 (9)0.93348 (15)0.0364 (4)
N20.50939 (18)0.52685 (8)0.74053 (16)0.0326 (4)
O10.79866 (17)0.40502 (8)0.84339 (14)0.0472 (4)
O20.72447 (15)0.44341 (7)0.65740 (13)0.0390 (4)
O30.90448 (17)0.14372 (8)0.55801 (14)0.0503 (4)
H3A0.86120.13140.47700.075*
O40.69289 (14)0.60029 (7)0.63604 (13)0.0349 (3)
O50.88734 (15)0.59867 (8)0.59074 (13)0.0419 (4)
O60.53361 (16)0.81021 (8)0.20163 (14)0.0473 (4)
H6A0.59400.83480.18160.071*
O70.93531 (15)0.53817 (7)0.80380 (14)0.0418 (4)
H7A0.97550.57460.84750.063*
H7B0.92810.55020.72270.063*
C10.7783 (2)0.39661 (10)0.73229 (19)0.0329 (5)
C20.8162 (2)0.33111 (10)0.68419 (18)0.0293 (4)
C30.8999 (2)0.28391 (10)0.76110 (18)0.0329 (5)
H30.93670.29420.84340.039*
C40.9297 (2)0.22205 (11)0.71799 (18)0.0359 (5)
H40.98710.19110.77060.043*
C50.8738 (2)0.20608 (10)0.59584 (19)0.0342 (5)
C60.7894 (2)0.25250 (11)0.51718 (19)0.0359 (5)
H60.75080.24170.43540.043*
C70.7633 (2)0.31490 (10)0.56143 (18)0.0329 (5)
H70.70930.34670.50810.040*
C80.7700 (2)0.61981 (10)0.57269 (18)0.0315 (5)
C90.7101 (2)0.67051 (10)0.47486 (18)0.0323 (5)
C100.5709 (2)0.67839 (12)0.4277 (2)0.0418 (5)
H100.51430.65160.45790.050*
C110.5143 (2)0.72511 (12)0.3370 (2)0.0442 (6)
H110.42050.72920.30590.053*
C120.5968 (2)0.76610 (11)0.29181 (19)0.0360 (5)
C130.7366 (2)0.75963 (11)0.3390 (2)0.0402 (5)
H130.79280.78750.31030.048*
C140.7924 (2)0.71194 (11)0.42857 (19)0.0386 (5)
H140.88630.70730.45850.046*
C150.8215 (3)0.56939 (13)1.0329 (2)0.0484 (6)
H150.90750.55841.02900.058*
C160.8100 (3)0.59469 (14)1.1398 (2)0.0607 (7)
H160.88660.60091.20690.073*
C170.6831 (3)0.61079 (14)1.1463 (2)0.0614 (8)
H170.67270.62861.21760.074*
C180.5722 (3)0.60022 (13)1.0462 (2)0.0532 (7)
H180.48550.61051.04920.064*
C190.5899 (2)0.57419 (10)0.9407 (2)0.0367 (5)
C200.4749 (2)0.55895 (11)0.82961 (19)0.0359 (5)
C210.3423 (3)0.57615 (13)0.8165 (2)0.0528 (6)
H210.31990.59840.87880.063*
C220.2426 (3)0.55975 (15)0.7089 (3)0.0590 (7)
H220.15260.57150.69810.071*
C230.2768 (3)0.52628 (13)0.6190 (2)0.0512 (6)
H230.21110.51420.54680.061*
C240.4112 (2)0.51086 (12)0.6382 (2)0.0424 (5)
H240.43510.48820.57700.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn0.03499 (15)0.02836 (14)0.03540 (15)0.00098 (10)0.01475 (11)−0.00214 (10)
N10.0381 (11)0.0359 (10)0.0350 (10)−0.0019 (8)0.0111 (8)−0.0014 (8)
N20.0357 (10)0.0325 (10)0.0333 (9)−0.0021 (7)0.0159 (8)−0.0029 (8)
O10.0717 (12)0.0333 (9)0.0397 (9)0.0048 (8)0.0215 (8)−0.0022 (7)
O20.0454 (9)0.0282 (8)0.0428 (9)0.0082 (7)0.0128 (7)0.0003 (7)
O30.0730 (12)0.0339 (9)0.0415 (9)0.0193 (8)0.0141 (8)−0.0036 (7)
O40.0375 (8)0.0302 (8)0.0424 (8)0.0048 (6)0.0204 (7)0.0063 (6)
O50.0306 (9)0.0527 (10)0.0440 (9)0.0025 (7)0.0140 (7)0.0054 (7)
O60.0439 (10)0.0430 (9)0.0572 (10)−0.0002 (7)0.0186 (8)0.0184 (8)
O70.0359 (9)0.0431 (9)0.0450 (9)−0.0054 (7)0.0103 (7)0.0000 (7)
C10.0329 (11)0.0263 (11)0.0414 (12)−0.0033 (9)0.0142 (10)−0.0021 (9)
C20.0296 (11)0.0252 (10)0.0364 (11)−0.0009 (8)0.0149 (9)0.0000 (8)
C30.0352 (12)0.0324 (11)0.0311 (11)0.0012 (9)0.0102 (9)−0.0009 (9)
C40.0408 (13)0.0321 (12)0.0341 (11)0.0101 (9)0.0105 (9)0.0062 (9)
C50.0407 (13)0.0275 (11)0.0387 (12)0.0044 (9)0.0187 (10)−0.0004 (9)
C60.0410 (13)0.0375 (12)0.0293 (11)0.0051 (9)0.0109 (9)−0.0023 (9)
C70.0339 (12)0.0301 (11)0.0357 (12)0.0064 (9)0.0121 (9)0.0054 (9)
C80.0338 (12)0.0277 (11)0.0337 (11)−0.0056 (9)0.0115 (9)−0.0065 (9)
C90.0339 (12)0.0300 (11)0.0345 (11)−0.0029 (9)0.0126 (9)0.0000 (9)
C100.0355 (13)0.0440 (13)0.0496 (14)−0.0061 (10)0.0186 (11)0.0098 (11)
C110.0295 (12)0.0501 (14)0.0534 (14)−0.0022 (10)0.0133 (10)0.0146 (11)
C120.0407 (13)0.0311 (11)0.0381 (12)−0.0024 (9)0.0151 (10)0.0023 (9)
C130.0374 (13)0.0403 (13)0.0460 (14)−0.0113 (10)0.0172 (10)0.0052 (10)
C140.0305 (12)0.0433 (13)0.0426 (13)−0.0080 (9)0.0121 (10)0.0016 (10)
C150.0475 (15)0.0535 (16)0.0415 (14)−0.0066 (11)0.0099 (11)0.0007 (12)
C160.069 (2)0.0658 (19)0.0397 (15)−0.0206 (15)0.0060 (13)−0.0063 (13)
C170.087 (2)0.0605 (18)0.0409 (15)−0.0099 (15)0.0252 (15)−0.0159 (13)
C180.0646 (18)0.0538 (16)0.0480 (15)0.0030 (13)0.0274 (13)−0.0110 (12)
C190.0453 (13)0.0275 (11)0.0409 (12)0.0003 (9)0.0186 (10)−0.0009 (9)
C200.0392 (13)0.0331 (12)0.0399 (12)0.0009 (9)0.0187 (10)0.0001 (10)
C210.0457 (15)0.0651 (17)0.0541 (16)0.0074 (12)0.0249 (13)−0.0058 (13)
C220.0365 (14)0.075 (2)0.0681 (19)0.0054 (13)0.0194 (13)0.0037 (15)
C230.0399 (14)0.0640 (18)0.0464 (14)−0.0067 (12)0.0082 (11)0.0046 (13)
C240.0448 (14)0.0463 (14)0.0377 (12)−0.0075 (11)0.0151 (11)−0.0042 (10)

Geometric parameters (Å, °)

Zn—O12.5300 (15)C7—H70.9300
Zn—O22.0045 (14)C8—C91.486 (3)
Zn—O42.0607 (14)C9—C101.383 (3)
Zn—O72.1375 (15)C9—C141.396 (3)
Zn—N12.0986 (18)C10—C111.377 (3)
Zn—N22.1275 (17)C10—H100.9300
N1—C151.343 (3)C11—C121.384 (3)
N1—C191.344 (3)C11—H110.9300
N2—C241.337 (3)C12—C131.386 (3)
N2—C201.344 (3)C13—C141.379 (3)
O1—C11.246 (2)C13—H130.9300
O2—C11.264 (2)C14—H140.9300
O3—C51.364 (2)C15—C161.369 (3)
O3—H3A0.9362C15—H150.9300
O4—C81.295 (2)C16—C171.375 (4)
O5—C81.239 (2)C16—H160.9300
O6—C121.355 (2)C17—C181.371 (4)
O6—H6A0.8744C17—H170.9300
O7—H7A0.8971C18—C191.384 (3)
O7—H7B0.9465C18—H180.9300
C1—C21.494 (3)C19—C201.487 (3)
C2—C31.384 (3)C20—C211.376 (3)
C2—C71.390 (3)C21—C221.386 (4)
C3—C41.377 (3)C21—H210.9300
C3—H30.9300C22—C231.364 (4)
C4—C51.386 (3)C22—H220.9300
C4—H40.9300C23—C241.373 (3)
C5—C61.386 (3)C23—H230.9300
C6—C71.380 (3)C24—H240.9300
C6—H60.9300
O1—Zn—O256.03 (5)O5—C8—C9120.47 (18)
O1—Zn—O4152.01 (5)O4—C8—C9116.13 (18)
O1—Zn—O781.49 (6)C10—C9—C14118.02 (19)
O1—Zn—N193.94 (6)C10—C9—C8120.87 (18)
O1—Zn—N2105.73 (6)C14—C9—C8121.11 (19)
O2—Zn—O498.60 (6)C11—C10—C9121.4 (2)
O2—Zn—O791.23 (6)C11—C10—H10119.3
O2—Zn—N1147.97 (7)C9—C10—H10119.3
O2—Zn—N298.85 (6)C10—C11—C12120.2 (2)
O4—Zn—O788.12 (6)C10—C11—H11119.9
O4—Zn—N1112.93 (6)C12—C11—H11119.9
O4—Zn—N288.48 (6)O6—C12—C11116.7 (2)
N1—Zn—O795.19 (7)O6—C12—C13123.98 (19)
N1—Zn—N277.25 (7)C11—C12—C13119.3 (2)
N2—Zn—O7169.74 (6)C14—C13—C12120.1 (2)
Zn—O1—C179.34 (12)C14—C13—H13119.9
Zn—O2—C1103.38 (13)C12—C13—H13119.9
Zn—O4—C8130.04 (13)C13—C14—C9121.0 (2)
C15—N1—C19118.2 (2)C13—C14—H14119.5
C15—N1—Zn125.83 (16)C9—C14—H14119.5
C19—N1—Zn115.97 (14)N1—C15—C16122.9 (2)
C24—N2—C20118.50 (19)N1—C15—H15118.6
C24—N2—Zn125.52 (15)C16—C15—H15118.6
C20—N2—Zn114.88 (14)C15—C16—C17118.8 (2)
C5—O3—H3A117.6C15—C16—H16120.6
C12—O6—H6A109.7C17—C16—H16120.6
Zn—O7—H7A119.6C18—C17—C16119.0 (2)
Zn—O7—H7B93.5C18—C17—H17120.5
H7A—O7—H7B104.0C16—C17—H17120.5
O1—C1—O2120.60 (19)C17—C18—C19119.6 (2)
O1—C1—C2121.04 (19)C17—C18—H18120.2
O2—C1—C2118.36 (18)C19—C18—H18120.2
C3—C2—C7118.38 (18)N1—C19—C18121.4 (2)
C3—C2—C1121.02 (18)N1—C19—C20115.53 (19)
C7—C2—C1120.54 (18)C18—C19—C20123.0 (2)
C4—C3—C2121.16 (19)N2—C20—C21121.4 (2)
C4—C3—H3119.4N2—C20—C19115.06 (19)
C2—C3—H3119.4C21—C20—C19123.5 (2)
C3—C4—C5119.73 (19)C20—C21—C22119.0 (2)
C3—C4—H4120.1C20—C21—H21120.5
C5—C4—H4120.1C22—C21—H21120.5
O3—C5—C4117.50 (18)C23—C22—C21119.8 (2)
O3—C5—C6122.40 (19)C23—C22—H22120.1
C4—C5—C6120.10 (19)C21—C22—H22120.1
C7—C6—C5119.36 (19)C22—C23—C24118.1 (2)
C7—C6—H6120.3C22—C23—H23120.9
C5—C6—H6120.3C24—C23—H23120.9
C6—C7—C2121.23 (19)N2—C24—C23123.2 (2)
C6—C7—H7119.4N2—C24—H24118.4
C2—C7—H7119.4C23—C24—H24118.4
O5—C8—O4123.39 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3A···O1i0.941.642.565 (2)169
O6—H6A···O4ii0.871.812.668 (2)168
O7—H7A···O3iii0.901.932.813 (2)168
O7—H7B···O50.951.732.636 (2)158

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, −y+3/2, z−1/2; (iii) −x+2, y+1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2727).

References

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