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Acta Cryst. (2007). E63, m2456    [ doi:10.1107/S160053680704250X ]

Poly[([mu]2-2,2'-bi-1H-imidazole)bis([mu]3-hydrogenphosphato)dizinc(II)]

M.-N. Cao, M. Wang, F.-H. Luo, C.-X. Cheng and Z.-Q. Hu

Abstract top

The ZnII ion in the title compound, [Zn2(HPO4)2(C6H6N4)], exhibits a tetrahedral geometry. It is coordinated by three O atoms from three hydrogenphosphate ions of three different structure units and one N atom of a centrosymmetric bridging 2,2'-biimidazole molecule. In this way, a three-dimensional polymer is built. The crystal packing is stabilized by O-H...O, N-H...O and C-H...O hydrogen bonds.

Comment top

Biimidazole (H2biim) is a bidentate chelating ligand with multiple proton-donor sites which can coordinate to a transition metal in its neutral (H2biim), singly-deprotonated (Hbiim−) and doubly-deprotonated (biim2−) forms. Coordinated H2biim usually forms hydrogen bonds with counteranions or solvent molecules (Xia et al., 2006); Kamar et al., 2004).

Here, we report the synthesis and crystal structure of the title compound, which contains Zn(II) ions, neutral H2biim molecules and hydrogen phosphate ions. The ZnII ion exhibits a distorted tetrahedral geometry. It is coordinated to three O atoms from a hydrogen phosphate ion and one N atom of a 2,2'-biimidazole.

The crystal packing is stabilized by O—H···O, N—H···O and C—H···O hydrogen. bonds.

Related literature top

For related literature, see: Xia et al. (2006); Kamar et al. (2004); Xiao & Shreeve (2005).

Experimental top

2,2'-biimidazole was synthesized according to the literature procedure (Xiao & Shreeve, 2005). A mixture of Zn(NO3)2·4H2O, 2,2'-biimidazole in 1:1 molar ratio with 0.2 ml H3PO4 and 10 ml water was sealed into a Teflon-lined pressure vessel and heated at 433 K for 72 h. After the mixture cooled to room temperature, colourless crystals were formed, collected by filtration, washed in deionized water, and finally dried in air.

Refinement top

After having located them in a difference map, H-atoms bonded to C were fixed geometrically at ideal positions and allowed to ride on their parent atoms with C–H=0.93 Å and Uiso(H)=1.2Ueq(C), 1.2Ueq(N), or 1.5Ueq(O). The coordinates of the H atoms bonded to N and O were refined.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I), showing 50% probability displacement ellipsoids for the non-hydrogen atoms. [Symmetry codes:(a) 3/2 − x, −y, 1/2 + z]
[Figure 2] Fig. 2. Part of the crystal structure of the title compound. Hydrogen bonds are shown as dashed lines.
Poly[(µ2-2,2'-bi-1H-imidazole)bis(µ3-hydrogenphosphato)dizinc(II)] top
Crystal data top
[Zn2(HPO4)2(C6H6N4)]F000 = 904
Mr = 456.88Dx = 2.349 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4008 reflections
a = 8.8050 (5) Åθ = 2.6–28.2º
b = 8.8051 (7) ŵ = 4.01 mm−1
c = 16.6614 (14) ÅT = 296 (2) K
V = 1291.75 (18) Å3Block, colourless
Z = 40.20 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1275 independent reflections
Radiation source: fine-focus sealed tube1167 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.094
T = 296(2) Kθmax = 26.0º
φ and ω scansθmin = 2.4º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −10→10
Tmin = 0.501, Tmax = 0.501k = −10→10
7551 measured reflectionsl = −20→19
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)] = 0.033H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.076  w = 1/[σ2(Fo2) + (0.0384P)2 + 0.9211P]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1275 reflectionsΔρmax = 0.62 e Å−3
106 parametersΔρmin = −0.63 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Zn2(HPO4)2(C6H6N4)]V = 1291.75 (18) Å3
Mr = 456.88Z = 4
Orthorhombic, PbcaMo Kα
a = 8.8050 (5) ŵ = 4.01 mm−1
b = 8.8051 (7) ÅT = 296 (2) K
c = 16.6614 (14) Å0.20 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		1275 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1167 reflections with I > 2σ(I)
Tmin = 0.501, Tmax = 0.501Rint = 0.094
7551 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.033106 parameters
wR(F2) = 0.076H atoms treated by a mixture of
independent and constrained refinement
S = 1.08Δρmax = 0.62 e Å−3
1275 reflectionsΔρmin = −0.63 e Å−3
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
Zn10.32416 (4)0.09443 (4)0.670742 (19)0.01604 (15)
C10.4213 (3)−0.0248 (3)0.50171 (16)0.0182 (6)
C20.2054 (4)−0.1293 (4)0.4651 (2)0.0295 (7)
H20.1320−0.18170.43610.035*
C30.1870 (3)−0.0582 (4)0.5357 (2)0.0270 (7)
H30.0966−0.05400.56450.032*
N10.3221 (3)0.0079 (3)0.55921 (14)0.0198 (5)
N20.3541 (3)−0.1087 (3)0.44472 (17)0.0258 (6)
H2A0.387 (4)−0.139 (4)0.405 (2)0.031*
O10.4899 (2)0.2367 (2)0.68551 (11)0.0201 (5)
O20.4137 (2)0.3524 (3)0.81871 (12)0.0204 (5)
H2B0.344 (4)0.389 (4)0.795 (3)0.031*
O30.3408 (2)−0.0739 (2)0.74787 (13)0.0190 (4)
O40.1231 (2)0.1699 (3)0.68453 (13)0.0240 (5)
P10.55013 (7)0.29324 (8)0.76628 (4)0.01433 (19)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0150 (2)0.0183 (2)0.0149 (2)0.00045 (13)0.00130 (12)−0.00147 (12)
C10.0196 (14)0.0219 (14)0.0131 (13)−0.0020 (12)0.0005 (11)−0.0027 (11)
C20.0226 (15)0.0432 (18)0.0227 (17)−0.0135 (15)0.0019 (14)−0.0065 (15)
C30.0175 (15)0.0409 (18)0.0224 (17)−0.0056 (14)0.0043 (13)−0.0038 (14)
N10.0174 (13)0.0265 (13)0.0153 (12)−0.0030 (10)0.0008 (9)−0.0017 (10)
N20.0233 (13)0.0360 (16)0.0179 (14)−0.0068 (12)0.0047 (11)−0.0104 (11)
O10.0189 (10)0.0256 (11)0.0157 (10)−0.0058 (9)0.0003 (8)−0.0038 (8)
O20.0130 (10)0.0300 (12)0.0182 (10)0.0073 (10)0.0001 (8)−0.0007 (8)
O30.0155 (10)0.0213 (10)0.0202 (11)0.0008 (8)0.0011 (8)0.0039 (8)
O40.0167 (10)0.0240 (11)0.0313 (12)0.0046 (9)0.0017 (9)−0.0075 (9)
P10.0108 (3)0.0179 (4)0.0143 (4)0.0012 (3)−0.0001 (3)−0.0012 (3)
Geometric parameters (Å, °) top
Zn1—O41.905 (2)C3—N11.381 (4)
Zn1—O11.939 (2)C3—H30.9300
Zn1—O31.967 (2)N2—H2A0.77 (4)
Zn1—N12.009 (2)O1—P11.530 (2)
C1—N11.328 (4)O2—P11.574 (2)
C1—N21.340 (4)O2—H2B0.80 (4)
C1—C1i1.454 (5)O3—P1ii1.532 (2)
C2—C31.343 (5)O4—P1iii1.505 (2)
C2—N21.365 (4)P1—O4iv1.505 (2)
C2—H20.9300P1—O3v1.532 (2)
O4—Zn1—O1117.29 (9)C1—N1—Zn1138.0 (2)
O4—Zn1—O3104.68 (9)C3—N1—Zn1115.46 (19)
O1—Zn1—O3110.36 (9)C1—N2—C2108.7 (3)
O4—Zn1—N1103.63 (9)C1—N2—H2A130 (3)
O1—Zn1—N1111.68 (9)C2—N2—H2A122 (3)
O3—Zn1—N1108.61 (9)P1—O1—Zn1125.65 (12)
N1—C1—N2109.9 (2)P1—O2—H2B116 (3)
N1—C1—C1i126.2 (3)P1ii—O3—Zn1121.44 (12)
N2—C1—C1i123.9 (3)P1iii—O4—Zn1135.61 (14)
C3—C2—N2105.8 (3)O4iv—P1—O1113.12 (13)
C3—C2—H2127.1O4iv—P1—O3v111.54 (12)
N2—C2—H2127.1O1—P1—O3v109.30 (12)
C2—C3—N1109.9 (3)O4iv—P1—O2105.22 (12)
C2—C3—H3125.0O1—P1—O2109.35 (12)
N1—C3—H3125.0O3v—P1—O2108.13 (12)
C1—N1—C3105.7 (2)
N2—C2—C3—N10.6 (4)C1i—C1—N2—C2−177.4 (4)
N2—C1—N1—C3−0.6 (3)C3—C2—N2—C1−1.0 (4)
C1i—C1—N1—C3177.8 (4)O4—Zn1—O1—P176.82 (17)
N2—C1—N1—Zn1168.2 (2)O3—Zn1—O1—P1−42.89 (18)
C1i—C1—N1—Zn1−13.4 (6)N1—Zn1—O1—P1−163.81 (14)
C2—C3—N1—C10.0 (4)O4—Zn1—O3—P1ii153.03 (13)
C2—C3—N1—Zn1−171.8 (2)O1—Zn1—O3—P1ii−79.90 (15)
O4—Zn1—N1—C1157.1 (3)N1—Zn1—O3—P1ii42.83 (16)
O1—Zn1—N1—C130.0 (3)O1—Zn1—O4—P1iii−29.4 (2)
O3—Zn1—N1—C1−92.0 (3)O3—Zn1—O4—P1iii93.3 (2)
O4—Zn1—N1—C3−34.8 (2)N1—Zn1—O4—P1iii−153.0 (2)
O1—Zn1—N1—C3−161.9 (2)Zn1—O1—P1—O4iv65.95 (18)
O3—Zn1—N1—C376.1 (2)Zn1—O1—P1—O3v−169.13 (14)
N1—C1—N2—C21.0 (4)Zn1—O1—P1—O2−50.94 (18)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) x−1/2, y, −z+3/2; (iv) x+1/2, y, −z+3/2; (v) −x+1, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2B···O3vi0.80 (4)1.84 (4)2.615 (3)165 (4)
N2—H2A···O1i0.77 (4)2.05 (4)2.804 (3)168 (4)
C2—H2···O2vii0.932.503.303 (4)145
Symmetry codes: (vi) −x+1/2, y+1/2, z; (i) −x+1, −y, −z+1; (vii) −x+1/2, −y, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2B···O3i0.80 (4)1.84 (4)2.615 (3)165 (4)
N2—H2A···O1ii0.77 (4)2.05 (4)2.804 (3)168 (4)
C2—H2···O2iii0.932.503.303 (4)145
Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) −x+1, −y, −z+1; (iii) −x+1/2, −y, z−1/2.
Acknowledgements top

The authors thank Xianggao Meng for assistance with refinement of the structure.

references
References top

Bruker (2001). SMART, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Kamar, K. K., Falvello, L. R., Fanwick, P. E., Kim, J. & Goswami, S. (2004). Dalton Trans. pp. 1827–1831.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Xia, C.-K., Lu, C.-Z., Yuan, D.-Q., Zhang, Q.-Z., Wu, X.-Y., Xiang, S.-C., Zhang, J.-J. & Wu, D.-M. (2006). CrystEngComm, 8, 281–291.

Xiao, J.-C. & Shreeve, J. M. (2005). J. Org. Chem. 70, 3072–3078.