Poly[(μ2-2,2′-bi-1H-imidazole)bis­(μ3-hydrogenphosphato)dizinc(II)]

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

doi:10.1107/S160053680704250X

Poly[(μ₂-2,2′-bi-1H-imidazole)bis(μ₃-hydrogenphosphato)dizinc(II)]

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

The Zn^II 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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704250X/bt2492sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680704250X/bt2492Isup2.hkl Contains datablock I

CCDC reference: 663550

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.005 Å
R factor = 0.032
wR factor = 0.076
Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       2.00 Ratio
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.89
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.14 Ratio

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.895
            Tmax scaled      0.448 Tmin scaled      0.448
PLAT793_ALERT_1_G Check the Absolute Configuration of P1     = ...          R
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       2.15

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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 (biim^2-) 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 Zn^II 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.

Structure description top

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

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

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

	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]
	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)]	F(000) = 904
M_r = 456.88	D_x = 2.349 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4008 reflections
a = 8.8050 (5) Å	θ = 2.6–28.2°
b = 8.8051 (7) Å	µ = 4.01 mm⁻¹
c = 16.6614 (14) Å	T = 296 K
V = 1291.75 (18) Å³	Block, colourless
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1275 independent reflections
Radiation source: fine-focus sealed tube	1167 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.094
φ and ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→10
T_min = 0.501, T_max = 0.501	k = −10→10
7551 measured reflections	l = −20→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0384P)² + 0.9211P] where P = (F_o² + 2F_c²)/3
1275 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.62 e Å⁻³
0 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

[Zn₂(HPO₄)₂(C₆H₆N₄)]	V = 1291.75 (18) Å³
M_r = 456.88	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 8.8050 (5) Å	µ = 4.01 mm⁻¹
b = 8.8051 (7) Å	T = 296 K
c = 16.6614 (14) Å	0.20 × 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)
T_min = 0.501, T_max = 0.501	R_int = 0.094
7551 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.076	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.62 e Å⁻³
1275 reflections	Δρ_min = −0.64 e Å⁻³
106 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

	x	y	z	U_iso*/U_eq
Zn1	0.32416 (4)	0.09443 (4)	0.670742 (19)	0.01604 (15)
C1	0.4213 (3)	−0.0248 (3)	0.50171 (16)	0.0182 (6)
C2	0.2054 (4)	−0.1293 (4)	0.4651 (2)	0.0295 (7)
H2	0.1320	−0.1817	0.4361	0.035*
C3	0.1870 (3)	−0.0582 (4)	0.5357 (2)	0.0270 (7)
H3	0.0966	−0.0540	0.5645	0.032*
N1	0.3221 (3)	0.0079 (3)	0.55921 (14)	0.0198 (5)
N2	0.3541 (3)	−0.1087 (3)	0.44472 (17)	0.0258 (6)
H2A	0.387 (4)	−0.139 (4)	0.405 (2)	0.031*
O1	0.4899 (2)	0.2367 (2)	0.68551 (11)	0.0201 (5)
O2	0.4137 (2)	0.3524 (3)	0.81871 (12)	0.0204 (5)
H2B	0.344 (4)	0.389 (4)	0.795 (3)	0.031*
O3	0.3408 (2)	−0.0739 (2)	0.74787 (13)	0.0190 (4)
O4	0.1231 (2)	0.1699 (3)	0.68453 (13)	0.0240 (5)
P1	0.55013 (7)	0.29324 (8)	0.76628 (4)	0.01433 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0150 (2)	0.0183 (2)	0.0149 (2)	0.00045 (13)	0.00130 (12)	−0.00147 (12)
C1	0.0196 (14)	0.0219 (14)	0.0131 (13)	−0.0020 (12)	0.0005 (11)	−0.0027 (11)
C2	0.0226 (15)	0.0432 (18)	0.0227 (17)	−0.0135 (15)	0.0019 (14)	−0.0065 (15)
C3	0.0175 (15)	0.0409 (18)	0.0224 (17)	−0.0056 (14)	0.0043 (13)	−0.0038 (14)
N1	0.0174 (13)	0.0265 (13)	0.0153 (12)	−0.0030 (10)	0.0008 (9)	−0.0017 (10)
N2	0.0233 (13)	0.0360 (16)	0.0179 (14)	−0.0068 (12)	0.0047 (11)	−0.0104 (11)
O1	0.0189 (10)	0.0256 (11)	0.0157 (10)	−0.0058 (9)	0.0003 (8)	−0.0038 (8)
O2	0.0130 (10)	0.0300 (12)	0.0182 (10)	0.0073 (10)	0.0001 (8)	−0.0007 (8)
O3	0.0155 (10)	0.0213 (10)	0.0202 (11)	0.0008 (8)	0.0011 (8)	0.0039 (8)
O4	0.0167 (10)	0.0240 (11)	0.0313 (12)	0.0046 (9)	0.0017 (9)	−0.0075 (9)
P1	0.0108 (3)	0.0179 (4)	0.0143 (4)	0.0012 (3)	−0.0001 (3)	−0.0012 (3)

Geometric parameters (Å, º) top

Zn1—O4	1.905 (2)	C3—N1	1.381 (4)
Zn1—O1	1.939 (2)	C3—H3	0.9300
Zn1—O3	1.967 (2)	N2—H2A	0.77 (4)
Zn1—N1	2.009 (2)	O1—P1	1.530 (2)
C1—N1	1.328 (4)	O2—P1	1.574 (2)
C1—N2	1.340 (4)	O2—H2B	0.80 (4)
C1—C1ⁱ	1.454 (5)	O3—P1ⁱⁱ	1.532 (2)
C2—C3	1.343 (5)	O4—P1ⁱⁱⁱ	1.505 (2)
C2—N2	1.365 (4)	P1—O4^iv	1.505 (2)
C2—H2	0.9300	P1—O3^v	1.532 (2)

O4—Zn1—O1	117.29 (9)	C1—N1—Zn1	138.0 (2)
O4—Zn1—O3	104.68 (9)	C3—N1—Zn1	115.46 (19)
O1—Zn1—O3	110.36 (9)	C1—N2—C2	108.7 (3)
O4—Zn1—N1	103.63 (9)	C1—N2—H2A	130 (3)
O1—Zn1—N1	111.68 (9)	C2—N2—H2A	122 (3)
O3—Zn1—N1	108.61 (9)	P1—O1—Zn1	125.65 (12)
N1—C1—N2	109.9 (2)	P1—O2—H2B	116 (3)
N1—C1—C1ⁱ	126.2 (3)	P1ⁱⁱ—O3—Zn1	121.44 (12)
N2—C1—C1ⁱ	123.9 (3)	P1ⁱⁱⁱ—O4—Zn1	135.61 (14)
C3—C2—N2	105.8 (3)	O4^iv—P1—O1	113.12 (13)
C3—C2—H2	127.1	O4^iv—P1—O3^v	111.54 (12)
N2—C2—H2	127.1	O1—P1—O3^v	109.30 (12)
C2—C3—N1	109.9 (3)	O4^iv—P1—O2	105.22 (12)
C2—C3—H3	125.0	O1—P1—O2	109.35 (12)
N1—C3—H3	125.0	O3^v—P1—O2	108.13 (12)
C1—N1—C3	105.7 (2)

N2—C2—C3—N1	0.6 (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—C3	177.8 (4)	O4—Zn1—O1—P1	76.82 (17)
N2—C1—N1—Zn1	168.2 (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—C1	0.0 (4)	O4—Zn1—O3—P1ⁱⁱ	153.03 (13)
C2—C3—N1—Zn1	−171.8 (2)	O1—Zn1—O3—P1ⁱⁱ	−79.90 (15)
O4—Zn1—N1—C1	157.1 (3)	N1—Zn1—O3—P1ⁱⁱ	42.83 (16)
O1—Zn1—N1—C1	30.0 (3)	O1—Zn1—O4—P1ⁱⁱⁱ	−29.4 (2)
O3—Zn1—N1—C1	−92.0 (3)	O3—Zn1—O4—P1ⁱⁱⁱ	93.3 (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—O4^iv	65.95 (18)
O3—Zn1—N1—C3	76.1 (2)	Zn1—O1—P1—O3^v	−169.13 (14)
N1—C1—N2—C2	1.0 (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, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···O3^vi	0.80 (4)	1.84 (4)	2.615 (3)	165 (4)
N2—H2A···O1ⁱ	0.77 (4)	2.05 (4)	2.804 (3)	168 (4)
C2—H2···O2^vii	0.93	2.50	3.303 (4)	145

Symmetry codes: (i) −x+1, −y, −z+1; (vi) −x+1/2, y+1/2, z; (vii) −x+1/2, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	[Zn₂(HPO₄)₂(C₆H₆N₄)]
M_r	456.88
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	8.8050 (5), 8.8051 (7), 16.6614 (14)
V (Å³)	1291.75 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.01
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.501, 0.501
No. of measured, independent and observed [I > 2σ(I)] reflections	7551, 1275, 1167
R_int	0.094
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.076, 1.08
No. of reflections	1275
No. of parameters	106
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.62, −0.64

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.