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Acta Cryst. (2007). E63, m2372    [ doi:10.1107/S1600536807040366 ]

Aqua(2,2'-biimidazole)(pyridine-2,6-dicarboxylato)copper(II) monohydrate

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

Abstract top

In the title compound, [Cu(C7H3NO4)(C6H6N4)(H2O)]·H2O, the central CuII ion exhibits a distorted mer-CuN3O3 octahedral geometry arising from one water O atom, an N,N-bidentate 2,2'-biimidazole molecule and an N,O,O-tridentate pyridine-2,6-dicarboxylate dianion. 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 (Whitesides et al., (1991); Rebek,1990).

Here, we report the synthesis and sructure of the the title compound, (I), which contains Cu(II) ions, neutral H2biim and pyridine-2,6-dicarboxylate (pda) dianions. The CuII ion in (I) exhibits a distorted mer-CuN3O3 octahedral geometry (Table 1), arising from N1, N2, N4 and O5 as equatorial atoms and O1 and O3 as axial atoms.

The packing for (I) is mainly governed by a combination of O(or N, C)–H···O hydrogen bonds (Table 2, Fig. 2) linking the constituent species together.

Related literature top

For related literature, see: Whitesides et al. (1991); Rebek (1990); Xiao & Shreeve (2005).

Experimental top

2,2'-biimidazole was synthesized according to the literature procedure (Xiao & Shreeve, 2005). A mixture of Cu(NO3)2·4H2O, pyridine-2,6-dicarboxylic acid, 2,2'-biimidazole and water in a molar ratio of 1:1:1:555 was sealed in a 23 ml polyfluoroethylene-lined stainless steel bomb and heated to 423 K under autogenous pressure for 72 h. After slowly cooling to room temperature and opening the bomb, blue plates of (I) were formed, collected by filtration, washed in deionized water, and finally dried.

Refinement top

The N– and O-bound H atoms were located in difference maps and refined with distance restraints [N–H = 0.86 (3) Å, O–H = 0.85 (3) Å, H···H = 1.39 (3) Å] and the constraints Uiso(H) = 1.2Ueq(N) or 1.5Ueq(O).

The C-bound H atoms were geometrically placed (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I), showing 50% probability displacement ellipsoids for the non-hydrogen atoms.
[Figure 2] Fig. 2. Part of the crystal structure of (I) showing the formation of the two-dimensinal network. Hydrogen bonds are shown as dashed lines.
Aqua(2,2'-biimidazole)(pyridine-2,6-dicarboxylato)copper(II) monohydrate top
Crystal data top
[Cu(C7H3NO4)(C6H6N4)(H2O)]·H2OZ = 2
Mr = 398.82F000 = 406
Triclinic, P1Dx = 1.711 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 6.5951 (4) ÅCell parameters from 3382 reflections
b = 10.6971 (7) Åθ = 2.5–27.8º
c = 11.6112 (7) ŵ = 1.46 mm−1
α = 97.210 (1)ºT = 296 (2) K
β = 94.384 (1)ºPlate, blue
γ = 106.411 (1)º0.35 × 0.10 × 0.06 mm
V = 774.16 (8) Å3
Data collection top
Bruker SMART CCD
diffractometer		2978 independent reflections
Radiation source: fine-focus sealed tube2595 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
T = 296(2) Kθmax = 26.0º
ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −8→8
Tmin = 0.630, Tmax = 0.918k = −13→13
7976 measured reflectionsl = −14→12
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)] = 0.049H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.148  w = 1/[σ2(Fo2) + (0.0837P)2 + 1.1035P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max < 0.001
2978 reflectionsΔρmax = 0.82 e Å−3
244 parametersΔρmin = −0.52 e Å−3
8 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cu(C7H3NO4)(C6H6N4)(H2O)]·H2Oγ = 106.411 (1)º
Mr = 398.82V = 774.16 (8) Å3
Triclinic, P1Z = 2
a = 6.5951 (4) ÅMo Kα
b = 10.6971 (7) ŵ = 1.46 mm−1
c = 11.6112 (7) ÅT = 296 (2) K
α = 97.210 (1)º0.35 × 0.10 × 0.06 mm
β = 94.384 (1)º
Data collection top
Bruker SMART CCD
diffractometer		2978 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2595 reflections with I > 2σ(I)
Tmin = 0.630, Tmax = 0.918Rint = 0.029
7976 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0498 restraints
wR(F2) = 0.148H atoms treated by a mixture of
independent and constrained refinement
S = 1.10Δρmax = 0.82 e Å−3
2978 reflectionsΔρmin = −0.52 e Å−3
244 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 > 2sigma(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
Cu10.72700 (7)0.86989 (4)0.73050 (4)0.0290 (2)
C10.6942 (6)0.5957 (3)0.7217 (3)0.0269 (8)
C20.5990 (7)0.4613 (4)0.6989 (4)0.0376 (10)
H20.66970.40320.72250.045*
C30.3954 (7)0.4149 (4)0.6399 (4)0.0411 (10)
H30.32900.32450.62290.049*
C40.2892 (6)0.5014 (4)0.6059 (4)0.0345 (9)
H40.15180.47110.56700.041*
C50.3952 (6)0.6344 (3)0.6320 (3)0.0261 (8)
C60.9129 (6)0.6668 (4)0.7889 (3)0.0277 (8)
C70.3065 (6)0.7458 (4)0.6035 (3)0.0281 (8)
C80.5874 (6)0.7965 (4)0.9848 (4)0.0348 (9)
H80.51830.70640.96790.042*
C90.6372 (6)0.8679 (4)1.0932 (4)0.0341 (9)
H90.61030.83691.16350.041*
C100.7441 (5)0.9956 (3)0.9642 (3)0.0252 (8)
C110.8339 (5)1.1019 (3)0.9001 (3)0.0266 (8)
C120.9225 (6)1.1865 (4)0.7462 (4)0.0348 (9)
H120.94761.19490.66940.042*
C130.9615 (7)1.2875 (4)0.8357 (4)0.0379 (10)
H131.01561.37690.83150.046*
N10.5914 (5)0.6780 (3)0.6882 (3)0.0240 (6)
N20.6540 (5)0.8769 (3)0.9036 (3)0.0286 (7)
N40.8402 (5)1.0698 (3)0.7868 (3)0.0292 (7)
N30.7358 (5)0.9956 (3)1.0784 (3)0.0301 (7)
H3A0.789 (7)1.059 (3)1.131 (3)0.036*
N50.9061 (5)1.2329 (3)0.9335 (3)0.0296 (7)
H5C0.908 (7)1.274 (4)1.000 (3)0.036*
O10.9727 (4)0.7904 (2)0.7902 (2)0.0286 (6)
O21.0086 (5)0.6037 (3)0.8420 (3)0.0425 (8)
O30.4277 (4)0.8609 (3)0.6434 (3)0.0380 (7)
O40.1318 (5)0.7184 (3)0.5452 (3)0.0406 (7)
O50.8806 (5)0.8899 (3)0.5814 (3)0.0366 (7)
H5A0.957 (7)0.844 (5)0.569 (4)0.055*
H5B0.808 (7)0.895 (5)0.520 (3)0.055*
O60.3788 (10)0.0955 (4)0.6068 (4)0.0869 (16)
H6A0.378 (13)0.025 (4)0.632 (7)0.130*
H6B0.480 (10)0.158 (5)0.639 (7)0.130*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0276 (3)0.0193 (3)0.0376 (3)0.00591 (19)−0.0040 (2)0.0020 (2)
C10.031 (2)0.0192 (16)0.0275 (19)0.0061 (14)−0.0043 (15)0.0013 (14)
C20.038 (2)0.0214 (18)0.053 (3)0.0122 (17)−0.0073 (19)0.0037 (18)
C30.039 (2)0.0196 (18)0.057 (3)0.0010 (17)−0.007 (2)0.0006 (18)
C40.029 (2)0.0236 (18)0.042 (2)0.0003 (15)−0.0056 (17)−0.0038 (17)
C50.0279 (19)0.0209 (17)0.0274 (19)0.0065 (14)−0.0038 (15)0.0015 (14)
C60.0250 (18)0.0266 (18)0.031 (2)0.0103 (15)−0.0012 (15)−0.0026 (15)
C70.0277 (19)0.0259 (18)0.033 (2)0.0121 (15)0.0000 (16)0.0039 (15)
C80.029 (2)0.0257 (19)0.049 (3)0.0062 (16)0.0053 (18)0.0071 (18)
C90.027 (2)0.037 (2)0.041 (2)0.0114 (17)0.0029 (17)0.0113 (18)
C100.0174 (16)0.0228 (17)0.036 (2)0.0088 (13)−0.0022 (14)0.0036 (15)
C110.0197 (17)0.0188 (16)0.039 (2)0.0060 (13)−0.0024 (15)−0.0001 (15)
C120.033 (2)0.0236 (18)0.046 (2)0.0059 (16)−0.0005 (18)0.0088 (17)
C130.035 (2)0.0228 (19)0.052 (3)0.0047 (16)−0.0067 (19)0.0087 (18)
N10.0237 (15)0.0190 (14)0.0272 (16)0.0061 (12)−0.0032 (12)0.0000 (12)
N20.0235 (15)0.0214 (15)0.0389 (19)0.0056 (12)0.0017 (13)0.0009 (13)
N40.0273 (16)0.0180 (14)0.041 (2)0.0069 (12)−0.0018 (14)0.0026 (13)
N30.0222 (16)0.0287 (16)0.037 (2)0.0071 (13)−0.0029 (13)−0.0002 (14)
N50.0276 (16)0.0180 (15)0.041 (2)0.0076 (12)−0.0036 (14)−0.0019 (13)
O10.0271 (13)0.0215 (12)0.0340 (15)0.0065 (10)−0.0060 (11)−0.0003 (11)
O20.0399 (17)0.0316 (15)0.055 (2)0.0174 (13)−0.0175 (14)0.0022 (14)
O30.0305 (15)0.0226 (13)0.0584 (19)0.0087 (11)−0.0122 (13)0.0053 (13)
O40.0340 (16)0.0369 (16)0.0474 (18)0.0156 (13)−0.0170 (13)−0.0050 (14)
O50.0457 (18)0.0357 (16)0.0323 (16)0.0185 (13)0.0007 (13)0.0065 (13)
O60.147 (5)0.045 (2)0.069 (3)0.048 (3)−0.043 (3)−0.004 (2)
Geometric parameters (Å, °) top
Cu1—N11.974 (3)C8—C91.353 (6)
Cu1—N42.056 (3)C8—N21.369 (5)
Cu1—O52.076 (3)C8—H80.9300
Cu1—N22.100 (3)C9—N31.376 (5)
Cu1—O32.120 (3)C9—H90.9300
Cu1—O12.141 (3)C10—N21.321 (5)
C1—N11.330 (5)C10—N31.331 (5)
C1—C21.378 (5)C10—C111.449 (5)
C1—C61.525 (5)C11—N41.324 (5)
C2—C31.384 (6)C11—N51.341 (5)
C2—H20.9300C12—C131.354 (6)
C3—C41.385 (6)C12—N41.371 (5)
C3—H30.9300C12—H120.9300
C4—C51.379 (5)C13—N51.369 (6)
C4—H40.9300C13—H130.9300
C5—N11.331 (5)N3—H3A0.83 (3)
C5—C71.529 (5)N5—H5C0.83 (3)
C6—O21.233 (5)O5—H5A0.80 (3)
C6—O11.267 (4)O5—H5B0.84 (3)
C7—O41.229 (5)O6—H6A0.84 (3)
C7—O31.270 (5)O6—H6B0.83 (3)
N1—Cu1—N4173.29 (12)N2—C8—H8125.2
N1—Cu1—O595.10 (12)C8—C9—N3106.1 (4)
N4—Cu1—O591.07 (13)C8—C9—H9127.0
N1—Cu1—N294.58 (12)N3—C9—H9127.0
N4—Cu1—N279.94 (12)N2—C10—N3111.8 (3)
O5—Cu1—N2164.58 (13)N2—C10—C11117.7 (3)
N1—Cu1—O377.85 (11)N3—C10—C11130.6 (3)
N4—Cu1—O399.15 (11)N4—C11—N5111.4 (3)
O5—Cu1—O393.90 (13)N4—C11—C10117.1 (3)
N2—Cu1—O399.86 (13)N5—C11—C10131.4 (4)
N1—Cu1—O177.50 (11)C13—C12—N4109.2 (4)
N4—Cu1—O1105.69 (11)C13—C12—H12125.4
O5—Cu1—O185.31 (11)N4—C12—H12125.4
N2—Cu1—O185.10 (11)C12—C13—N5106.8 (3)
O3—Cu1—O1155.16 (10)C12—C13—H13126.6
N1—C1—C2120.4 (4)N5—C13—H13126.6
N1—C1—C6112.9 (3)C1—N1—C5121.7 (3)
C2—C1—C6126.6 (4)C1—N1—Cu1119.1 (2)
C1—C2—C3118.3 (4)C5—N1—Cu1119.0 (2)
C1—C2—H2120.8C10—N2—C8105.5 (3)
C3—C2—H2120.8C10—N2—Cu1110.9 (2)
C2—C3—C4120.8 (4)C8—N2—Cu1141.3 (3)
C2—C3—H3119.6C11—N4—C12105.8 (3)
C4—C3—H3119.6C11—N4—Cu1113.0 (2)
C5—C4—C3117.4 (4)C12—N4—Cu1141.3 (3)
C5—C4—H4121.3C10—N3—C9107.0 (3)
C3—C4—H4121.3C10—N3—H3A127 (3)
N1—C5—C4121.3 (3)C9—N3—H3A126 (3)
N1—C5—C7112.9 (3)C11—N5—C13106.8 (3)
C4—C5—C7125.7 (3)C11—N5—H5C127 (3)
O2—C6—O1125.9 (4)C13—N5—H5C126 (3)
O2—C6—C1119.3 (3)C6—O1—Cu1114.4 (2)
O1—C6—C1114.7 (3)C7—O3—Cu1115.6 (2)
O4—C7—O3126.3 (3)Cu1—O5—H5A116 (4)
O4—C7—C5119.2 (3)Cu1—O5—H5B117 (4)
O3—C7—C5114.4 (3)H5A—O5—H5B113 (4)
C9—C8—N2109.7 (3)H6A—O6—H6B112 (5)
C9—C8—H8125.2
N1—C1—C2—C30.3 (6)N4—Cu1—N2—C10−10.2 (2)
C6—C1—C2—C3177.6 (4)O5—Cu1—N2—C1044.9 (6)
C1—C2—C3—C4−0.7 (7)O3—Cu1—N2—C10−107.9 (2)
C2—C3—C4—C50.7 (7)O1—Cu1—N2—C1096.7 (3)
C3—C4—C5—N1−0.3 (6)N1—Cu1—N2—C814.6 (4)
C3—C4—C5—C7−179.4 (4)N4—Cu1—N2—C8−169.3 (4)
N1—C1—C6—O2167.6 (3)O5—Cu1—N2—C8−114.1 (5)
C2—C1—C6—O2−9.9 (6)O3—Cu1—N2—C893.1 (4)
N1—C1—C6—O1−8.0 (5)O1—Cu1—N2—C8−62.4 (4)
C2—C1—C6—O1174.5 (4)N5—C11—N4—C120.5 (4)
N1—C5—C7—O4175.4 (4)C10—C11—N4—C12177.6 (3)
C4—C5—C7—O4−5.4 (6)N5—C11—N4—Cu1−179.2 (2)
N1—C5—C7—O3−3.9 (5)C10—C11—N4—Cu1−2.1 (4)
C4—C5—C7—O3175.3 (4)C13—C12—N4—C11−0.9 (4)
N2—C8—C9—N30.4 (5)C13—C12—N4—Cu1178.6 (3)
N2—C10—C11—N4−7.3 (5)O5—Cu1—N4—C11−160.8 (3)
N3—C10—C11—N4172.6 (4)N2—Cu1—N4—C116.6 (3)
N2—C10—C11—N5169.0 (4)O3—Cu1—N4—C11105.0 (3)
N3—C10—C11—N5−11.1 (7)O1—Cu1—N4—C11−75.4 (3)
N4—C12—C13—N51.0 (5)O5—Cu1—N4—C1219.6 (4)
C2—C1—N1—C50.0 (6)N2—Cu1—N4—C12−173.0 (4)
C6—C1—N1—C5−177.6 (3)O3—Cu1—N4—C12−74.5 (4)
C2—C1—N1—Cu1176.5 (3)O1—Cu1—N4—C12105.1 (4)
C6—C1—N1—Cu1−1.1 (4)N2—C10—N3—C91.2 (4)
C4—C5—N1—C1−0.1 (6)C11—C10—N3—C9−178.7 (4)
C7—C5—N1—C1179.1 (3)C8—C9—N3—C10−0.9 (4)
C4—C5—N1—Cu1−176.5 (3)N4—C11—N5—C130.1 (4)
C7—C5—N1—Cu12.6 (4)C10—C11—N5—C13−176.4 (4)
O5—Cu1—N1—C189.7 (3)C12—C13—N5—C11−0.6 (4)
N2—Cu1—N1—C1−78.3 (3)O2—C6—O1—Cu1−162.8 (3)
O3—Cu1—N1—C1−177.4 (3)C1—C6—O1—Cu112.5 (4)
O1—Cu1—N1—C15.7 (3)N1—Cu1—O1—C6−10.3 (3)
O5—Cu1—N1—C5−93.7 (3)N4—Cu1—O1—C6163.6 (3)
N2—Cu1—N1—C598.3 (3)O5—Cu1—O1—C6−106.6 (3)
O3—Cu1—N1—C5−0.8 (3)N2—Cu1—O1—C685.5 (3)
O1—Cu1—N1—C5−177.8 (3)O3—Cu1—O1—C6−17.4 (4)
N3—C10—N2—C8−0.9 (4)O4—C7—O3—Cu1−176.0 (3)
C11—C10—N2—C8179.0 (3)C5—C7—O3—Cu13.2 (4)
N3—C10—N2—Cu1−167.5 (2)N1—Cu1—O3—C7−1.5 (3)
C11—C10—N2—Cu112.4 (4)N4—Cu1—O3—C7−175.4 (3)
C9—C8—N2—C100.3 (4)O5—Cu1—O3—C792.9 (3)
C9—C8—N2—Cu1160.1 (3)N2—Cu1—O3—C7−94.1 (3)
N1—Cu1—N2—C10173.7 (3)O1—Cu1—O3—C75.6 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H6A···O3i0.84 (3)1.90 (4)2.700 (5)160 (9)
O5—H5B···O6ii0.84 (3)1.88 (3)2.719 (5)174 (5)
O5—H5A···O4iii0.80 (3)2.01 (3)2.813 (4)175 (5)
N5—H5C···O2iv0.83 (3)2.05 (3)2.871 (5)166 (4)
N3—H3A···O1iv0.83 (3)1.97 (3)2.729 (4)152 (4)
C3—H3···O60.932.553.359 (6)146
C13—H13···O2v0.932.433.298 (5)156
C4—H4···O4vi0.932.483.294 (5)147
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) −x+2, −y+2, −z+2; (v) x, y+1, z; (vi) −x, −y+1, −z+1.
Selected geometric parameters (Å) top
Cu1—N11.974 (3)Cu1—N22.100 (3)
Cu1—N42.056 (3)Cu1—O32.120 (3)
Cu1—O52.076 (3)Cu1—O12.141 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O6—H6A···O3i0.84 (3)1.90 (4)2.700 (5)160 (9)
O5—H5B···O6ii0.84 (3)1.88 (3)2.719 (5)174 (5)
O5—H5A···O4iii0.80 (3)2.01 (3)2.813 (4)175 (5)
N5—H5C···O2iv0.83 (3)2.05 (3)2.871 (5)166 (4)
N3—H3A···O1iv0.83 (3)1.97 (3)2.729 (4)152 (4)
C3—H3···O60.932.553.359 (6)146
C13—H13···O2v0.932.433.298 (5)156
C4—H4···O4vi0.932.483.294 (5)147
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) −x+2, −y+2, −z+2; (v) x, y+1, z; (vi) −x, −y+1, −z+1.
Acknowledgements top

We thank Xianggao Meng for assistance.

references
References top

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