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Acta Cryst. (2009). E65, m543-m544    [ doi:10.1107/S1600536809013701 ]

Bis([mu]-2,2'-bi-1H-imidazole-1,1'-diacetato)bis[diaquacobalt(II)] hexahydrate

T. Zhang, T. Zhang, F. Xu and H. Liang

Abstract top

The dinuclear title compound, [Co2(C10H8N4O4)2(H2O)4]·6H2O, lies about an inversion centre. Each CoII atom is six-coordinated by two water molecules, two carboxylate O atoms and two N atoms of two symmetry-related 2,2'-bi-1H-imidazole-1,1'-diacetate (L2-) ligands in a slightly distorted octahedral geometry. Molecules are linked into a three-dimensional framework via O-H...O and C-H...O hydrogen bonds.

Comment top

Although N-substituted derivatives of 2,2'-biimidazole have recently been developed (Atencio et al., 2004; Ghosh et al., 2006; Tadokoro & Nakasuji, 2000; Zhang & Liang, 2009), few corresponding metal complexes have been reported. Here we report the crystal structure of Co2L2(H2O)4.6H2O [H2L = 2,2'-(2,2'-biimidazole-1,1'-diyl)diacetic acid]. The complex molecule lies about an inversion centre, as shown in Fig. 1, and the CoII atoms show a slightly distorted octahedral geometry. The dihedral angle between the two imidazole rings of each L2- is 72.50 (6)°. Each CoII atom is six-coordinated by two O atoms from different monodentate carboxylate groups, two O atoms from the coordinating water molecules and two N atoms from two symmetry-related L2- ligands. Selected bond distances and angles are listed in Table 1. The Co—O/N distances are in the ranges 2.0796 (13)–2.1727 (14) Å and 2.1103 (14)–2.1153 (15) Å, respectively. The Co···Co distance is 5.4881 Å, indicating that there is no interaction between the two metal centres.

An extensive network of O—H···O hydrogen bonds links the complex and water molecules to produce a number of substructures in two dimensions. A typical two-dimensional sheet, approximately parallel to [001], is shown in Fig. 2. Additional weak C—H···O hydrogen bonds (Table 2) generate a three-dimensional framework.

Related literature top

For background to 2,2'-biimidazole derivatives, see: Atencio et al. (2004); Ghosh et al. (2006); Tadokoro & Nakasuji (2000); Zhang & Liang (2009). For the preparation of the ligand, see: Zhang et al. (2009).

Experimental top

2,2'-(2,2'-Biimidazole-1,1'-diyl)diacetic acid (Zhang et al., 2009) (0.1 g, 0.4 mmol) and Co(OH)2 (0.0372 g, 0.4 mmol) freshly prepared from CoCl2.6H2O and NaOH were added to distilled water (10 ml). The reaction mixture was adjusted to pH 6 with aqueous NaOH solution and stirred at room temperature for 20 min during which time a clear pink solution resulted. Red single crystals of (I) appeared within several weeks by slow evaporation at room temperature.

Refinement top

H atoms bound to C atoms were placed in geometrically calculated positions and were refined using a riding model, with Uiso(H) = 1.2Ueq(C). H atoms attached to O atoms were found in a difference Fourier synthesis and were refined using a riding model, with the O—H distances fixed as initially found and with Uiso(H) values set at 1.5Ueq(O).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of (I), showing the labelling of the non-H atoms and 45% probability ellipsoids. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. A perspective view of a two-dimensional sheet running parallel to [001], showing the packing mode and the O—H···O hydrogen-bonding interactions drawn as dashed lines. All H atoms not involved in the hydrogen-bond motifs have been omitted for clarity.
Bis(µ-2,2'-bi-1H-imidazole-1,1'-diacetato)bis[diaquacobalt(II)] hexahydrate top
Crystal data top
[Co2(C10H8N4O4)2(H2O)4]·6H2OF(000) = 1640
Mr = 794.43Dx = 1.658 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 15337 reflections
a = 15.902 (3) Åθ = 3.1–27.4°
b = 14.202 (3) ŵ = 1.13 mm−1
c = 14.998 (3) ÅT = 295 K
β = 110.06 (3)°Block, red
V = 3181.7 (13) Å30.50 × 0.42 × 0.18 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3625 independent reflections
Radiation source: fine-focus sealed tube3151 reflections with I > 2σ(I)
graphiteRint = 0.029
ω scansθmax = 27.4°, θmin = 3.1°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −20→19
Tmin = 0.570, Tmax = 0.813k = −18→18
15337 measured reflectionsl = −19→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)] = 0.027H-atom parameters constrained
wR(F2) = 0.074 w = 1/[σ2(Fo2) + (0.0275P)2 + 4.2044P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.002
3625 reflectionsΔρmax = 0.41 e Å−3
218 parametersΔρmin = −0.29 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0061 (3)
Crystal data top
[Co2(C10H8N4O4)2(H2O)4]·6H2OV = 3181.7 (13) Å3
Mr = 794.43Z = 4
Monoclinic, C2/cMo Kα radiation
a = 15.902 (3) ŵ = 1.13 mm−1
b = 14.202 (3) ÅT = 295 K
c = 14.998 (3) Å0.50 × 0.42 × 0.18 mm
β = 110.06 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3625 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3151 reflections with I > 2σ(I)
Tmin = 0.570, Tmax = 0.813Rint = 0.029
15337 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.027H-atom parameters constrained
wR(F2) = 0.074Δρmax = 0.41 e Å−3
S = 1.10Δρmin = −0.29 e Å−3
3625 reflectionsAbsolute structure: ?
218 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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 base. 0 d 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
Co11.023692 (15)0.749865 (14)0.077182 (15)0.01916 (9)
N10.91453 (10)0.82568 (10)0.29571 (10)0.0224 (3)
N20.88351 (10)0.58280 (10)0.21753 (10)0.0243 (3)
N30.88985 (10)0.91865 (10)0.17141 (10)0.0248 (3)
N40.93715 (9)0.67422 (10)0.13078 (9)0.0209 (3)
O20.89286 (9)0.98537 (9)−0.05853 (9)0.0285 (3)
O30.92283 (9)0.84716 (9)0.01511 (9)0.0323 (3)
O41.11054 (11)0.82618 (9)0.02372 (11)0.0389 (4)
H4D1.10430.88250.02950.047*
H4C1.14090.8131−0.01810.047*
O50.96590 (9)0.67292 (9)−0.05502 (9)0.0319 (3)
H5D1.00170.6536−0.07970.038*
H5C0.93040.6160−0.05240.038*
O60.87182 (9)0.64981 (8)0.38539 (9)0.0280 (3)
O70.87743 (10)0.50471 (9)0.44485 (9)0.0344 (3)
O80.19082 (11)0.79054 (12)0.88353 (11)0.0472 (4)
H8C0.25070.79900.89410.057*
H8D0.15750.80730.82300.057*
O90.10278 (12)0.61000 (12)0.88740 (11)0.0501 (4)
H9D0.14440.65860.88430.060*
H9C0.11960.56600.93360.060*
O100.89665 (17)0.84232 (17)0.80245 (13)0.0832 (7)
H10C0.89540.89280.84490.100*
H10D0.91550.79560.85580.100*
C10.95208 (11)0.87378 (11)0.24321 (11)0.0198 (3)
C20.82375 (12)0.83991 (14)0.25327 (13)0.0301 (4)
H2A0.78000.81440.27430.036*
C60.95635 (11)0.62664 (11)0.21149 (11)0.0187 (3)
C70.81313 (12)0.60473 (14)0.13716 (14)0.0324 (4)
H7A0.75410.58500.12180.039*
C30.80770 (13)0.89635 (14)0.17667 (13)0.0317 (4)
H3A0.75210.91610.13570.038*
C80.84668 (12)0.66100 (13)0.08439 (13)0.0282 (4)
H8A0.81370.68680.02580.034*
C40.90598 (15)0.98220 (12)0.10244 (13)0.0312 (4)
H4B0.96271.01400.13240.037*
H4A0.85951.02980.08490.037*
C50.90808 (11)0.93378 (12)0.01265 (12)0.0221 (3)
C90.88299 (15)0.51645 (13)0.29141 (14)0.0329 (4)
H9A0.93700.47860.30800.039*
H9B0.83240.47430.26570.039*
C100.87762 (11)0.56101 (12)0.38158 (12)0.0240 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02548 (14)0.01487 (13)0.01840 (13)0.00047 (8)0.00914 (9)0.00001 (8)
N10.0240 (7)0.0230 (7)0.0228 (7)0.0021 (6)0.0112 (6)0.0027 (6)
N20.0274 (7)0.0254 (7)0.0227 (7)−0.0072 (6)0.0119 (6)−0.0030 (6)
N30.0320 (8)0.0233 (7)0.0214 (7)0.0078 (6)0.0119 (6)0.0055 (6)
N40.0218 (7)0.0216 (7)0.0185 (6)−0.0003 (5)0.0058 (5)0.0003 (5)
O20.0384 (7)0.0241 (6)0.0231 (6)−0.0005 (5)0.0105 (5)0.0048 (5)
O30.0421 (8)0.0207 (6)0.0303 (7)0.0092 (5)0.0076 (6)0.0011 (5)
O40.0662 (10)0.0198 (6)0.0475 (8)−0.0039 (6)0.0412 (8)−0.0004 (6)
O50.0413 (8)0.0264 (7)0.0284 (7)−0.0011 (6)0.0125 (6)−0.0068 (5)
O60.0312 (7)0.0204 (6)0.0337 (7)−0.0046 (5)0.0129 (6)−0.0023 (5)
O70.0513 (9)0.0243 (6)0.0302 (7)−0.0067 (6)0.0173 (6)0.0013 (5)
O80.0448 (9)0.0605 (10)0.0420 (8)0.0034 (8)0.0223 (7)0.0040 (8)
O90.0700 (11)0.0437 (9)0.0418 (9)0.0050 (8)0.0260 (8)0.0003 (7)
O100.1034 (17)0.1029 (17)0.0366 (10)0.0215 (14)0.0152 (11)−0.0105 (10)
C10.0246 (9)0.0172 (7)0.0190 (7)0.0025 (6)0.0091 (6)0.0002 (6)
C20.0239 (9)0.0388 (10)0.0316 (9)0.0046 (8)0.0145 (7)0.0050 (8)
C60.0215 (8)0.0153 (7)0.0199 (7)−0.0008 (6)0.0080 (7)−0.0015 (6)
C70.0213 (8)0.0408 (11)0.0335 (10)−0.0072 (8)0.0075 (7)−0.0082 (8)
C30.0264 (9)0.0390 (10)0.0295 (9)0.0116 (8)0.0091 (8)0.0044 (8)
C80.0229 (8)0.0342 (10)0.0237 (8)0.0009 (7)0.0032 (7)−0.0017 (7)
C40.0508 (12)0.0193 (8)0.0260 (9)0.0080 (8)0.0163 (8)0.0070 (7)
C50.0207 (8)0.0219 (8)0.0228 (8)0.0022 (6)0.0062 (6)0.0021 (7)
C90.0479 (12)0.0218 (8)0.0364 (10)−0.0103 (8)0.0241 (9)−0.0018 (8)
C100.0236 (8)0.0228 (8)0.0269 (8)−0.0067 (7)0.0103 (7)−0.0019 (7)
Geometric parameters (Å, °) top
Co1—O32.0796 (13)O6—C101.267 (2)
Co1—N42.1103 (14)O6—Co1i2.1108 (13)
Co1—O6i2.1108 (13)O7—C101.242 (2)
Co1—N1i2.1153 (15)O8—H8C0.9180
Co1—O42.1177 (14)O8—H8D0.9119
Co1—O52.1727 (14)O9—H9D0.9684
N1—C11.329 (2)O9—H9C0.9028
N1—C21.378 (2)O10—H10C0.9636
N1—Co1i2.1153 (15)O10—H10D1.0029
N2—C61.345 (2)C1—C1i1.467 (3)
N2—C71.370 (2)C2—C31.351 (3)
N2—C91.457 (2)C2—H2A0.9300
N3—C11.347 (2)C6—C6i1.470 (3)
N3—C31.373 (2)C7—C81.356 (3)
N3—C41.460 (2)C7—H7A0.9300
N4—C61.327 (2)C3—H3A0.9300
N4—C81.379 (2)C8—H8A0.9300
O2—C51.248 (2)C4—C51.523 (2)
O3—C51.251 (2)C4—H4B0.9700
O4—H4D0.8143C4—H4A0.9700
O4—H4C0.9320C9—C101.522 (3)
O5—H5D0.8252C9—H9A0.9700
O5—H5C0.9945C9—H9B0.9700
O3—Co1—N490.29 (6)H10C—O10—H10D91.9
O3—Co1—O6i169.21 (5)N1—C1—N3111.15 (15)
N4—Co1—O6i96.47 (5)N1—C1—C1i125.05 (16)
O3—Co1—N1i96.53 (6)N3—C1—C1i123.68 (16)
N4—Co1—N1i94.46 (6)C3—C2—N1110.01 (16)
O6i—Co1—N1i91.32 (6)C3—C2—H2A125.0
O3—Co1—O489.63 (6)N1—C2—H2A125.0
N4—Co1—O4179.80 (5)N4—C6—N2111.28 (14)
O6i—Co1—O483.63 (6)N4—C6—C6i125.21 (15)
N1i—Co1—O485.36 (6)N2—C6—C6i123.35 (16)
O3—Co1—O584.59 (6)C8—C7—N2106.34 (16)
N4—Co1—O587.97 (5)C8—C7—H7A126.8
O6i—Co1—O587.26 (6)N2—C7—H7A126.8
N1i—Co1—O5177.31 (5)C2—C3—N3106.24 (16)
O4—Co1—O592.21 (6)C2—C3—H3A126.9
C1—N1—C2105.27 (14)N3—C3—H3A126.9
C1—N1—Co1i129.17 (12)C7—C8—N4109.68 (16)
C2—N1—Co1i125.45 (12)C7—C8—H8A125.2
C6—N2—C7107.33 (15)N4—C8—H8A125.2
C6—N2—C9125.47 (16)N3—C4—C5114.20 (15)
C7—N2—C9126.89 (16)N3—C4—H4B108.7
C1—N3—C3107.32 (14)C5—C4—H4B108.7
C1—N3—C4126.82 (16)N3—C4—H4A108.7
C3—N3—C4125.82 (16)C5—C4—H4A108.7
C6—N4—C8105.35 (14)H4B—C4—H4A107.6
C6—N4—Co1129.08 (11)O2—C5—O3125.60 (16)
C8—N4—Co1125.51 (11)O2—C5—C4115.77 (15)
C5—O3—Co1140.80 (12)O3—C5—C4118.62 (15)
Co1—O4—H4D110.1N2—C9—C10115.06 (15)
Co1—O4—H4C135.1N2—C9—H9A108.5
H4D—O4—H4C112.2C10—C9—H9A108.5
Co1—O5—H5D115.8N2—C9—H9B108.5
Co1—O5—H5C116.2C10—C9—H9B108.5
H5D—O5—H5C103.6H9A—C9—H9B107.5
C10—O6—Co1i128.25 (12)O7—C10—O6125.95 (17)
H8C—O8—H8D110.6O7—C10—C9115.27 (15)
H9D—O9—H9C120.2O6—C10—C9118.76 (15)
Symmetry codes: (i) −x+2, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4D···O2ii0.811.922.7309 (19)171
O4—H4C···O8iii0.931.932.855 (2)173
O5—H5D···O9iii0.831.942.752 (2)169
O5—H5C···O7iv0.991.902.888 (2)170
O8—H8C···O6v0.922.102.991 (2)162
O8—H8D···O10vi0.911.852.756 (3)173
O9—H9D···O80.972.022.931 (3)157
O9—H9C···O7vi0.902.012.850 (2)155
O10—H10C···O2vii0.961.972.927 (3)174
O10—H10C···O3vii0.962.523.072 (2)116
O10—H10D···O5vii1.002.183.155 (3)165
O10—H10D···O3vii1.002.463.072 (2)119
Symmetry codes: (ii) −x+2, −y+2, −z; (iii) x+1, y, z−1; (iv) x, −y+1, z−1/2; (v) x−1/2, −y+3/2, z+1/2; (vi) −x+1, y, −z+3/2; (vii) x, y, z+1.
Table 1
Selected geometric parameters (Å, °) top
Co1—O32.0796 (13)Co1—N1i2.1153 (15)
Co1—N42.1103 (14)Co1—O42.1177 (14)
Co1—O6i2.1108 (13)Co1—O52.1727 (14)
O3—Co1—N490.29 (6)N4—Co1—N1i94.46 (6)
O3—Co1—O6i169.21 (5)O6i—Co1—N1i91.32 (6)
N4—Co1—O6i96.47 (5)O4—Co1—O592.21 (6)
O3—Co1—N1i96.53 (6)
Symmetry codes: (i) −x+2, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O4—H4D···O2ii0.811.922.7309 (19)171
O4—H4C···O8iii0.931.932.855 (2)173
O5—H5D···O9iii0.831.942.752 (2)169
O5—H5C···O7iv0.991.902.888 (2)170
O8—H8C···O6v0.922.102.991 (2)162
O8—H8D···O10vi0.911.852.756 (3)173
O9—H9D···O80.972.022.931 (3)157
O9—H9C···O7vi0.902.012.850 (2)155
O10—H10C···O2vii0.961.972.927 (3)174
O10—H10C···O3vii0.962.523.072 (2)116
O10—H10D···O5vii1.002.183.155 (3)165
O10—H10D···O3vii1.002.463.072 (2)119
Symmetry codes: (ii) −x+2, −y+2, −z; (iii) x+1, y, z−1; (iv) x, −y+1, z−1/2; (v) x−1/2, −y+3/2, z+1/2; (vi) −x+1, y, −z+3/2; (vii) x, y, z+1.
Acknowledgements top

This project was sponsored by the Scientific Research Foundation of the State Education Ministry for Returned Overseas Chinese Scholars (grant No. 2006701), the Critical Projects in Science and Technology Department of Zhejiang Province (grant No. 2007C21113), the Education Committee of Zhejiang Province (grant Nos. 2005545, 20061696 and 2008934), the Natural Science Foundation of Ningbo City (grant No. 2007A610021) and the K. C. Wong Magna Fund in Ningbo University. The authors thank Mr W. Xu for collecting the X-ray data.

references
References top

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