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Acta Cryst. (2009). E65, m370-m371    [ doi:10.1107/S1600536809007478 ]

Poly[[[diaquacobalt(II)]-bis[[mu]2-1,1'-(butane-1,4-diyl)diimidazole-[kappa]2N3:N3']] dichloride tetrahydrate]

Y. Su, Y.-J. Hou, Z.-Z. Sun, G.-F. Hou and J.-S. Gao

Abstract top

In the title compound, {[Co(C10H14N4)2(H2O)2]Cl2·4H2O}n, the CoII atom and the mid-point of the 1,1'-butane-1,4-diyldiimidazole ligands lie on inversion centers. The CoII atom is six-coordinated in a slightly distorted octahedral environment by four N atoms from four different ligands and by two O atoms from the water molecules. The CoII atoms are bridged by the ligands into a (4,4) net. Adjacent nets are linked to the chloride anions and uncoordinated water molecules via O-H...Cl and O-H...O hydrogen bonds, generating a three-dimensional supramolecular structure.

Comment top

The L molecules as a flexible ligand exhibit a variety of supramolecular aggregation patterns (Ma et al., 2003; Dong et al., 2006; Yu et al., 2008). In this paper, we report the new title compound, (I), synthssized by the reaction of L molecules and cobalt dichloride in aqua solution.

In (I), each CoII atom is located on a inversion centre and is six-coordinated in an octahedral environment by four N atoms from four different L molecules and two O atoms form the two water molecules (Fig. 1). The Co—N and Co—O distances are normal (Table 1). The CoII atoms are bridged by ligands, generating a two-dimensional (4,4)-network (Fig. 2).

The hydrogen bonding cluster, containing the O—H···Cl and O—H···O hydrogen bonding interaction between the chloride anions, uncoordinated water molecules and the coordinated water molecules (Fig. 3), which linke the adjacent fishnet planes to a three-dimensional supramolecular structure (Fig. 4, Table 2).

Related literature top

For the synthesis of 1,1'-butane-1,4-diyldiimidazole, see: Ma et al.(2003); Yu et al. (2008). For a related Co complex, see: Dong & Zhang (2006).

Experimental top

L was prepared from imidazole and 1,4-dibromobutane in DMSO (Ma et al., 2003). L (0.76 g, 4 mmol) and cobalt dichloride (0.51 g, 4 mmol) were dissolved in hot aqua solution (10 ml) to give a clear solution. The resulting solution was allowed to stand in a desiccator at room temperature for a week, red crystals of (I) were obtained.

Refinement top

H atoms bound to C atoms were placed in calculated positions and treated as riding on their parent atoms, with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene), and with Uiso(H) = 1.2Ueq(C). Water H atoms were initially located in a difference Fourier map, but they were treated as riding on their parent atoms with O—H = 0.85 Å and with with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: RAPID-AUTO (Rigaku 1998); cell refinement: RAPID-AUTO (Rigaku 1998); data reduction: CrystalStructure (Rigaku/MSC 2002); 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. The molecular structure of (I), showing displacement ellipsoids at the 30% probability level for non-H atoms. Dashed lines indicate the hydrogen-bonding interactions [Symmetry code; (I) -x + 1, -y + 1, -z + 1; (II) -x + 2, -y, -z + 2: (III) -x, -y + 1, -z + 2]
[Figure 2] Fig. 2. A partial packing view, showing the two-dimensional (4,4)-network. C-bond H atoms have beeb omitted.
[Figure 3] Fig. 3. A showing of the hydrogen bonding cluster in I.
[Figure 4] Fig. 4. A Partial packing view, shoving the three-dimensional supramolecular structure. Dashed lines indicate the hydrogen-bonding interactions and no involving H atoms have beeb omitted.
Poly[[[diaquacobalt(II)]-bis[µ2-1,1'-(butane-1,4-diyl)diimidazole- κ2N3:N3']] dichloride tetrahydrate] top
Crystal data top
[Co(C10H14N4)2(H2O)2]Cl2·4H2OZ = 1
Mr = 618.43F(000) = 325
Triclinic, P1Dx = 1.393 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.969 (6) ÅCell parameters from 6505 reflections
b = 9.979 (6) Åθ = 3.3–27.5°
c = 10.259 (7) ŵ = 0.81 mm−1
α = 114.97 (2)°T = 291 K
β = 90.83 (3)°Block, red
γ = 93.70 (3)°0.44 × 0.37 × 0.22 mm
V = 737.3 (8) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3348 independent reflections
Radiation source: fine-focus sealed tube3018 reflections with I > 2σ(I)
graphiteRint = 0.017
ω scanθmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −10→10
Tmin = 0.718, Tmax = 0.842k = −12→12
7288 measured reflectionsl = −13→13
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.0444P)2 + 0.1566P]
where P = (Fo2 + 2Fc2)/3
3348 reflections(Δ/σ)max < 0.001
169 parametersΔρmax = 0.33 e Å−3
0 restraintsΔρmin = −0.22 e Å−3
Crystal data top
[Co(C10H14N4)2(H2O)2]Cl2·4H2Oγ = 93.70 (3)°
Mr = 618.43V = 737.3 (8) Å3
Triclinic, P1Z = 1
a = 7.969 (6) ÅMo Kα radiation
b = 9.979 (6) ŵ = 0.81 mm−1
c = 10.259 (7) ÅT = 291 K
α = 114.97 (2)°0.44 × 0.37 × 0.22 mm
β = 90.83 (3)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		3348 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		3018 reflections with I > 2σ(I)
Tmin = 0.718, Tmax = 0.842Rint = 0.017
7288 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.084Δρmax = 0.33 e Å−3
S = 1.14Δρmin = −0.22 e Å−3
3348 reflectionsAbsolute structure: ?
169 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 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
C10.6521 (2)0.1455 (2)0.94674 (17)0.0354 (4)
H10.66950.21571.04160.043*
C20.5873 (2)0.16729 (19)0.83506 (17)0.0330 (3)
H20.55160.25650.84090.040*
C30.64306 (19)−0.06103 (17)0.75067 (16)0.0283 (3)
H30.6543−0.15960.68850.034*
C40.7646 (2)−0.0765 (2)0.9698 (2)0.0382 (4)
H40.7167−0.17830.93120.046*
H50.7386−0.02881.07050.046*
C50.9543 (2)−0.07561 (17)0.95821 (18)0.0335 (3)
H60.9958−0.14430.99310.040*
H70.9803−0.11070.85760.040*
C60.2259 (2)0.22255 (18)0.64249 (18)0.0331 (3)
H80.28730.29930.63140.040*
C70.1451 (2)0.00888 (18)0.63070 (18)0.0325 (3)
H90.1409−0.09160.60930.039*
C80.0303 (2)0.10224 (18)0.70471 (18)0.0344 (4)
H10−0.06580.07840.74320.041*
C90.0058 (2)0.3775 (2)0.7958 (2)0.0406 (4)
H11−0.11510.36290.77600.049*
H120.04950.45290.76630.049*
C100.0423 (3)0.43001 (19)0.9552 (2)0.0438 (4)
H130.16300.44870.97510.053*
H140.00380.35220.98320.053*
Cl10.74821 (7)0.35621 (5)0.32791 (5)0.04818 (14)
Co10.50000.00000.50000.02144 (9)
N10.58238 (16)0.03688 (14)0.71136 (13)0.0274 (3)
N20.68668 (16)−0.00004 (15)0.89242 (14)0.0299 (3)
N30.26947 (15)0.08534 (14)0.59164 (13)0.0265 (3)
N40.08195 (17)0.23842 (15)0.71246 (15)0.0312 (3)
O10.59361 (16)0.22377 (12)0.53595 (13)0.0381 (3)
H150.58270.30490.60890.057*
H160.62730.24290.46700.057*
O20.1615 (2)0.38041 (17)0.36469 (18)0.0668 (5)
H170.18120.44900.44890.100*
H180.05540.37000.34900.100*
O30.4231 (2)0.49280 (17)0.24618 (19)0.0670 (5)
H190.33780.45750.27340.100*
H200.51210.46390.26930.100*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0329 (8)0.0426 (9)0.0241 (7)0.0052 (7)0.0005 (6)0.0074 (7)
C20.0328 (8)0.0345 (8)0.0280 (7)0.0091 (6)0.0016 (6)0.0086 (7)
C30.0268 (7)0.0319 (8)0.0256 (7)0.0010 (6)−0.0018 (6)0.0120 (6)
C40.0357 (9)0.0503 (10)0.0395 (9)−0.0060 (7)−0.0089 (7)0.0314 (8)
C50.0354 (9)0.0321 (8)0.0369 (8)0.0016 (6)−0.0083 (7)0.0188 (7)
C60.0291 (8)0.0340 (8)0.0418 (9)0.0078 (6)0.0106 (7)0.0205 (7)
C70.0335 (8)0.0283 (8)0.0337 (8)0.0033 (6)0.0067 (6)0.0110 (7)
C80.0306 (8)0.0358 (8)0.0378 (8)0.0041 (6)0.0110 (7)0.0161 (7)
C90.0412 (10)0.0369 (9)0.0508 (10)0.0190 (7)0.0179 (8)0.0228 (8)
C100.0513 (11)0.0324 (9)0.0497 (11)0.0197 (8)0.0149 (9)0.0166 (8)
Cl10.0565 (3)0.0506 (3)0.0353 (2)−0.0058 (2)0.0008 (2)0.0175 (2)
Co10.02117 (15)0.02402 (15)0.01902 (14)0.00459 (10)0.00162 (10)0.00862 (11)
N10.0255 (6)0.0329 (7)0.0226 (6)0.0051 (5)0.0004 (5)0.0104 (5)
N20.0247 (6)0.0420 (7)0.0260 (6)0.0001 (5)−0.0020 (5)0.0179 (6)
N30.0235 (6)0.0316 (6)0.0256 (6)0.0061 (5)0.0038 (5)0.0127 (5)
N40.0290 (7)0.0328 (7)0.0353 (7)0.0105 (5)0.0103 (5)0.0166 (6)
O10.0505 (8)0.0261 (6)0.0355 (6)0.0007 (5)0.0115 (5)0.0110 (5)
O20.0597 (10)0.0521 (9)0.0657 (10)0.0088 (7)−0.0033 (8)0.0025 (8)
O30.0763 (12)0.0472 (9)0.0683 (10)0.0111 (8)0.0051 (9)0.0147 (8)
Geometric parameters (Å, °) top
C1—C21.354 (3)C8—N41.363 (2)
C1—N21.367 (2)C8—H100.9300
C1—H10.9300C9—N41.466 (2)
C2—N11.380 (2)C9—C101.508 (3)
C2—H20.9300C9—H110.9700
C3—N11.319 (2)C9—H120.9700
C3—N21.348 (2)C10—C10ii1.518 (3)
C3—H30.9300C10—H130.9700
C4—N21.468 (2)C10—H140.9700
C4—C51.518 (3)Co1—N1iii2.1265 (18)
C4—H40.9700Co1—N12.1265 (18)
C4—H50.9700Co1—N32.1355 (18)
C5—C5i1.513 (3)Co1—N3iii2.1355 (18)
C5—H60.9700Co1—O12.1819 (17)
C5—H70.9700Co1—O1iii2.1819 (17)
C6—N31.316 (2)O1—H150.8500
C6—N41.345 (2)O1—H160.8501
C6—H80.9300O2—H170.8501
C7—C81.347 (2)O2—H180.8499
C7—N31.378 (2)O3—H190.8500
C7—H90.9300O3—H200.8501
C2—C1—N2106.40 (14)C9—C10—H13109.1
C2—C1—H1126.8C10ii—C10—H13109.1
N2—C1—H1126.8C9—C10—H14109.1
C1—C2—N1109.55 (16)C10ii—C10—H14109.1
C1—C2—H2125.2H13—C10—H14107.8
N1—C2—H2125.2N1iii—Co1—N1180.0
N1—C3—N2111.34 (14)N1iii—Co1—N393.49 (6)
N1—C3—H3124.3N1—Co1—N386.51 (6)
N2—C3—H3124.3N1iii—Co1—N3iii86.51 (6)
N2—C4—C5112.55 (14)N1—Co1—N3iii93.49 (6)
N2—C4—H4109.1N3—Co1—N3iii180.0
C5—C4—H4109.1N1iii—Co1—O188.40 (6)
N2—C4—H5109.1N1—Co1—O191.60 (6)
C5—C4—H5109.1N3—Co1—O188.99 (6)
H4—C4—H5107.8N3iii—Co1—O191.01 (6)
C5i—C5—C4113.60 (19)N1iii—Co1—O1iii91.60 (6)
C5i—C5—H6108.8N1—Co1—O1iii88.40 (6)
C4—C5—H6108.8N3—Co1—O1iii91.01 (6)
C5i—C5—H7108.8N3iii—Co1—O1iii88.99 (6)
C4—C5—H7108.8O1—Co1—O1iii180.0
H6—C5—H7107.7C3—N1—C2105.50 (14)
N3—C6—N4111.80 (15)C3—N1—Co1126.67 (11)
N3—C6—H8124.1C2—N1—Co1127.81 (12)
N4—C6—H8124.1C3—N2—C1107.20 (14)
C8—C7—N3109.45 (15)C3—N2—C4125.39 (15)
C8—C7—H9125.3C1—N2—C4127.34 (14)
N3—C7—H9125.3C6—N3—C7105.19 (14)
C7—C8—N4106.96 (15)C6—N3—Co1128.87 (11)
C7—C8—H10126.5C7—N3—Co1125.19 (11)
N4—C8—H10126.5C6—N4—C8106.59 (14)
N4—C9—C10111.41 (14)C6—N4—C9126.86 (15)
N4—C9—H11109.3C8—N4—C9126.17 (14)
C10—C9—H11109.3Co1—O1—H15128.5
N4—C9—H12109.3Co1—O1—H16121.2
C10—C9—H12109.3H15—O1—H16108.9
H11—C9—H12108.0H17—O2—H18106.8
C9—C10—C10ii112.6 (2)H19—O3—H20109.6
Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x, −y+1, −z+2; (iii) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H15···O3iv0.851.942.781 (2)169
O1—H16···Cl10.852.353.1728 (19)165
O2—H17···Cl1iv0.852.323.172 (2)176
O2—H18···Cl1v0.852.443.292 (3)175
O3—H19···O20.851.992.829 (3)171
O3—H20···Cl10.852.413.261 (3)174
Symmetry codes: (iv) −x+1, −y+1, −z+1; (v) x−1, y, z.
Table 1
Selected geometric parameters (Å, °) top
Co1—N12.1265 (18)Co1—O12.1819 (17)
Co1—N32.1355 (18)
N1i—Co1—N1180.0N1—Co1—O191.60 (6)
N1—Co1—N386.51 (6)N3—Co1—O188.99 (6)
N3—Co1—N3i180.0N1—Co1—O1i88.40 (6)
Symmetry codes: (i) −x+1, −y, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H15···O3ii0.851.942.781 (2)169
O1—H16···Cl10.852.353.1728 (19)165
O2—H17···Cl1ii0.852.323.172 (2)176
O2—H18···Cl1iii0.852.443.292 (3)175
O3—H19···O20.851.992.829 (3)171
O3—H20···Cl10.852.413.261 (3)174
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z.
Acknowledgements top

The authors acknowledge financial support from the National Natural Science Foundation of China (Nos. 20872030), the Research Foundation of Heilongjiang Provincial Education Department (Nos. 11513073), the Project of the Special Fund of the Science and Technology Innovation People of Harbin (Nos. RC2006QN018001) and Heilongjiang University.

references
References top

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Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yu, Y.-H., Shi, A.-E., Su, Y., Hou, G.-F. & Gao, J.-S. (2008). Acta Cryst. E64, m628.