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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m991.
Published online 2009 July 25. doi:  10.1107/S1600536809027846
PMCID: PMC2977247

Di-μ-chlorido-bis­[aqua­(2,2′-bipyridine-κ2 N,N′)chloridocobalt(II)]

Abstract

The title complex, [Co2Cl4(C10H8N2)2(H2O)2], is composed of two CoII atoms, each hexa­coordinated by three Cl atoms, one 2,2′-bipyridine (bpy) ligand and one water mol­ecule in a distorted octa­hedral geometry. Neighboring CoII atoms are linked together by two Cl bridges, forming a dinuclear CoII complex with inversion symmetry. There are inter­molecular O—H(...)Cl hydrogen bonds and inter­molecular π–π stacking inter­actions between adjacent bpy ligands [centroid–centroid distance = 3.617 (2) Å] in the structure.

Related literature

For Cl atoms acting as the bridging anions in transition metal complexes in multi-dimensional mol­ecule-based magnetic materials, see: Jian et al. (2005 [triangle]). For related structures, see: Leznoff et al. (2003 [triangle]); Liu et al.(2004 [triangle]); Puschmann et al. (2001 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m991-scheme1.jpg

Experimental

Crystal data

  • [Co2Cl4(C10H8N2)2(H2O)2]
  • M r = 608.06
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m991-efi1.jpg
  • a = 11.2939 (10) Å
  • b = 6.8969 (6) Å
  • c = 15.1339 (13) Å
  • β = 91.958 (3)°
  • V = 1178.14 (18) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 1.89 mm−1
  • T = 293 K
  • 0.26 × 0.20 × 0.20 mm

Data collection

  • Rigaku SCXmini diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.641, T max = 0.688
  • 11707 measured reflections
  • 2693 independent reflections
  • 2149 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.085
  • S = 1.03
  • 2693 reflections
  • 145 parameters
  • H-atom parameters constrained
  • Δρmax = 0.41 e Å−3
  • Δρmin = −0.49 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027846/at2843sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027846/at2843Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

In the study of multidimensional molecule-based magnetic materials and other areas, the Cl atoms acting as the bridging anions has frequently been used to bridge transition metal complexes (Jian et al., 2005). Many such compounds have been reported (Leznoff et al., 2003; Liu et al., 2004; Puschmann et al., 2001). Herein, we reported the structure of the title CoII compound (I).

The two Co atoms are bridged by two Cl anions into a four-membered Co2Cl2 ring. The Co atom is six-coordinated by three Cl atoms, one water molecules and one 2,2'-bipy ligand in an octahedral geometry. The molecule has an inversion symmetry (Fig. 1). In the crystal structure, the intermolecular O—H···Cl hydrogen bonds connect the molecules of (I) into a one-dimensional chain structure. There are π-π stacking interactions between adjacent bpy (2,2'-bipyridine) ligands, where the centroid–centroid separations are 3.617 (2) Å. π-π stacking interaction existing in every two O—H···Cl hydrogen bonds chains, and forming pairs of complex molecules into a two-dimensional structure (Fig. 2). A supramolecular network structure is consolidated by π-π stacking and hydrogen bonds.

Experimental

All chemicals used (reagent grade) were commercially available. To a 10 ml MeCN solution of cobalt dichloride hexahydrate (0.0238 g, 0.1 mmol), a 4 ml CH2Cl2 solution of 2,2'-bipyridine (0.0156 g, 0.1 mmol) was added dropwise with stirring. The resulting solution was continuously stirred for about 30 min, and then filtered. The filtrate was slowly evaporated at room temperature over several days, and colourless prism crystals suitable for X-ray analysis were obtained.

Refinement

The positions of the C-bound H atoms were calculated geometrically and refined using a riding model with C-H = 0.93Å and Uiso(H) = 1.2Ueq(C). The positional parameters for the H atoms of the water molecule were placed geometrically and refined with a fixed Uiso of 0.05.

Figures

Fig. 1.
The molecular structure of the title compound with the atom-numbering scheme and all hydrogen atoms. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code A: 2 - x, -y, 1 - z]
Fig. 2.
Crystal packing of the compound (I). Hydrogen bonds are shown as dashed lines.

Crystal data

[Co2Cl4(C10H8N2)2(H2O)2]F(000) = 612
Mr = 608.06Dx = 1.714 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 10382 reflections
a = 11.2939 (10) Åθ = 3.2–27.7°
b = 6.8969 (6) ŵ = 1.89 mm1
c = 15.1339 (13) ÅT = 293 K
β = 91.958 (3)°Prism, colourless
V = 1178.14 (18) Å30.26 × 0.20 × 0.20 mm
Z = 2

Data collection

Rigaku SCXmini diffractometer2693 independent reflections
Radiation source: fine-focus sealed tube2149 reflections with I > 2σ(I)
graphiteRint = 0.054
Detector resolution: 8.192 pixels mm-1θmax = 27.5°, θmin = 3.3°
ω scansh = −14→14
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −8→8
Tmin = 0.641, Tmax = 0.688l = −19→19
11707 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0346P)2 + 0.3472P] where P = (Fo2 + 2Fc2)/3
2693 reflections(Δ/σ)max = 0.001
145 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.49 e Å3

Special details

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)

xyzUiso*/Ueq
Co10.84715 (3)0.03942 (5)0.50354 (2)0.02938 (12)
O10.90322 (17)0.3279 (3)0.55130 (12)0.0420 (5)
H1B0.96290.31710.58330.050*
H1C0.86390.42800.53570.050*
N10.71222 (19)0.0653 (3)0.59523 (14)0.0328 (5)
N20.70852 (19)0.1700 (3)0.42759 (14)0.0340 (5)
C10.7206 (3)0.0099 (4)0.67984 (19)0.0418 (7)
H1A0.7894−0.05240.69990.050*
C20.6322 (3)0.0407 (5)0.7389 (2)0.0504 (8)
H2A0.64180.00350.79770.060*
C30.5291 (3)0.1284 (4)0.7079 (2)0.0500 (8)
H3A0.46730.14930.74590.060*
C40.5178 (3)0.1848 (4)0.6209 (2)0.0441 (7)
H4A0.44850.24370.59950.053*
C50.6114 (2)0.1524 (4)0.56541 (18)0.0325 (6)
C60.6095 (2)0.2104 (4)0.47093 (19)0.0345 (6)
C70.5126 (3)0.2985 (4)0.4275 (2)0.0430 (7)
H7A0.44480.32720.45810.052*
C80.5184 (3)0.3423 (4)0.3396 (2)0.0513 (9)
H8A0.45430.40110.31020.062*
C90.6192 (3)0.2994 (4)0.2947 (2)0.0493 (8)
H9A0.62420.32750.23480.059*
C100.7123 (3)0.2134 (4)0.34111 (19)0.0430 (7)
H10A0.78070.18420.31130.052*
Cl10.79648 (6)−0.29082 (10)0.45617 (5)0.0445 (2)
Cl20.99818 (6)0.07599 (10)0.39243 (4)0.03617 (17)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.0223 (2)0.0359 (2)0.0300 (2)0.00151 (15)0.00089 (14)0.00302 (16)
O10.0374 (11)0.0386 (11)0.0496 (12)−0.0004 (9)−0.0023 (9)−0.0006 (10)
N10.0269 (12)0.0365 (12)0.0349 (12)−0.0016 (10)0.0014 (9)−0.0011 (10)
N20.0264 (12)0.0348 (12)0.0405 (13)−0.0018 (9)−0.0020 (10)0.0042 (10)
C10.0373 (17)0.0510 (17)0.0373 (15)−0.0046 (13)0.0049 (13)0.0032 (13)
C20.052 (2)0.063 (2)0.0364 (16)−0.0128 (17)0.0123 (15)−0.0067 (15)
C30.0406 (18)0.0510 (19)0.060 (2)−0.0077 (15)0.0227 (15)−0.0188 (16)
C40.0323 (16)0.0383 (16)0.062 (2)−0.0014 (13)0.0101 (14)−0.0134 (15)
C50.0263 (14)0.0254 (13)0.0459 (15)−0.0025 (11)0.0025 (12)−0.0061 (12)
C60.0268 (14)0.0259 (13)0.0503 (16)−0.0012 (11)−0.0052 (12)−0.0037 (12)
C70.0308 (15)0.0313 (15)0.066 (2)0.0051 (12)−0.0099 (14)−0.0088 (14)
C80.051 (2)0.0340 (16)0.066 (2)0.0049 (14)−0.0279 (17)0.0019 (15)
C90.051 (2)0.0462 (18)0.0489 (18)−0.0039 (15)−0.0170 (15)0.0133 (15)
C100.0374 (16)0.0493 (18)0.0420 (16)−0.0032 (13)−0.0043 (13)0.0103 (14)
Cl10.0343 (4)0.0364 (4)0.0624 (5)−0.0001 (3)−0.0050 (3)−0.0031 (3)
Cl20.0264 (3)0.0535 (4)0.0286 (3)0.0013 (3)0.0003 (3)0.0078 (3)

Geometric parameters (Å, °)

Co1—N12.103 (2)C2—H2A0.9300
Co1—N22.112 (2)C3—C41.375 (4)
Co1—O12.2021 (18)C3—H3A0.9300
Co1—Cl2i2.4445 (7)C4—C51.391 (4)
Co1—Cl22.4488 (7)C4—H4A0.9300
Co1—Cl12.4497 (8)C5—C61.484 (4)
O1—H1B0.8200C6—C71.396 (4)
O1—H1C0.8500C7—C81.368 (4)
N1—C11.336 (3)C7—H7A0.9300
N1—C51.351 (3)C8—C91.377 (5)
N2—C101.345 (3)C8—H8A0.9300
N2—C61.345 (3)C9—C101.379 (4)
C1—C21.378 (4)C9—H9A0.9300
C1—H1A0.9300C10—H10A0.9300
C2—C31.380 (5)Cl2—Co1i2.4445 (7)
N1—Co1—N277.44 (8)C1—C2—H2A121.0
N1—Co1—O185.04 (8)C3—C2—H2A121.0
N2—Co1—O189.59 (8)C4—C3—C2119.9 (3)
N1—Co1—Cl2i96.93 (6)C4—C3—H3A120.1
N2—Co1—Cl2i171.68 (7)C2—C3—H3A120.1
O1—Co1—Cl2i83.78 (5)C3—C4—C5119.0 (3)
N1—Co1—Cl2169.00 (6)C3—C4—H4A120.5
N2—Co1—Cl295.92 (6)C5—C4—H4A120.5
O1—Co1—Cl286.16 (5)N1—C5—C4121.3 (3)
Cl2i—Co1—Cl288.66 (2)N1—C5—C6115.2 (2)
N1—Co1—Cl196.01 (6)C4—C5—C6123.5 (3)
N2—Co1—Cl194.35 (6)N2—C6—C7120.8 (3)
O1—Co1—Cl1176.05 (5)N2—C6—C5115.4 (2)
Cl2i—Co1—Cl192.31 (3)C7—C6—C5123.8 (3)
Cl2—Co1—Cl193.21 (3)C8—C7—C6119.4 (3)
Co1—O1—H1B109.5C8—C7—H7A120.3
Co1—O1—H1C120.1C6—C7—H7A120.3
H1B—O1—H1C130.4C7—C8—C9120.0 (3)
C1—N1—C5118.6 (2)C7—C8—H8A120.0
C1—N1—Co1125.36 (19)C9—C8—H8A120.0
C5—N1—Co1116.00 (17)C8—C9—C10118.0 (3)
C10—N2—C6118.9 (2)C8—C9—H9A121.0
C10—N2—Co1125.24 (19)C10—C9—H9A121.0
C6—N2—Co1115.86 (18)N2—C10—C9122.9 (3)
N1—C1—C2123.2 (3)N2—C10—H10A118.6
N1—C1—H1A118.4C9—C10—H10A118.6
C2—C1—H1A118.4Co1i—Cl2—Co191.34 (2)
C1—C2—C3118.0 (3)
N2—Co1—N1—C1−179.5 (2)C1—N1—C5—C6179.7 (2)
O1—Co1—N1—C1−88.8 (2)Co1—N1—C5—C62.2 (3)
Cl2i—Co1—N1—C1−5.7 (2)C3—C4—C5—N10.6 (4)
Cl2—Co1—N1—C1−125.8 (3)C3—C4—C5—C6−178.9 (3)
Cl1—Co1—N1—C187.3 (2)C10—N2—C6—C7−0.9 (4)
N2—Co1—N1—C5−2.25 (17)Co1—N2—C6—C7179.38 (19)
O1—Co1—N1—C588.43 (18)C10—N2—C6—C5178.2 (2)
Cl2i—Co1—N1—C5171.53 (17)Co1—N2—C6—C5−1.5 (3)
Cl2—Co1—N1—C551.4 (4)N1—C5—C6—N2−0.5 (3)
Cl1—Co1—N1—C5−95.39 (17)C4—C5—C6—N2179.1 (2)
N1—Co1—N2—C10−177.7 (2)N1—C5—C6—C7178.7 (2)
O1—Co1—N2—C1097.3 (2)C4—C5—C6—C7−1.8 (4)
Cl2—Co1—N2—C1011.2 (2)N2—C6—C7—C80.7 (4)
Cl1—Co1—N2—C10−82.5 (2)C5—C6—C7—C8−178.4 (3)
N1—Co1—N2—C61.99 (18)C6—C7—C8—C90.0 (4)
O1—Co1—N2—C6−83.02 (18)C7—C8—C9—C10−0.4 (4)
Cl2—Co1—N2—C6−169.12 (17)C6—N2—C10—C90.5 (4)
Cl1—Co1—N2—C697.19 (18)Co1—N2—C10—C9−179.8 (2)
C5—N1—C1—C2−1.3 (4)C8—C9—C10—N20.1 (4)
Co1—N1—C1—C2175.9 (2)N1—Co1—Cl2—Co1i120.8 (3)
N1—C1—C2—C31.8 (5)N2—Co1—Cl2—Co1i173.04 (6)
C1—C2—C3—C4−1.0 (5)O1—Co1—Cl2—Co1i83.85 (5)
C2—C3—C4—C5−0.1 (4)Cl2i—Co1—Cl2—Co1i0.0
C1—N1—C5—C40.1 (4)Cl1—Co1—Cl2—Co1i−92.24 (3)
Co1—N1—C5—C4−177.4 (2)

Symmetry codes: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1B···Cl1i0.822.813.407 (2)132
O1—H1C···Cl1ii0.852.393.213 (2)162

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2843).

References

  • Jian, F.-F., Wang, K.-F., Xiao, H.-L. & Qiao, Y.-B. (2005). Acta Cryst. E61, m1324–m1325.
  • Leznoff, D. B., Draper, N. D. & Batchelor, R. J. (2003). Polyhedron, 22, 1735–1743.
  • Liu, L., Zhang, Q.-F. & Leung, W.-H. (2004). Acta Cryst. E60, m394–m395.
  • Puschmann, H., Batsanov, A. S., Howard, J. A. K., Soto, B., Bonne, R. & Au-Alvarez, O. (2001). Acta Cryst. E57, m524–m526.
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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