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Acta Cryst. (2007). E63, m1880    [ doi:10.1107/S1600536807028073 ]

A polymorph of cis-dichloridobis(1,10-phenanthroline-[kappa]2N,N')cobalt(II)

L.-L. Li, D.-X. Liu and T.-F. Liu

Abstract top

A new polymorph of the title cobalt(II) complex, [CoCl2(C12H8N2)2], is reported here. A previous study reported a monoclinic form of this complex [Zhong, Zeng & Luo (2006), Acta Cryst. E62, m3330-m3332]. In the present orthorhombic structure, the CoII ion is located in a distorted octahedral geometry and coordinated by four N atoms from two 1,10-phenanthroline ligands and two Cl- anions. The molecules are linked into a two-dimensional framework via weak C-H...Cl hydrogen bonding.

Comment top

Herein, we report a polymorph of the title complex. This complex was determined with monoclinic P 21/c space group by Zhong et al. (2006). The corresponding six-coordinate complex with water and carbonate anion have been reported (Liu et al., 2004; Fu et al., 2006; Zhong et al., 2007).

In the present structure, the CoII ion is located in a distorted octahedral geometry (Fig. 1) and coordinated by four N atoms from two 1,10-phenanthroline ligands and two Cl− anions. The average Co—Cl bond distance of 2.168 (2) Å and Co—N bond distance of 2.4138 (5) Å (Table 1) are somewhat shorter than those found in the reported monoclinic structure [average 2.326 (2) Å and 2.4435 (8) Å].

The molecules are linked into a two-dimensional framework (Fig. 2) via weak intermolecular C—H···Cl hydrogen bonding (Table 2). But in the reported monoclinic structure, the molecules are linked into a three-dimensional framework by C—H···Cl hydrogen bonding and the π-π stacking.

Related literature top

For related structures, see: Zhong et al. (2006); Liu et al. (2004); Fu et al. (2006); Zhong et al. (2007).

Experimental top

A methanol solution (5 ml) of 1,10-phenanthroline (0.5 mmol) was added to an aqueous solution (10 ml) of cobalt dichloride (1.0 mmol) with stirring. The mixture was stirred continuously for 2 h at room temperature, and then filtered. Slow evaporation of the solution gave single crystals of the title compound.

Refinement top

H atoms were placed in calculated positions with C—H = 0.93 Å and refined in riding mode with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); 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, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, displacement ellipsoids are drawn at the 30% probability.
[Figure 2] Fig. 2. The unit cell packing diagram.
cis-dichloridobis(1,10-phenanthroline-κ2N,N')cobalt(II) top
Crystal data top
[CoCl2(C12H8N2)2]F000 = 996
Mr = 490.24Dx = 1.564 Mg m−3
Orthorhombic, Pna21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 5332 reflections
a = 21.2371 (14) Åθ = 2.5–28.2º
b = 7.7364 (5) ŵ = 1.10 mm−1
c = 12.6733 (9) ÅT = 273 (2) K
V = 2082.2 (2) Å3Block, red
Z = 40.43 × 0.21 × 0.13 mm
Data collection top
Bruker CCD area-detector
diffractometer		4821 independent reflections
Radiation source: fine-focus sealed tube4496 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.012
T = 273(2) Kθmax = 28.3º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1990)		h = −8→28
Tmin = 0.649, Tmax = 0.870k = −9→10
8974 measured reflectionsl = −15→16
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.022  w = 1/[σ2(Fo2) + (0.0247P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.055(Δ/σ)max = 0.003
S = 1.02Δρmax = 0.20 e Å−3
4821 reflectionsΔρmin = −0.15 e Å−3
280 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), with 2121 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.028 (9)
Secondary atom site location: difference Fourier map
Crystal data top
[CoCl2(C12H8N2)2]V = 2082.2 (2) Å3
Mr = 490.24Z = 4
Orthorhombic, Pna21Mo Kα
a = 21.2371 (14) ŵ = 1.10 mm−1
b = 7.7364 (5) ÅT = 273 (2) K
c = 12.6733 (9) Å0.43 × 0.21 × 0.13 mm
Data collection top
Bruker CCD area-detector
diffractometer		4821 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1990)		4496 reflections with I > 2σ(I)
Tmin = 0.649, Tmax = 0.870Rint = 0.012
8974 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.055Δρmax = 0.20 e Å−3
S = 1.02Δρmin = −0.15 e Å−3
4821 reflectionsAbsolute structure: Flack (1983), with 2121 Friedel pairs
280 parametersFlack parameter: 0.028 (9)
1 restraint
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
Co10.836180 (9)0.68890 (3)0.71778 (2)0.03249 (6)
Cl20.92419 (2)0.85110 (6)0.64460 (4)0.04752 (11)
Cl10.81796 (2)0.51066 (6)0.56653 (4)0.04825 (11)
C110.70676 (7)0.8328 (2)0.71241 (17)0.0357 (3)
N40.85782 (7)0.82299 (17)0.86690 (12)0.0360 (3)
N30.90037 (6)0.51456 (18)0.79647 (11)0.0344 (3)
N20.76570 (6)0.87682 (19)0.68047 (11)0.0369 (3)
C230.91076 (7)0.7581 (2)0.91265 (14)0.0344 (3)
C120.69965 (8)0.6750 (2)0.77073 (14)0.0365 (4)
N10.75226 (6)0.58222 (18)0.79065 (12)0.0379 (3)
C220.83464 (9)0.9694 (3)0.90508 (17)0.0466 (5)
H220.79761.01280.87630.056*
C190.94340 (9)0.8446 (2)0.99313 (14)0.0411 (4)
C70.65355 (9)0.9379 (3)0.69216 (16)0.0493 (5)
C100.77303 (10)1.0268 (2)0.63089 (17)0.0484 (5)
H100.81321.05870.60920.058*
C240.93201 (7)0.5905 (2)0.87816 (13)0.0335 (3)
C150.99882 (10)0.3426 (3)0.89786 (19)0.0527 (5)
H151.03150.28410.93120.063*
C40.63959 (9)0.6242 (3)0.80633 (17)0.0504 (5)
C60.59281 (9)0.8773 (3)0.7262 (2)0.0653 (6)
H60.55720.94270.71070.078*
C210.86354 (11)1.0611 (3)0.98676 (17)0.0550 (5)
H210.84521.16181.01260.066*
C90.72273 (13)1.1385 (3)0.61005 (19)0.0627 (6)
H90.72961.24270.57530.075*
C20.68866 (13)0.3801 (3)0.8858 (2)0.0669 (7)
H20.68630.27850.92480.080*
C130.91756 (8)0.3573 (2)0.76871 (15)0.0418 (4)
H130.89630.30430.71330.050*
C80.66375 (11)1.0931 (3)0.6412 (2)0.0639 (6)
H80.63011.16700.62820.077*
C200.91877 (11)1.0023 (3)1.02858 (16)0.0510 (5)
H200.93981.06601.07990.061*
C160.98266 (8)0.5114 (3)0.92949 (15)0.0418 (4)
C50.58623 (9)0.7304 (4)0.7792 (2)0.0667 (7)
H50.54610.69510.79930.080*
C140.96628 (10)0.2657 (3)0.81833 (16)0.0505 (5)
H140.97620.15390.79710.061*
C10.74660 (11)0.4377 (3)0.84612 (17)0.0537 (5)
H10.78240.37200.85920.064*
C30.63605 (12)0.4745 (3)0.8664 (2)0.0683 (7)
H30.59750.43890.89350.082*
C180.99832 (9)0.7653 (3)1.03787 (16)0.0500 (5)
H181.02210.82621.08700.060*
C171.01607 (9)0.6046 (3)1.01017 (17)0.0521 (5)
H171.05030.55321.04350.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02694 (9)0.03490 (11)0.03564 (11)−0.00102 (7)−0.00133 (10)0.00495 (11)
Cl20.0369 (2)0.0532 (3)0.0524 (3)−0.01210 (18)0.0080 (2)0.0052 (2)
Cl10.0511 (2)0.0495 (3)0.0442 (2)−0.0074 (2)−0.0059 (2)−0.0020 (2)
C110.0306 (7)0.0412 (8)0.0354 (8)0.0027 (6)−0.0049 (8)−0.0030 (8)
N40.0356 (7)0.0363 (8)0.0363 (8)0.0000 (6)−0.0002 (6)−0.0007 (6)
N30.0340 (7)0.0355 (7)0.0336 (7)0.0000 (5)0.0012 (6)0.0005 (6)
N20.0342 (7)0.0376 (8)0.0390 (8)−0.0024 (6)−0.0049 (6)0.0078 (6)
C230.0350 (8)0.0353 (9)0.0328 (9)−0.0035 (7)0.0024 (7)0.0020 (7)
C120.0314 (8)0.0449 (10)0.0333 (9)−0.0058 (6)0.0013 (7)−0.0038 (7)
N10.0361 (7)0.0384 (8)0.0391 (8)−0.0052 (6)0.0000 (6)0.0075 (6)
C220.0472 (10)0.0444 (11)0.0483 (12)0.0092 (8)0.0040 (9)−0.0037 (9)
C190.0457 (10)0.0451 (10)0.0323 (9)−0.0117 (8)−0.0020 (7)0.0031 (8)
C70.0411 (9)0.0571 (12)0.0497 (13)0.0139 (8)−0.0093 (8)−0.0115 (9)
C100.0540 (11)0.0422 (10)0.0490 (12)−0.0047 (8)−0.0059 (9)0.0122 (9)
C240.0293 (7)0.0391 (9)0.0321 (9)−0.0019 (6)0.0001 (6)0.0030 (7)
C150.0498 (11)0.0555 (12)0.0527 (13)0.0194 (9)−0.0034 (10)0.0087 (10)
C40.0380 (9)0.0663 (13)0.0469 (11)−0.0157 (9)0.0096 (9)−0.0109 (10)
C60.0345 (9)0.0851 (15)0.0764 (16)0.0168 (9)−0.0009 (12)−0.0137 (17)
C210.0740 (14)0.0408 (11)0.0501 (12)0.0028 (10)0.0056 (11)−0.0091 (9)
C90.0804 (16)0.0418 (11)0.0659 (15)0.0045 (11)−0.0179 (12)0.0141 (10)
C20.0836 (17)0.0579 (14)0.0592 (15)−0.0278 (12)0.0075 (13)0.0191 (12)
C130.0454 (10)0.0406 (9)0.0394 (10)0.0034 (7)0.0009 (8)0.0006 (8)
C80.0679 (15)0.0544 (13)0.0695 (15)0.0256 (10)−0.0208 (13)0.0012 (12)
C200.0676 (13)0.0447 (11)0.0408 (11)−0.0100 (9)−0.0028 (9)−0.0059 (8)
C160.0364 (9)0.0499 (11)0.0391 (10)0.0018 (7)−0.0022 (7)0.0040 (8)
C50.0284 (10)0.0954 (18)0.0762 (17)−0.0009 (10)0.0113 (9)−0.0159 (15)
C140.0606 (12)0.0438 (10)0.0471 (12)0.0153 (9)0.0029 (10)0.0015 (9)
C10.0614 (12)0.0493 (11)0.0504 (12)−0.0080 (10)−0.0044 (10)0.0154 (9)
C30.0603 (14)0.0819 (17)0.0627 (15)−0.0322 (13)0.0154 (12)0.0036 (13)
C180.0473 (10)0.0597 (12)0.0428 (11)−0.0119 (9)−0.0148 (9)0.0023 (9)
C170.0403 (10)0.0709 (15)0.0450 (12)−0.0009 (9)−0.0140 (8)0.0051 (10)
Geometric parameters (Å, °) top
Co1—N12.1703 (14)C24—C161.398 (2)
Co1—N22.1395 (14)C15—C141.359 (3)
Co1—N32.1615 (14)C15—C161.409 (3)
Co1—N42.2043 (15)C15—H150.9300
Co1—Cl12.3928 (6)C4—C31.388 (3)
Co1—Cl22.4348 (5)C4—C51.441 (3)
C11—N21.359 (2)C6—C51.327 (4)
C11—C71.416 (2)C6—H60.9300
C11—C121.435 (2)C21—C201.365 (3)
N4—C221.326 (2)C21—H210.9300
N4—C231.361 (2)C9—C81.360 (4)
N3—C131.318 (2)C9—H90.9300
N3—C241.367 (2)C2—C31.357 (4)
N2—C101.328 (2)C2—C11.402 (3)
C23—C191.403 (2)C2—H20.9300
C23—C241.441 (2)C13—C141.403 (3)
C12—N11.352 (2)C13—H130.9300
C12—C41.409 (2)C8—H80.9300
N1—C11.326 (2)C20—H200.9300
C22—C211.397 (3)C16—C171.438 (3)
C22—H220.9300C5—H50.9300
C19—C201.401 (3)C14—H140.9300
C19—C181.435 (3)C1—H10.9300
C7—C81.380 (3)C3—H30.9300
C7—C61.439 (3)C18—C171.346 (3)
C10—C91.400 (3)C18—H180.9300
C10—H100.9300C17—H170.9300
N2—Co1—N3165.28 (5)C16—C24—C23119.57 (15)
N2—Co1—N177.17 (5)C14—C15—C16119.53 (18)
N3—Co1—N194.83 (5)C14—C15—H15120.2
N2—Co1—N490.89 (5)C16—C15—H15120.2
N3—Co1—N476.51 (5)C3—C4—C12117.2 (2)
N1—Co1—N489.16 (6)C3—C4—C5124.3 (2)
N2—Co1—Cl195.82 (4)C12—C4—C5118.4 (2)
N3—Co1—Cl196.43 (4)C5—C6—C7121.67 (18)
N1—Co1—Cl189.37 (4)C5—C6—H6119.2
N4—Co1—Cl1172.63 (4)C7—C6—H6119.2
N2—Co1—Cl295.89 (4)C20—C21—C22119.74 (19)
N3—Co1—Cl290.76 (4)C20—C21—H21120.1
N1—Co1—Cl2171.28 (4)C22—C21—H21120.1
N4—Co1—Cl285.64 (4)C8—C9—C10119.2 (2)
Cl1—Co1—Cl296.66 (2)C8—C9—H9120.4
N2—C11—C7122.52 (17)C10—C9—H9120.4
N2—C11—C12117.60 (14)C3—C2—C1119.1 (2)
C7—C11—C12119.86 (16)C3—C2—H2120.4
C22—N4—C23117.78 (16)C1—C2—H2120.4
C22—N4—Co1129.59 (13)N3—C13—C14123.42 (18)
C23—N4—Co1111.34 (11)N3—C13—H13118.3
C13—N3—C24117.56 (15)C14—C13—H13118.3
C13—N3—Co1128.87 (13)C9—C8—C7120.35 (19)
C24—N3—Co1113.04 (11)C9—C8—H8119.8
C10—N2—C11117.87 (15)C7—C8—H8119.8
C10—N2—Co1128.02 (12)C21—C20—C19119.10 (18)
C11—N2—Co1114.11 (11)C21—C20—H20120.4
N4—C23—C19122.83 (15)C19—C20—H20120.4
N4—C23—C24117.47 (15)C24—C16—C15117.42 (18)
C19—C23—C24119.67 (15)C24—C16—C17119.43 (18)
N1—C12—C4122.70 (17)C15—C16—C17123.14 (19)
N1—C12—C11117.45 (14)C6—C5—C4121.75 (18)
C4—C12—C11119.85 (17)C6—C5—H5119.1
C1—N1—C12118.15 (16)C4—C5—H5119.1
C1—N1—Co1128.36 (13)C15—C14—C13119.11 (19)
C12—N1—Co1113.41 (11)C15—C14—H14120.4
N4—C22—C21122.74 (19)C13—C14—H14120.4
N4—C22—H22118.6N1—C1—C2122.5 (2)
C21—C22—H22118.6N1—C1—H1118.7
C20—C19—C23117.63 (17)C2—C1—H1118.7
C20—C19—C18123.31 (18)C2—C3—C4120.2 (2)
C23—C19—C18119.01 (17)C2—C3—H3119.9
C8—C7—C11117.33 (18)C4—C3—H3119.9
C8—C7—C6124.36 (19)C17—C18—C19121.32 (17)
C11—C7—C6118.3 (2)C17—C18—H18119.3
N2—C10—C9122.6 (2)C19—C18—H18119.3
N2—C10—H10118.7C18—C17—C16120.67 (18)
C9—C10—H10118.7C18—C17—H17119.7
N3—C24—C16122.87 (16)C16—C17—H17119.7
N3—C24—C23117.55 (14)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1i0.932.743.665 (2)171
C9—H9···Cl1ii0.932.803.561 (3)140
Symmetry codes: (i) −x+3/2, y−1/2, z+1/2; (ii) x, y+1, z.
Table 1
Selected geometric parameters (Å) top
Co1—N12.1703 (14)Co1—N42.2043 (15)
Co1—N22.1395 (14)Co1—Cl12.3928 (6)
Co1—N32.1615 (14)Co1—Cl22.4348 (5)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1i0.932.743.665 (2)171
C9—H9···Cl1ii0.932.803.561 (3)140
Symmetry codes: (i) −x+3/2, y−1/2, z+1/2; (ii) x, y+1, z.
Acknowledgements top

The authors acknowledge the support of the Natural Science Foundation Council of China (No. 20401003) and the Excellent Young Scholars Research Fund of Beijing Institute of Technology (No. 000Y07–26).

references
References top

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