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Acta Crystallogr Sect E Struct Rep Online. 2010 January 1; 66(Pt 1): m102.
Published online 2009 December 24. doi:  10.1107/S1600536809054671
PMCID: PMC2980258

Chloridobis(1,10-phenanthroline-κ2 N,N′)(2,2,2-trichloro­acetato-κO)cobalt(II)

Abstract

The title compound, [Co(C2Cl3O2)Cl(C12H8N2)2], was obtained by the reaction of trichloro­acetic acid and CoCl2 in the presence of 1,10-phenanthroline. The CoII ion exhibits a distorted octa­hedral geometry, with three N atoms from two 1,10-phenanthroline ligands and the Cl ion in the equatorial plane and one O atom from the trichloro­acetate ligand and one phenanthroline N atom in axial positions. This compound is isostructural with the analogous MnII complex. The trichloro­methyl group of the trichloro­acetate ligand is disordered over two positions with occupancies of 0.190 (5) and 0.810 (5).

Related literature

For the structure of isostructural MnII complex, see: Chen et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0m102-scheme1.jpg

Experimental

Crystal data

  • [Co(C2Cl3O2)Cl(C12H8N2)2]
  • M r = 617.16
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0m102-efi1.jpg
  • a = 18.2170 (6) Å
  • b = 10.4612 (4) Å
  • c = 14.6638 (7) Å
  • β = 112.685 (1)°
  • V = 2578.32 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.12 mm−1
  • T = 293 K
  • 0.26 × 0.20 × 0.18 mm

Data collection

  • Bruker SMART APEX diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2005 [triangle]) T min = 0.760, T max = 0.824
  • 13155 measured reflections
  • 4536 independent reflections
  • 3821 reflections with I > 2σ(I)
  • R int = 0.047

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.086
  • S = 1.01
  • 4536 reflections
  • 344 parameters
  • H-atom parameters constrained
  • Δρmax = 0.56 e Å−3
  • Δρmin = −0.62 e Å−3

Data collection: SMART (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; 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: SHELXL97.

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809054671/gk2250sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054671/gk2250Isup2.hkl

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

supplementary crystallographic information

Comment

The molecular structure of the title compound is shown in Fig. 1. The Co atom exhibits a distorted octahedral geometry. The metal ion deviates from the plane defined by three N atoms from two phenantroline molecules and the chlorido ligand by 0.0881 (2) Å.

Experimental

The reaction was carried out by the hydrothermal method. Trichloroacetic acid (0.082 g, 0.5 mmol), CoCl2.6H2O.(0.119 g, 0.5 mmol) and 1,10-phenanthroline (0.180 g, 1 mmol) were added to the airtight vessel containing 20 ml of water/methanol mixture in 2:1 ratio. The reaction was carried out at 303 K for 4 days and than cooled down. Resulting brown solution was filtered and brown block-shaped crystals appeared within a few days. Yield 76%; analysis calc. for C26H16Cl4CoN4O2: C 50.60, H 2.61, N 9.08%; found: C 50.91, H 2.25, N 9.34%. The elemental analyses were performed with PERKIN ELMER Model 2400 Series II.

Refinement

H atoms were positioned geometrically and treated as riding with with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The trichloromethyl group is disordered. Occupancies of Cl atoms in two positions refined at 0.190 (5) and 0.810 (5).. No restraints were imposed on the geometry of the disordered group.

Figures

Fig. 1.
The molecular structure of title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms.

Crystal data

[Co(C2Cl3O2)Cl(C12H8N2)2]F(000) = 1244
Mr = 617.16Dx = 1.595 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 7284 reflections
a = 18.2170 (6) Åθ = 2.3–28.1°
b = 10.4612 (4) ŵ = 1.12 mm1
c = 14.6638 (7) ÅT = 293 K
β = 112.685 (1)°Block, brown
V = 2578.32 (18) Å30.26 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer4536 independent reflections
Radiation source: fine-focus sealed tube3821 reflections with I > 2σ(I)
graphiteRint = 0.047
Detector resolution: 0 pixels mm-1θmax = 25.1°, θmin = 2.3°
phi and ω scansh = −17→21
Absorption correction: multi-scan (SADABS; Sheldrick, 2005)k = −11→12
Tmin = 0.760, Tmax = 0.824l = −17→16
13155 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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.042P)2 + 0.9036P] where P = (Fo2 + 2Fc2)/3
4536 reflections(Δ/σ)max = 0.001
344 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = −0.62 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*/UeqOcc. (<1)
Co10.290424 (16)0.88315 (3)0.12391 (2)0.03091 (10)
N10.39845 (10)0.79092 (17)0.12432 (13)0.0340 (4)
N20.36251 (10)1.04002 (17)0.10756 (13)0.0360 (4)
N30.19137 (10)1.00424 (18)0.11353 (13)0.0347 (4)
N40.22255 (11)0.89736 (17)−0.03298 (13)0.0349 (4)
O10.11352 (10)0.7113 (2)0.04032 (17)0.0690 (6)
O20.24513 (9)0.69856 (14)0.10847 (11)0.0389 (4)
Cl10.1960 (6)0.5139 (6)−0.0763 (5)0.0730 (5)0.190 (5)
Cl20.229 (3)0.430 (3)0.132 (4)0.0645 (8)0.190 (5)
Cl30.0807 (13)0.462 (2)−0.0130 (11)0.1180 (11)0.190 (5)
Cl1'0.23758 (16)0.50950 (12)−0.04800 (13)0.0730 (5)0.810 (5)
Cl2'0.2220 (6)0.4154 (7)0.1267 (8)0.0645 (8)0.810 (5)
Cl3'0.0798 (3)0.4598 (4)−0.0455 (2)0.1180 (11)0.810 (5)
Cl40.34432 (3)0.89244 (5)0.30104 (4)0.04054 (15)
C10.17636 (16)0.5183 (2)0.02503 (19)0.0511 (6)
C20.17667 (13)0.6599 (2)0.06043 (16)0.0364 (5)
C40.41513 (14)0.6677 (2)0.13065 (18)0.0424 (5)
H40.37590.61000.12940.051*
C50.48902 (15)0.6199 (2)0.13921 (19)0.0500 (6)
H50.49800.53220.14230.060*
C60.54786 (14)0.7022 (3)0.14301 (19)0.0491 (6)
H60.59750.67120.14960.059*
C70.53335 (13)0.8331 (2)0.13705 (16)0.0395 (5)
C80.45653 (12)0.8735 (2)0.12710 (15)0.0325 (5)
C90.43734 (12)1.0069 (2)0.11826 (15)0.0327 (5)
C100.49480 (14)1.0973 (2)0.11934 (17)0.0405 (5)
C110.47207 (15)1.2252 (2)0.10689 (19)0.0505 (6)
H110.50821.28820.10710.061*
C120.39604 (16)1.2573 (2)0.0943 (2)0.0547 (7)
H120.37971.34220.08500.066*
C130.34353 (14)1.1621 (2)0.09570 (19)0.0467 (6)
H130.29221.18560.08780.056*
C140.57281 (14)1.0536 (3)0.13301 (19)0.0498 (6)
H140.61181.11310.13680.060*
C150.59105 (14)0.9289 (3)0.14048 (19)0.0506 (6)
H150.64200.90370.14800.061*
C160.23604 (15)0.8363 (3)−0.10371 (17)0.0446 (6)
H160.28080.7844−0.08650.054*
C170.18590 (17)0.8463 (3)−0.20312 (18)0.0590 (7)
H170.19630.7997−0.25080.071*
C180.12179 (17)0.9246 (3)−0.22945 (19)0.0578 (7)
H180.08900.9340−0.29580.069*
C190.10473 (14)0.9916 (2)−0.15691 (17)0.0431 (5)
C200.15708 (12)0.9720 (2)−0.05844 (16)0.0344 (5)
C210.14063 (12)1.0312 (2)0.01997 (16)0.0328 (5)
C220.07409 (13)1.1109 (2)−0.00170 (18)0.0389 (5)
C230.06112 (14)1.1647 (2)0.0780 (2)0.0465 (6)
H230.01771.21820.06710.056*
C240.11226 (15)1.1384 (3)0.1715 (2)0.0498 (6)
H240.10441.17410.22510.060*
C250.17703 (15)1.0572 (2)0.18682 (17)0.0440 (6)
H250.21151.03970.25140.053*
C260.02322 (14)1.1322 (2)−0.1033 (2)0.0487 (6)
H26−0.02071.1857−0.11850.058*
C270.03816 (15)1.0759 (3)−0.17682 (19)0.0509 (6)
H270.00461.0919−0.24200.061*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Co10.02742 (16)0.03019 (17)0.03545 (17)0.00155 (11)0.01248 (13)0.00274 (12)
N10.0299 (9)0.0333 (10)0.0382 (10)0.0020 (8)0.0124 (8)0.0025 (8)
N20.0326 (10)0.0319 (10)0.0427 (10)−0.0007 (8)0.0135 (8)0.0015 (8)
N30.0319 (9)0.0373 (10)0.0358 (9)0.0029 (8)0.0141 (8)0.0018 (8)
N40.0331 (9)0.0361 (10)0.0379 (10)0.0018 (8)0.0165 (8)0.0033 (8)
O10.0364 (10)0.0618 (12)0.1007 (16)0.0080 (9)0.0175 (10)−0.0022 (12)
O20.0374 (9)0.0346 (8)0.0444 (9)−0.0048 (7)0.0153 (7)0.0011 (7)
Cl10.0975 (14)0.0771 (6)0.0503 (7)0.0091 (8)0.0352 (9)−0.0132 (5)
Cl20.085 (2)0.039 (2)0.0671 (15)0.0147 (14)0.0268 (15)0.0094 (15)
Cl30.0788 (7)0.0729 (7)0.132 (2)−0.0317 (5)−0.0366 (18)−0.0075 (18)
Cl1'0.0975 (14)0.0771 (6)0.0503 (7)0.0091 (8)0.0352 (9)−0.0132 (5)
Cl2'0.085 (2)0.039 (2)0.0671 (15)0.0147 (14)0.0268 (15)0.0094 (15)
Cl3'0.0788 (7)0.0729 (7)0.132 (2)−0.0317 (5)−0.0366 (18)−0.0075 (18)
Cl40.0363 (3)0.0438 (3)0.0378 (3)0.0023 (2)0.0102 (2)0.0029 (2)
C10.0529 (15)0.0415 (14)0.0488 (14)−0.0056 (12)0.0083 (12)−0.0031 (12)
C20.0328 (12)0.0406 (12)0.0364 (11)0.0010 (10)0.0141 (10)0.0060 (10)
C40.0405 (13)0.0347 (12)0.0517 (14)0.0037 (10)0.0175 (11)0.0037 (11)
C50.0478 (15)0.0431 (14)0.0580 (16)0.0132 (12)0.0191 (13)0.0008 (12)
C60.0373 (13)0.0576 (16)0.0536 (15)0.0134 (12)0.0187 (11)−0.0004 (13)
C70.0326 (12)0.0509 (14)0.0351 (12)0.0039 (11)0.0132 (10)−0.0011 (11)
C80.0291 (11)0.0394 (12)0.0281 (10)−0.0001 (9)0.0101 (9)0.0000 (9)
C90.0296 (11)0.0386 (12)0.0288 (10)−0.0033 (9)0.0100 (9)−0.0014 (9)
C100.0383 (13)0.0444 (14)0.0375 (12)−0.0103 (10)0.0131 (10)−0.0036 (10)
C110.0487 (15)0.0430 (15)0.0584 (15)−0.0164 (12)0.0190 (13)−0.0025 (12)
C120.0532 (15)0.0335 (13)0.0740 (18)−0.0048 (11)0.0207 (14)0.0020 (13)
C130.0406 (13)0.0348 (13)0.0637 (16)0.0012 (11)0.0189 (12)0.0033 (12)
C140.0342 (13)0.0600 (17)0.0561 (15)−0.0138 (12)0.0185 (11)−0.0052 (13)
C150.0294 (12)0.0687 (18)0.0535 (15)−0.0018 (12)0.0159 (11)−0.0054 (14)
C160.0477 (13)0.0512 (14)0.0424 (13)0.0060 (12)0.0257 (11)0.0028 (12)
C170.0686 (18)0.077 (2)0.0373 (13)0.0120 (16)0.0266 (13)−0.0001 (13)
C180.0593 (17)0.0757 (19)0.0336 (13)0.0056 (15)0.0126 (12)0.0058 (13)
C190.0401 (13)0.0494 (14)0.0367 (12)−0.0021 (11)0.0114 (10)0.0057 (11)
C200.0304 (11)0.0355 (12)0.0370 (11)−0.0028 (9)0.0128 (9)0.0039 (10)
C210.0270 (11)0.0298 (11)0.0405 (12)−0.0017 (9)0.0118 (9)0.0034 (9)
C220.0293 (11)0.0332 (12)0.0515 (14)−0.0003 (9)0.0128 (10)0.0035 (10)
C230.0375 (13)0.0414 (13)0.0639 (16)0.0083 (11)0.0233 (12)0.0014 (12)
C240.0509 (15)0.0520 (15)0.0535 (15)0.0090 (12)0.0278 (13)−0.0039 (13)
C250.0454 (13)0.0492 (14)0.0395 (12)0.0066 (11)0.0186 (11)−0.0003 (11)
C260.0337 (12)0.0450 (14)0.0580 (16)0.0089 (11)0.0073 (11)0.0098 (12)
C270.0426 (14)0.0561 (16)0.0428 (13)0.0062 (12)0.0040 (11)0.0097 (13)

Geometric parameters (Å, °)

Co1—O22.078 (2)C9—C101.406 (3)
Co1—N42.155 (2)C10—C111.392 (4)
Co1—N32.161 (2)C10—C141.431 (3)
Co1—N22.172 (2)C11—C121.367 (4)
Co1—N12.190 (2)C11—H110.9300
Co1—Cl42.3985 (6)C12—C131.386 (3)
N1—C41.320 (3)C12—H120.9300
N1—C81.355 (3)C13—H130.9300
N2—C131.316 (3)C14—C151.340 (4)
N2—C91.356 (3)C14—H140.9300
N3—C251.321 (3)C15—H150.9300
N3—C211.356 (3)C16—C171.394 (3)
N4—C161.320 (3)C16—H160.9300
N4—C201.352 (3)C17—C181.355 (4)
O1—C21.199 (3)C17—H170.9300
O2—C21.240 (3)C18—C191.405 (4)
Cl1—C11.658 (6)C18—H180.9300
Cl2—C11.75 (5)C19—C201.405 (3)
Cl3—C11.72 (2)C19—C271.435 (4)
Cl1'—C11.822 (3)C20—C211.436 (3)
Cl2'—C11.766 (11)C21—C221.403 (3)
Cl3'—C11.770 (4)C22—C231.398 (3)
C1—C21.569 (3)C22—C261.436 (3)
C4—C51.395 (3)C23—C241.355 (4)
C4—H40.9300C23—H230.9300
C5—C61.359 (4)C24—C251.400 (3)
C5—H50.9300C24—H240.9300
C6—C71.390 (4)C25—H250.9300
C6—H60.9300C26—C271.346 (4)
C7—C81.415 (3)C26—H260.9300
C7—C151.439 (3)C27—H270.9300
C8—C91.432 (3)
O2—Co1—N484.70 (6)N2—C9—C10122.7 (2)
O2—Co1—N3104.56 (6)N2—C9—C8117.34 (19)
N4—Co1—N376.40 (7)C10—C9—C8120.0 (2)
O2—Co1—N2157.18 (6)C11—C10—C9117.6 (2)
N4—Co1—N287.28 (7)C11—C10—C14123.7 (2)
N3—Co1—N294.21 (7)C9—C10—C14118.8 (2)
O2—Co1—N184.80 (6)C12—C11—C10119.2 (2)
N4—Co1—N1100.27 (7)C12—C11—H11120.4
N3—Co1—N1169.56 (7)C10—C11—H11120.4
N2—Co1—N175.65 (7)C11—C12—C13119.4 (2)
O2—Co1—Cl497.77 (5)C11—C12—H12120.3
N4—Co1—Cl4168.35 (5)C13—C12—H12120.3
N3—Co1—Cl491.98 (5)N2—C13—C12123.4 (2)
N2—Co1—Cl494.39 (5)N2—C13—H13118.3
N1—Co1—Cl491.31 (5)C12—C13—H13118.3
C4—N1—C8117.74 (19)C15—C14—C10121.6 (2)
C4—N1—Co1127.80 (15)C15—C14—H14119.2
C8—N1—Co1114.18 (14)C10—C14—H14119.2
C13—N2—C9117.68 (19)C14—C15—C7121.3 (2)
C13—N2—Co1127.44 (15)C14—C15—H15119.3
C9—N2—Co1114.68 (14)C7—C15—H15119.3
C25—N3—C21117.66 (19)N4—C16—C17122.7 (2)
C25—N3—Co1127.58 (15)N4—C16—H16118.7
C21—N3—Co1114.71 (14)C17—C16—H16118.7
C16—N4—C20118.3 (2)C18—C17—C16119.2 (2)
C16—N4—Co1126.95 (16)C18—C17—H17120.4
C20—N4—Co1114.59 (14)C16—C17—H17120.4
C2—O2—Co1129.44 (15)C17—C18—C19120.3 (2)
C2—C1—Cl1110.4 (3)C17—C18—H18119.9
C2—C1—Cl3107.9 (8)C19—C18—H18119.9
Cl1—C1—Cl3104.0 (7)C20—C19—C18116.4 (2)
C2—C1—Cl2105.5 (12)C20—C19—C27119.0 (2)
Cl1—C1—Cl2123.8 (18)C18—C19—C27124.7 (2)
Cl3—C1—Cl2104.3 (15)N4—C20—C19123.0 (2)
C2—C1—Cl2'110.8 (3)N4—C20—C21117.54 (19)
C2—C1—Cl3'113.3 (2)C19—C20—C21119.4 (2)
Cl2'—C1—Cl3'108.8 (3)N3—C21—C22123.0 (2)
C2—C1—Cl1'108.47 (17)N3—C21—C20116.70 (18)
Cl2'—C1—Cl1'105.7 (4)C22—C21—C20120.3 (2)
Cl3'—C1—Cl1'109.5 (2)C23—C22—C21117.4 (2)
O1—C2—O2130.7 (2)C23—C22—C26123.7 (2)
O1—C2—C1117.5 (2)C21—C22—C26118.9 (2)
O2—C2—C1111.7 (2)C24—C23—C22119.5 (2)
N1—C4—C5123.0 (2)C24—C23—H23120.3
N1—C4—H4118.5C22—C23—H23120.3
C5—C4—H4118.5C23—C24—C25119.6 (2)
C6—C5—C4119.7 (2)C23—C24—H24120.2
C6—C5—H5120.2C25—C24—H24120.2
C4—C5—H5120.2N3—C25—C24122.9 (2)
C5—C6—C7119.6 (2)N3—C25—H25118.6
C5—C6—H6120.2C24—C25—H25118.6
C7—C6—H6120.2C27—C26—C22120.9 (2)
C6—C7—C8117.2 (2)C27—C26—H26119.5
C6—C7—C15124.4 (2)C22—C26—H26119.5
C8—C7—C15118.4 (2)C26—C27—C19121.5 (2)
N1—C8—C7122.8 (2)C26—C27—H27119.3
N1—C8—C9117.28 (18)C19—C27—H27119.3
C7—C8—C9119.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C17—H17···O2i0.932.543.364 (3)148
C11—H11···Cl4ii0.932.733.548 (2)148
C23—H23···O1iii0.932.423.249 (3)149

Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x, −y+2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2250).

References

  • Bruker (2005). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, L., Wang, X.-W., Chen, F.-P., Chen, Y. & Chen, J.-Z. (2006). Acta Cryst. E62, m1743–m1745.
  • Sheldrick, G. M. (2005). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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