cis-Dichloridobis(1,10-phenanthroline)cobalt(II) dimethyl-formamide solvate.

In the title complex, [CoCl(2)(C(12)H(8)N(2))(2)]·C(3)H(7)NO, which has twofold rotation symmetry, the Co(II) cation is coordinated by two 1,10-phenanthroline (phen) mol-ecules and two chloride ligands in a distorted octa-hedral geometry. In the crystal structure, a cavity is created by six complex mol-ecules connected by C-H⋯π inter-actions and non-classical C-H⋯Cl hydrogen bonds. The cavities are occupied by the disordered dimethyl-formamide solvent mol-ecule. The C and N atoms of the C-N bond in the solvent mol-ecule also lie on a crystallographic twofold rotation axis; the remaining atoms of the solvent are statistically disordered (ratio 0.5:0.5) about this axis.

Related literature

For general background, see: Forster et al. (2000 ▶); Holder et al. (2007 ▶); Ma et al. (2002 ▶). Matsumoto et al. (2002 ▶); Xie et al. (2006 ▶). For a related structure, see: Hazell et al. (1997 ▶).

Experimental

Crystal data

[CoCl2(C12H8N2)2]·C3H7NO

M = 563.33

Orthorhombic,

a = 16.345 (3) Å

b = 12.342 (2) Å

c = 12.342 (2) Å

V = 2489.8 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.94 mm−1

T = 293 (2) K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury70 CCD diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku & Mol­ecular Structure Corporation, 2000 ▶) T min = 0.829, T max = 0.829

14711 measured reflections

2204 independent reflections

2168 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.063

S = 1.09

2204 reflections

180 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrystalClear (Rigaku & Molecular Structure Corporation, 2000 ▶); cell refinement: CrystalClear; data reduction: CrystalClear program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2005 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶) and PLATON (Spek; 2003 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030341/sj2538sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030341/sj2538Isup2.hkl

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

[CoCl2(C12H8N2)2]·C3H7NO	F(000) = 1156
Mr = 563.33	Dx = 1.503 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 6370 reflections
a = 16.345 (3) Å	θ = 2.1–25.0°
b = 12.342 (2) Å	µ = 0.94 mm−1
c = 12.342 (2) Å	T = 293 K
V = 2489.8 (8) Å3	Block, colorless
Z = 4	0.20 × 0.20 × 0.20 mm

Rigaku Mercury70 CCD diffractometer	2204 independent reflections
Radiation source: fine-focus sealed tube	2168 reflections with I > 2σ(I)
graphite	Rint = 0.017
ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (CrystalClear; Rigaku & Molecular Structure Corporation, 2000)	h = −17→19
Tmin = 0.829, Tmax = 0.829	k = −14→14
14711 measured reflections	l = −13→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.063	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0288P)2 + 1.9948P] where P = (Fo2 + 2Fc2)/3
2204 reflections	(Δ/σ)max < 0.001
180 parameters	Δρmax = 0.34 e Å−3
2 restraints	Δρmin = −0.21 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.5000	0.71666 (2)	0.2500	0.01272 (10)
Cl1	0.41390 (2)	0.59903 (3)	0.14376 (3)	0.01956 (11)
N2	0.59089 (8)	0.72168 (10)	0.12398 (11)	0.0151 (3)
C11	0.65206 (9)	0.79462 (12)	0.14122 (12)	0.0141 (3)
N1	0.57879 (8)	0.84851 (11)	0.29957 (11)	0.0162 (3)
C7	0.72069 (9)	0.80426 (13)	0.07300 (13)	0.0171 (3)
C12	0.64445 (9)	0.86417 (12)	0.23421 (13)	0.0148 (3)
C3	0.69394 (10)	1.00860 (14)	0.34665 (14)	0.0228 (4)
H3A	0.7317	1.0626	0.3628	0.027*
C10	0.59726 (10)	0.65659 (13)	0.03895 (13)	0.0187 (3)
H10A	0.5558	0.6065	0.0264	0.022*
C1	0.57135 (10)	0.91093 (14)	0.38597 (14)	0.0215 (4)
H1A	0.5264	0.9007	0.4311	0.026*
C6	0.78081 (10)	0.88565 (14)	0.09568 (14)	0.0209 (4)
H6A	0.8261	0.8924	0.0507	0.025*
C5	0.77263 (10)	0.95285 (14)	0.18162 (14)	0.0218 (4)
H5A	0.8120	1.0059	0.1940	0.026*
C2	0.62797 (10)	0.99184 (15)	0.41280 (15)	0.0253 (4)
H2A	0.6208	1.0336	0.4748	0.030*
C8	0.72538 (11)	0.73320 (13)	−0.01602 (14)	0.0210 (4)
H8A	0.7699	0.7360	−0.0629	0.025*
C9	0.66376 (10)	0.65987 (14)	−0.03293 (14)	0.0222 (4)
H9A	0.6660	0.6126	−0.0916	0.027*
C4	0.70425 (10)	0.94361 (13)	0.25393 (13)	0.0176 (3)
O1	0.5517 (2)	0.0842 (2)	0.1510 (3)	0.0433 (7)	0.50
N3	0.5000	0.2344 (2)	0.2500	0.0453 (7)
C13	0.5478 (6)	0.1828 (7)	0.1772 (8)	0.048 (3)	0.50
H13A	0.5840	0.2276	0.1400	0.057*	0.50
C14	0.5000	0.3523 (3)	0.2500	0.0553 (10)
H14A	0.5551	0.3783	0.2427	0.083*	0.50
H14B	0.4772	0.3783	0.3168	0.083*	0.50
H14C	0.4677	0.3783	0.1904	0.083*	0.50
C15	0.5421 (7)	0.1760 (10)	0.1657 (9)	0.067 (4)	0.50
H15A	0.5375	0.2151	0.0987	0.100*	0.50
H15B	0.5180	0.1055	0.1575	0.100*	0.50
H15C	0.5988	0.1685	0.1846	0.100*	0.50

	U11	U22	U33	U12	U13	U23
Co1	0.01000 (16)	0.01385 (16)	0.01430 (17)	0.000	−0.00028 (11)	0.000
Cl1	0.0170 (2)	0.0213 (2)	0.0203 (2)	−0.00516 (15)	−0.00274 (15)	−0.00162 (16)
N2	0.0134 (6)	0.0161 (6)	0.0159 (7)	−0.0002 (5)	−0.0015 (5)	0.0012 (5)
C11	0.0124 (7)	0.0146 (7)	0.0152 (8)	0.0011 (6)	−0.0018 (6)	0.0033 (6)
N1	0.0131 (6)	0.0174 (7)	0.0181 (7)	0.0004 (5)	−0.0004 (5)	−0.0016 (6)
C7	0.0148 (8)	0.0187 (8)	0.0177 (8)	0.0012 (6)	0.0003 (6)	0.0036 (6)
C12	0.0130 (7)	0.0147 (7)	0.0168 (8)	0.0012 (6)	−0.0027 (6)	0.0023 (6)
C3	0.0203 (8)	0.0208 (8)	0.0272 (9)	−0.0047 (7)	−0.0045 (7)	−0.0045 (7)
C10	0.0185 (8)	0.0180 (8)	0.0195 (8)	−0.0006 (6)	−0.0012 (7)	−0.0031 (7)
C1	0.0176 (8)	0.0252 (9)	0.0218 (9)	0.0001 (7)	0.0035 (7)	−0.0054 (7)
C6	0.0156 (8)	0.0263 (8)	0.0208 (8)	−0.0033 (7)	0.0022 (7)	0.0047 (7)
C5	0.0181 (8)	0.0236 (8)	0.0238 (9)	−0.0078 (7)	−0.0018 (7)	0.0036 (7)
C2	0.0227 (9)	0.0270 (9)	0.0262 (9)	−0.0020 (7)	0.0003 (7)	−0.0109 (8)
C8	0.0185 (8)	0.0249 (8)	0.0197 (8)	0.0025 (7)	0.0055 (7)	0.0018 (7)
C9	0.0240 (9)	0.0224 (8)	0.0203 (8)	0.0012 (7)	0.0022 (7)	−0.0048 (7)
C4	0.0155 (8)	0.0179 (8)	0.0194 (8)	−0.0003 (7)	−0.0034 (6)	0.0015 (6)
O1	0.0492 (19)	0.0294 (16)	0.0512 (19)	0.0003 (14)	−0.0046 (15)	−0.0048 (14)
N3	0.0390 (15)	0.0223 (12)	0.075 (2)	0.000	−0.0214 (14)	0.000
C13	0.065 (7)	0.018 (4)	0.060 (5)	−0.007 (4)	0.030 (5)	0.001 (3)
C14	0.049 (2)	0.0259 (16)	0.090 (3)	0.000	−0.0091 (19)	0.000
C15	0.047 (5)	0.057 (7)	0.095 (7)	0.001 (5)	−0.041 (5)	−0.028 (5)

Co1—N2	2.1517 (13)	C6—C5	1.353 (2)
Co1—N2i	2.1517 (13)	C6—H6A	0.9300
Co1—N1	2.1636 (13)	C5—C4	1.435 (2)
Co1—N1i	2.1636 (13)	C5—H5A	0.9300
Co1—Cl1	2.4099 (5)	C2—H2A	0.9300
Co1—Cl1i	2.4099 (5)	C8—C9	1.370 (2)
N2—C10	1.326 (2)	C8—H8A	0.9300
N2—C11	1.362 (2)	C9—H9A	0.9300
C11—C7	1.408 (2)	O1—C13	1.260 (9)
C11—C12	1.439 (2)	N3—C13	1.351 (7)
N1—C1	1.321 (2)	N3—C15	1.441 (8)
N1—C12	1.356 (2)	N3—C14	1.456 (4)
C7—C8	1.408 (2)	N3—C13i	1.351 (7)
C7—C6	1.433 (2)	N3—C15i	1.441 (8)
C12—C4	1.406 (2)	C13—H13A	0.9300
C3—C2	1.368 (2)	C14—H14A	0.9600
C3—C4	1.408 (2)	C14—H14B	0.9600
C3—H3A	0.9300	C14—H14C	0.9600
C10—C9	1.404 (2)	C15—H15A	0.9600
C10—H10A	0.9300	C15—H15B	0.9600
C1—C2	1.401 (2)	C15—H15C	0.9600
C1—H1A	0.9300
N2—Co1—N2i	176.70 (7)	C5—C6—C7	121.01 (15)
N2—Co1—N1	76.81 (5)	C5—C6—H6A	119.5
N2i—Co1—N1	100.65 (5)	C7—C6—H6A	119.5
N2—Co1—N1i	100.65 (5)	C6—C5—C4	121.05 (15)
N2i—Co1—N1i	76.81 (5)	C6—C5—H5A	119.5
N1—Co1—N1i	82.44 (7)	C4—C5—H5A	119.5
N2—Co1—Cl1	91.56 (4)	C3—C2—C1	119.15 (16)
N2i—Co1—Cl1	90.43 (4)	C3—C2—H2A	120.4
N1—Co1—Cl1	162.67 (4)	C1—C2—H2A	120.4
N1i—Co1—Cl1	87.23 (4)	C9—C8—C7	119.36 (15)
N2—Co1—Cl1i	90.43 (4)	C9—C8—H8A	120.3
N2i—Co1—Cl1i	91.56 (4)	C7—C8—H8A	120.3
N1—Co1—Cl1i	87.23 (4)	C8—C9—C10	119.48 (15)
N1i—Co1—Cl1i	162.67 (4)	C8—C9—H9A	120.3
Cl1—Co1—Cl1i	105.91 (2)	C10—C9—H9A	120.3
C10—N2—C11	117.80 (14)	C12—C4—C3	117.06 (15)
C10—N2—Co1	127.52 (11)	C12—C4—C5	119.30 (15)
C11—N2—Co1	114.39 (10)	C3—C4—C5	123.62 (15)
N2—C11—C7	123.19 (14)	C13i—N3—C13	123.8 (8)
N2—C11—C12	117.10 (14)	C13—N3—C15i	121.4 (4)
C7—C11—C12	119.71 (14)	C13i—N3—C15	121.4 (4)
C1—N1—C12	118.02 (14)	C15i—N3—C15	120.0 (11)
C1—N1—Co1	127.74 (11)	C13—N3—C14	118.1 (4)
C12—N1—Co1	114.20 (10)	C15—N3—C14	120.0 (6)
C11—C7—C8	117.23 (15)	O1—C13—N3	130.9 (6)
C11—C7—C6	119.27 (15)	O1—C13—H13A	114.6
C8—C7—C6	123.49 (15)	N3—C13—H13A	114.6
N1—C12—C4	123.13 (14)	N3—C14—H14A	109.5
N1—C12—C11	117.25 (14)	N3—C14—H14B	109.5
C4—C12—C11	119.62 (14)	H14A—C14—H14B	109.5
C2—C3—C4	119.56 (16)	N3—C14—H14C	109.5
C2—C3—H3A	120.2	H14A—C14—H14C	109.5
C4—C3—H3A	120.2	H14B—C14—H14C	109.5
N2—C10—C9	122.94 (15)	N3—C15—H15A	109.5
N2—C10—H10A	118.5	N3—C15—H15B	109.5
C9—C10—H10A	118.5	H15A—C15—H15B	109.5
N1—C1—C2	123.06 (16)	N3—C15—H15C	109.5
N1—C1—H1A	118.5	H15A—C15—H15C	109.5
C2—C1—H1A	118.5	H15B—C15—H15C	109.5
N1—Co1—N2—C10	178.15 (14)	N2—C11—C12—N1	2.6 (2)
N1i—Co1—N2—C10	−102.31 (13)	C7—C11—C12—N1	−177.44 (14)
Cl1—Co1—N2—C10	−14.83 (13)	N2—C11—C12—C4	−177.75 (14)
Cl1i—Co1—N2—C10	91.10 (13)	C7—C11—C12—C4	2.2 (2)
N1—Co1—N2—C11	4.54 (10)	C11—N2—C10—C9	0.1 (2)
N1i—Co1—N2—C11	84.08 (11)	Co1—N2—C10—C9	−173.37 (12)
Cl1—Co1—N2—C11	171.56 (10)	C12—N1—C1—C2	−0.1 (2)
Cl1i—Co1—N2—C11	−82.51 (10)	Co1—N1—C1—C2	177.45 (13)
C10—N2—C11—C7	0.5 (2)	C11—C7—C6—C5	0.2 (2)
Co1—N2—C11—C7	174.73 (12)	C8—C7—C6—C5	179.06 (16)
C10—N2—C11—C12	−179.63 (14)	C7—C6—C5—C4	1.1 (3)
Co1—N2—C11—C12	−5.35 (17)	C4—C3—C2—C1	−0.8 (3)
N2—Co1—N1—C1	179.24 (15)	N1—C1—C2—C3	0.6 (3)
N2i—Co1—N1—C1	1.40 (15)	C11—C7—C8—C9	0.7 (2)
N1i—Co1—N1—C1	76.37 (14)	C6—C7—C8—C9	−178.19 (16)
Cl1—Co1—N1—C1	130.31 (14)	C7—C8—C9—C10	−0.2 (2)
Cl1i—Co1—N1—C1	−89.67 (14)	N2—C10—C9—C8	−0.2 (3)
N2—Co1—N1—C12	−3.15 (10)	N1—C12—C4—C3	0.1 (2)
N2i—Co1—N1—C12	179.00 (10)	C11—C12—C4—C3	−179.44 (14)
N1i—Co1—N1—C12	−106.02 (12)	N1—C12—C4—C5	178.67 (15)
Cl1—Co1—N1—C12	−52.08 (19)	C11—C12—C4—C5	−0.9 (2)
Cl1i—Co1—N1—C12	87.94 (10)	C2—C3—C4—C12	0.4 (2)
N2—C11—C7—C8	−0.8 (2)	C2—C3—C4—C5	−178.04 (17)
C12—C11—C7—C8	179.25 (14)	C6—C5—C4—C12	−0.7 (2)
N2—C11—C7—C6	178.10 (14)	C6—C5—C4—C3	177.71 (16)
C12—C11—C7—C6	−1.8 (2)	C13i—N3—C13—O1	9.9 (10)
C1—N1—C12—C4	−0.3 (2)	C15i—N3—C13—O1	18 (2)
Co1—N1—C12—C4	−178.17 (12)	C15—N3—C13—O1	−62 (7)
C1—N1—C12—C11	179.28 (14)	C14—N3—C13—O1	−170.1 (10)
Co1—N1—C12—C11	1.42 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···Cl1	0.93	2.74	3.3408 (17)	124.
C6—H6A···Cl1ii	0.93	2.80	3.6743 (18)	158.
C5—H5A···Cl1iii	0.93	2.85	3.6375 (17)	144.
C2—H2A···Cg1iv	0.93	2.99	3.768 (2)	142
C8—H8A···Cg2v	0.93	2.90	3.608 (2)	134

Co1—N2	2.1517 (13)
Co1—N1	2.1636 (13)
Co1—Cl1	2.4099 (5)

N2—Co1—N2i	176.70 (7)
N2—Co1—N1	76.81 (5)
N2—Co1—N1i	100.65 (5)
N1—Co1—N1i	82.44 (7)
N2—Co1—Cl1	91.56 (4)
N2i—Co1—Cl1	90.43 (4)
N1—Co1—Cl1	162.67 (4)
N1i—Co1—Cl1	87.23 (4)
Cl1—Co1—Cl1i	105.91 (2)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯Cl1	0.93	2.74	3.3408 (17)	124
C6—H6A⋯Cl1ii	0.93	2.80	3.6743 (18)	158
C5—H5A⋯Cl1iii	0.93	2.85	3.6375 (17)	144
C2—H2A⋯Cg1iv	0.93	2.99	3.768 (2)	142
C8—H8A⋯Cg2v	0.93	2.90	3.608 (2)	134

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) .