Bis[μ-1,1′-methyl­enebis(1H-imidazole)-κ²N³:N^3′]bis­­[di­chloridocobalt(II)]

The title compound, [Co₂Cl₄(C₇H₈N₄)₂], contains a dinuclear complex molecule in which each Co^II atom is tetra­hedrally coordinated by two N atoms and two chloride ions. The 1,1′-methyl­enebis(1H-imidazole) ligands adopt a bis-monodentate bridging mode linking two Co^II atoms.

Related literature

For background to the design and synthesis of new organic–inorganic hybrid materials, see: Wang et al. (2007a,b). For a related structure, see: Wang et al. (2007b).

Experimental

Crystal data

• [Co₂Cl₄(C₇H₈N₄)₂]

• M_r = 556.01

• Monoclinic, P 2₁ /c

• a = 8.7137 (17) Å

• b = 8.7948 (18) Å

• c = 14.560 (3) Å

• β = 98.75 (3)°

• V = 1102.8 (4) ų

• Z = 2

• Mo Kα radiation

• μ = 2.01 mm⁻¹

• T = 293 K

• 0.3 × 0.3 × 0.3 mm

Data collection

• Rigaku SCX-mini diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.789, T_max = 1.0

• 11057 measured reflections

• 2501 independent reflections

• 2004 reflections with I > 2σ(I)

• R_int = 0.040

Refinement

• R[F² > 2σ(F²)] = 0.040

• wR(F²) = 0.075

• S = 1.13

• 2501 reflections

• 127 parameters

• H-atom parameters constrained

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.33 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; 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: publCIF (Westrip, 2010).

Supporting information

S1. Comment

Currently, increasing attention has been attracted to the design and synthesis of new organic-inorganic hybrid materials (Wang et al., 2007a). One of interesting strategies is using organic ligand to linking the metal salt. In our work the bridged ligand 1,1'-methylenedi-1H-imidazole (L) was selected to assemble novel organic-inorganic hybrid materials. Unexpectedly,the title compound, (I), was obtained with a dinuclear structure (Wang et al., 2007b). As shown in Fig. 1, the crystal structure of (I) the two CoCl₂ uints linked by two L ligands. In the complex the Co^II ion coordinated by two nitrogen atoms and and two Cl^- giving a tetrahedral geometry. The bond distances are normal range with of Co—N 2.020 (2) Å-2.029 (2)Å and Co—Cl 2.2478 (9) Å-2.2676 (9) Å. The L ligands all adopt a bis-monodentate bridging mode linking two Co^II atoms. atoms. The Cl^- anions coordinated to the Co^II atom in monodentate mode. By that way a diunclear complex was formed. The diunclear complex packing one by one in the soild state(Fig. 2).

Related literature

For background to the design and synthesis of new organic–inorganic hybrid materials, see: Wang et al. (2007a,b). For a related structure, see: Wang et al. (2007b). Please note that the Related literature section should be subdivided – "For related literature, see:" followed by all the references is not acceptable.

S2. Experimental

In a typical synthesis, a mixture of Co(Cl)₂.6H₂O (0.05 mmol), 1,1'-methylenedi-1H-imidazole(0.05 mmol) and H₂O (10 ml), was added to a 20 ml Teflon-lined reactor under autogenous pressure at 120 °C for 3 days. The resulting solution was slowly cooled to room temperature to yield single-crystal of the title compound.

S3. Refinement

All H atoms were positioned geometrically (C—H = 0.97Å and N—H = 0.90 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.2U_eq(parent atom).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-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: publCIF (Westrip, 2010).

Figures

	Fig. 1. A view of the title compound.Ellipsoids are drawn at the 30% probability level.H atoms have been omitted for clarity. [Symmetry codes: (a) -x + 1, -y, -z + 1].
	Fig. 2. Packing diagram of the title compound.

Bis[µ-1,1'-methylenebis(1H-imidazole)- κ²N³:N^3']bis[dichloridocobalt(II)]

Crystal data

[Co2Cl4(C7H8N4)2]	F(000) = 556
Mr = 556.01	Dx = 1.674 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9628 reflections
a = 8.7137 (17) Å	θ = 3.3–27.4°
b = 8.7948 (18) Å	µ = 2.01 mm^−1
c = 14.560 (3) Å	T = 293 K
β = 98.75 (3)°	Block, red
V = 1102.8 (4) Å^3	0.3 × 0.3 × 0.3 mm
Z = 2

Data collection

Rigaku SCX-mini diffractometer	2501 independent reflections
Radiation source: fine-focus sealed tube	2004 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
ω scans	θmax = 27.4°, θmin = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→11
Tmin = 0.789, Tmax = 1.0	k = −11→11
11057 measured reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.075	H-atom parameters constrained
S = 1.13	w = 1/[σ^2(Fo^2) + (0.024P)^2 + 0.5905P] where P = (Fo^2 + 2Fc^2)/3
2501 reflections	(Δ/σ)max = 0.001
127 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.71310 (4)	0.17519 (4)	0.29288 (2)	0.03334 (12)
Cl1	0.67525 (10)	0.16673 (10)	0.13677 (5)	0.0560 (2)
Cl2	0.86129 (8)	0.37006 (8)	0.35849 (5)	0.04539 (19)
N1	0.7895 (3)	−0.0223 (3)	0.35434 (15)	0.0392 (5)
N2	0.2068 (2)	0.2229 (2)	0.55419 (15)	0.0376 (5)
N3	0.3271 (2)	0.2738 (2)	0.41927 (15)	0.0345 (5)
N4	0.5028 (2)	0.2027 (2)	0.33439 (14)	0.0349 (5)
C1	0.4789 (3)	0.2715 (3)	0.41130 (18)	0.0355 (6)
H1	0.5570	0.3132	0.4546	0.043*
C2	0.3577 (3)	0.1591 (4)	0.2905 (2)	0.0465 (7)
H2	0.3378	0.1069	0.2344	0.056*
C3	0.2496 (3)	0.2042 (4)	0.3417 (2)	0.0502 (8)
H3	0.1429	0.1906	0.3272	0.060*
C4	0.2601 (3)	0.3409 (3)	0.4956 (2)	0.0432 (7)
H4A	0.1734	0.4054	0.4708	0.052*
H4B	0.3373	0.4037	0.5328	0.052*
C5	0.7094 (3)	−0.1052 (3)	0.4060 (2)	0.0441 (7)
H5	0.6075	−0.0847	0.4139	0.053*
C6	0.9327 (3)	−0.0932 (3)	0.3608 (2)	0.0459 (7)
H6	1.0142	−0.0610	0.3312	0.055*
C7	0.0639 (3)	0.2160 (3)	0.5834 (2)	0.0454 (7)
H7	−0.0186	0.2829	0.5678	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0356 (2)	0.0363 (2)	0.02950 (19)	0.00285 (16)	0.00930 (14)	0.00304 (16)
Cl1	0.0651 (5)	0.0732 (6)	0.0305 (4)	0.0026 (4)	0.0097 (3)	−0.0049 (4)
Cl2	0.0397 (4)	0.0467 (4)	0.0481 (4)	−0.0015 (3)	0.0016 (3)	−0.0035 (3)
N1	0.0421 (13)	0.0367 (13)	0.0423 (13)	0.0051 (11)	0.0175 (10)	0.0076 (11)
N2	0.0400 (13)	0.0338 (12)	0.0429 (14)	0.0061 (10)	0.0193 (11)	0.0092 (10)
N3	0.0344 (12)	0.0344 (12)	0.0364 (12)	0.0011 (10)	0.0114 (10)	0.0051 (10)
N4	0.0326 (12)	0.0410 (13)	0.0316 (12)	−0.0009 (10)	0.0065 (9)	−0.0017 (10)
C1	0.0325 (14)	0.0416 (15)	0.0328 (14)	−0.0034 (12)	0.0061 (11)	−0.0009 (12)
C2	0.0420 (16)	0.060 (2)	0.0367 (16)	−0.0092 (15)	0.0035 (13)	−0.0091 (14)
C3	0.0313 (15)	0.068 (2)	0.0510 (19)	−0.0085 (15)	0.0052 (14)	−0.0006 (16)
C4	0.0526 (17)	0.0362 (16)	0.0461 (17)	0.0055 (13)	0.0243 (14)	0.0076 (13)
C5	0.0396 (15)	0.0417 (16)	0.0553 (18)	0.0098 (13)	0.0206 (14)	0.0113 (14)
C6	0.0401 (16)	0.0467 (17)	0.0552 (19)	0.0014 (14)	0.0213 (14)	0.0086 (15)
C7	0.0346 (15)	0.0460 (17)	0.0590 (19)	0.0066 (13)	0.0182 (14)	0.0092 (15)

Geometric parameters (Å, º)

Co1—N1	2.020 (2)	N4—C2	1.381 (3)
Co1—N4	2.029 (2)	C1—H1	0.9300
Co1—Cl1	2.2478 (9)	C2—C3	1.347 (4)
Co1—Cl2	2.2676 (9)	C2—H2	0.9300
N1—C5	1.320 (3)	C3—H3	0.9300
N1—C6	1.385 (3)	C4—H4A	0.9700
N2—C5^i	1.346 (3)	C4—H4B	0.9700
N2—C7	1.377 (3)	C5—N2^i	1.346 (3)
N2—C4	1.464 (3)	C5—H5	0.9300
N3—C1	1.346 (3)	C6—C7^i	1.349 (4)
N3—C3	1.369 (4)	C6—H6	0.9300
N3—C4	1.456 (3)	C7—C6^i	1.349 (4)
N4—C1	1.317 (3)	C7—H7	0.9300
N1—Co1—N4	102.85 (9)	C3—C2—N4	109.3 (3)
N1—Co1—Cl1	114.03 (7)	C3—C2—H2	125.4
N4—Co1—Cl1	107.75 (7)	N4—C2—H2	125.4
N1—Co1—Cl2	109.58 (7)	C2—C3—N3	106.9 (2)
N4—Co1—Cl2	105.46 (7)	C2—C3—H3	126.6
Cl1—Co1—Cl2	115.95 (4)	N3—C3—H3	126.6
C5—N1—C6	105.2 (2)	N3—C4—N2	111.0 (2)
C5—N1—Co1	124.02 (18)	N3—C4—H4A	109.4
C6—N1—Co1	130.55 (18)	N2—C4—H4A	109.4
C5^i—N2—C7	106.9 (2)	N3—C4—H4B	109.4
C5^i—N2—C4	126.6 (2)	N2—C4—H4B	109.4
C7—N2—C4	126.4 (2)	H4A—C4—H4B	108.0
C1—N3—C3	106.9 (2)	N1—C5—N2^i	111.7 (2)
C1—N3—C4	125.8 (2)	N1—C5—H5	124.1
C3—N3—C4	127.3 (2)	N2^i—C5—H5	124.1
C1—N4—C2	105.6 (2)	C7^i—C6—N1	109.8 (2)
C1—N4—Co1	125.08 (18)	C7^i—C6—H6	125.1
C2—N4—Co1	129.31 (18)	N1—C6—H6	125.1
N4—C1—N3	111.4 (2)	C6^i—C7—N2	106.4 (2)
N4—C1—H1	124.3	C6^i—C7—H7	126.8
N3—C1—H1	124.3	N2—C7—H7	126.8
N4—Co1—N1—C5	1.3 (3)	C1—N4—C2—C3	0.6 (3)
Cl1—Co1—N1—C5	−115.1 (2)	Co1—N4—C2—C3	−178.2 (2)
Cl2—Co1—N1—C5	113.1 (2)	N4—C2—C3—N3	−1.2 (4)
N4—Co1—N1—C6	−172.0 (2)	C1—N3—C3—C2	1.3 (3)
Cl1—Co1—N1—C6	71.6 (3)	C4—N3—C3—C2	−179.8 (3)
Cl2—Co1—N1—C6	−60.2 (3)	C1—N3—C4—N2	−108.0 (3)
N1—Co1—N4—C1	88.2 (2)	C3—N3—C4—N2	73.3 (4)
Cl1—Co1—N4—C1	−151.0 (2)	C5^i—N2—C4—N3	53.1 (4)
Cl2—Co1—N4—C1	−26.6 (2)	C7—N2—C4—N3	−130.9 (3)
N1—Co1—N4—C2	−93.2 (2)	C6—N1—C5—N2^i	0.8 (3)
Cl1—Co1—N4—C2	27.6 (3)	Co1—N1—C5—N2^i	−173.89 (18)
Cl2—Co1—N4—C2	152.0 (2)	C5—N1—C6—C7^i	−0.5 (3)
C2—N4—C1—N3	0.3 (3)	Co1—N1—C6—C7^i	173.8 (2)
Co1—N4—C1—N3	179.13 (17)	C5^i—N2—C7—C6^i	−0.5 (3)
C3—N3—C1—N4	−1.0 (3)	C4—N2—C7—C6^i	−177.2 (3)
C4—N3—C1—N4	−179.9 (2)

Symmetry code: (i) −x+1, −y, −z+1.