Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ2N,N′)cobalt(II)

Akbarzadeh Torbati, N.; Rezvani, A.R.; Safari, N.; Amani, V.; Khavasi, H.R.

doi:10.1107/S1600536810035531

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page m1236

doi:10.1107/S1600536810035531

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Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ²N,N′)cobalt(II)

Niloufar Akbarzadeh Torbati,^a Ali Reza Rezvani,^a ^* Nasser Safari,^b Vahid Amani ^b and Hamid Reza Khavasi ^b

^aDepartment of Chemistry, University of Sistan and Baluchestan, PO Box 98135-674, Zahedan, Iran, and ^bDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: ali@hamoon.usb.ac.ir

(Received 27 August 2010; accepted 3 September 2010; online 11 September 2010)

In the title compound, [CoCl₂(C₁₄H₁₂N₂)], the Co^II atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand and two Cl atoms. The Co atom and the phenanthroline unit are located on a mirror plane. The methyl H atoms are disordered about the mirror plane and areeach half-occupied. In the crystal structure, π–π interactions between the pyridine and benzene rings and between the pyridine rings [centroid–centroid distances = 3.8821 (9) and 3.9502 (10) Å, respectively] stabilize the structure.

Related literature

For related structures, see: Alizadeh et al. (2009 ); Buttery et al. (2006 ); Ding et al. (2006 ); Fanizzi et al. (1991 ); Lemoine et al. (2003 ); Preston & Kennard (1969 ); Robinson & Sinn (1975 ).

Experimental

Crystal data

[CoCl₂(C₁₄H₁₂N₂)]
M_r = 338.09
Orthorhombic, P n m a
a = 11.2434 (12) Å
b = 7.441 (1) Å
c = 17.690 (3) Å
V = 1480.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 1.51 mm⁻¹
T = 298 K
0.50 × 0.22 × 0.20 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 2002 ) T_min = 0.681, T_max = 0.749
9742 measured reflections
2124 independent reflections
1871 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.139
S = 1.20
2124 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Table 1
Selected bond lengths (Å)

N1—Co1	2.046 (3)
N2—Co1	2.046 (3)
Cl1—Co1	2.2030 (9)

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035531/hy2350sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035531/hy2350Isup2.hkl

checkCIF report

Comment top

2,9-Dimethyl-1,10-phenanthroline (dmphen) is a good bidentate ligand, and numerous complexes with dmphen have been prepared, such as those of mercury (Alizadeh et al., 2009), zinc (Preston & Kennard, 1969), copper (Lemoine et al., 2003), nickel (Ding et al., 2006), gold (Robinson & Sinn, 1975), platinum (Fanizzi et al., 1991) and lithium (Buttery et al., 2006). Here, we report the synthesis and structure of the title compound.

In the title compound (Fig. 1), the Co^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from one dmphen ligand and two Cl atoms (Table 1). In the crystal structure, π–π interactions (Fig. 2) between the pyridyl and benzene rings, Cg3···Cg4ⁱ and Cg3···Cg3ⁱⁱ [symmetry codes: (i) -x, 1-y, 2-z; (ii) -x, -1/2+y, 2-z; where Cg3 and Cg4 are the centroids of the N2, C8–C11, C13 ring and C5–C8, C13–C14 ring], with centroid–centroid distances of 3.8821 (9) and 3.9502 (10) Å, stabilize the structure.

Related literature top

For related structures, see: Alizadeh et al. (2009); Buttery et al. (2006); Ding et al. (2006); Fanizzi et al. (1991); Lemoine et al. (2003); Preston & Kennard (1969); Robinson & Sinn (1975).

Experimental top

For the preparation of the title compound, a solution of dmphen (0.42 g, 2.00 mmol) in methanol (20 ml) was added to a solution of CoCl₂.6H₂O (0.48 g, 2.00 mmol) in methanol (20 ml) at room temperature. Crystals suitable for X-ray diffraction analysis were obtained by methanol diffusion into a blue solution of the title compound in DMSO after one week (yield: 0.50 g, 73.9%; m.p. > 573 K).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) x, 3/2-y, z.]
	Fig. 2. Crystal packing diagram for the title compound.

Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ²N,N')cobalt(II) top

Crystal data top

[CoCl₂(C₁₄H₁₂N₂)]	F(000) = 684
M_r = 338.09	D_x = 1.517 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1670 reflections
a = 11.2434 (12) Å	θ = 2.2–29.3°
b = 7.441 (1) Å	µ = 1.51 mm⁻¹
c = 17.690 (3) Å	T = 298 K
V = 1480.0 (4) Å³	Block, blue
Z = 4	0.50 × 0.22 × 0.20 mm

Data collection top

Stoe IPDS-2 diffractometer	2124 independent reflections
Radiation source: fine-focus sealed tube	1871 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
rotation method scans	θ_max = 29.3°, θ_min = 2.2°
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 2002)	h = −14→15
T_min = 0.681, T_max = 0.749	k = −10→10
9742 measured reflections	l = −15→24

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 1.20	w = 1/[σ²(F_o²) + (0.0692P)² + 0.4334P] where P = (F_o² + 2F_c²)/3
2124 reflections	(Δ/σ)_max = 0.001
114 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

[CoCl₂(C₁₄H₁₂N₂)]	V = 1480.0 (4) Å³
M_r = 338.09	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 11.2434 (12) Å	µ = 1.51 mm⁻¹
b = 7.441 (1) Å	T = 298 K
c = 17.690 (3) Å	0.50 × 0.22 × 0.20 mm

Data collection top

Stoe IPDS-2 diffractometer	2124 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 2002)	1871 reflections with I > 2σ(I)
T_min = 0.681, T_max = 0.749	R_int = 0.067
9742 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.20	Δρ_max = 0.51 e Å⁻³
2124 reflections	Δρ_min = −0.55 e Å⁻³
114 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.5096 (3)	0.7500	0.9952 (3)	0.0677 (12)
H1A	0.4953	0.6880	0.9484	0.102*	0.50
H1B	0.5719	0.6904	1.0224	0.102*	0.50
H1C	0.5329	0.8716	0.9849	0.102*	0.50
C2	0.3980 (3)	0.7500	1.0417 (2)	0.0502 (8)
C3	0.4022 (4)	0.7500	1.1208 (3)	0.0670 (12)
H3	0.4754	0.7500	1.1454	0.080*
C4	0.3002 (4)	0.7500	1.1619 (2)	0.0661 (11)
H4	0.3038	0.7500	1.2145	0.079*
C5	0.1893 (3)	0.7500	1.1254 (2)	0.0470 (7)
C6	0.0776 (4)	0.7500	1.1635 (2)	0.0599 (10)
H6	0.0763	0.7500	1.2161	0.072*
C7	−0.0259 (4)	0.7500	1.1254 (3)	0.0602 (10)
H7	−0.0974	0.7500	1.1518	0.072*
C8	−0.0270 (3)	0.7500	1.0444 (2)	0.0486 (8)
C9	−0.1318 (3)	0.7500	1.0008 (3)	0.0648 (11)
H9	−0.2057	0.7500	1.0244	0.078*
C10	−0.1246 (4)	0.7500	0.9245 (3)	0.0687 (12)
H10	−0.1939	0.7500	0.8959	0.082*
C11	−0.0128 (4)	0.7500	0.8877 (2)	0.0556 (9)
C12	−0.0018 (5)	0.7500	0.8039 (3)	0.0775 (14)
H12A	−0.0718	0.8026	0.7821	0.116*	0.50
H12B	0.0067	0.6287	0.7861	0.116*	0.50
H12C	0.0668	0.8187	0.7894	0.116*	0.50
C13	0.0806 (3)	0.7500	1.00504 (19)	0.0393 (6)
C14	0.1911 (3)	0.7500	1.04563 (19)	0.0387 (6)
N1	0.2938 (2)	0.7500	1.00521 (16)	0.0392 (5)
N2	0.0873 (2)	0.7500	0.92773 (17)	0.0423 (6)
Cl1	0.31373 (7)	0.49607 (9)	0.83732 (5)	0.0645 (2)
Co1	0.26015 (4)	0.7500	0.89154 (3)	0.04234 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0351 (16)	0.082 (3)	0.086 (3)	0.000	0.0071 (19)	0.000
C2	0.0353 (14)	0.058 (2)	0.058 (2)	0.000	−0.0052 (14)	0.000
C3	0.050 (2)	0.093 (3)	0.058 (2)	0.000	−0.0196 (18)	0.000
C4	0.062 (2)	0.093 (3)	0.043 (2)	0.000	−0.0126 (18)	0.000
C5	0.0494 (18)	0.0531 (18)	0.0387 (16)	0.000	0.0011 (13)	0.000
C6	0.064 (2)	0.073 (2)	0.0425 (19)	0.000	0.0116 (17)	0.000
C7	0.0507 (19)	0.070 (2)	0.060 (2)	0.000	0.0188 (17)	0.000
C8	0.0363 (15)	0.0488 (17)	0.061 (2)	0.000	0.0026 (14)	0.000
C9	0.0357 (16)	0.070 (3)	0.088 (3)	0.000	−0.0046 (18)	0.000
C10	0.0415 (18)	0.075 (3)	0.089 (3)	0.000	−0.024 (2)	0.000
C11	0.056 (2)	0.0505 (19)	0.061 (2)	0.000	−0.0229 (17)	0.000
C12	0.096 (4)	0.087 (3)	0.049 (2)	0.000	−0.033 (2)	0.000
C13	0.0353 (13)	0.0386 (13)	0.0441 (16)	0.000	−0.0016 (12)	0.000
C14	0.0353 (13)	0.0421 (14)	0.0388 (14)	0.000	−0.0013 (11)	0.000
N1	0.0331 (11)	0.0438 (13)	0.0409 (14)	0.000	−0.0001 (10)	0.000
N2	0.0413 (13)	0.0436 (13)	0.0420 (14)	0.000	−0.0063 (11)	0.000
Cl1	0.0738 (5)	0.0488 (4)	0.0707 (5)	0.0020 (3)	0.0176 (4)	−0.0121 (3)
Co1	0.0470 (3)	0.0423 (3)	0.0378 (3)	0.000	0.00572 (17)	0.000

Geometric parameters (Å, º) top

C1—C2	1.500 (5)	C8—C9	1.408 (5)
C1—H1A	0.9600	C9—C10	1.352 (8)
C1—H1B	0.9600	C9—H9	0.9300
C1—H1C	0.9600	C10—C11	1.416 (7)
C2—N1	1.337 (4)	C10—H10	0.9300
C2—C3	1.401 (6)	C11—N2	1.330 (4)
C3—C4	1.358 (7)	C11—C12	1.487 (6)
C3—H3	0.9300	C12—H12A	0.9600
C4—C5	1.405 (6)	C12—H12B	0.9600
C4—H4	0.9300	C12—H12C	0.9600
C5—C14	1.411 (5)	C13—N2	1.370 (4)
C5—C6	1.426 (5)	C13—C14	1.434 (4)
C6—C7	1.345 (6)	C14—N1	1.359 (4)
C6—H6	0.9300	N1—Co1	2.046 (3)
C7—C8	1.433 (6)	N2—Co1	2.046 (3)
C7—H7	0.9300	Cl1—Co1	2.2030 (9)
C8—C13	1.396 (5)	Co1—Cl1ⁱ	2.2030 (9)

C2—C1—H1A	109.5	C9—C10—C11	120.9 (4)
C2—C1—H1B	109.5	C9—C10—H10	119.6
H1A—C1—H1B	109.5	C11—C10—H10	119.6
C2—C1—H1C	109.5	N2—C11—C10	120.4 (4)
H1A—C1—H1C	109.5	N2—C11—C12	117.4 (4)
H1B—C1—H1C	109.5	C10—C11—C12	122.2 (4)
N1—C2—C3	120.8 (4)	C11—C12—H12A	109.5
N1—C2—C1	117.9 (4)	C11—C12—H12B	109.5
C3—C2—C1	121.4 (4)	H12A—C12—H12B	109.5
C4—C3—C2	120.4 (4)	C11—C12—H12C	109.5
C4—C3—H3	119.8	H12A—C12—H12C	109.5
C2—C3—H3	119.8	H12B—C12—H12C	109.5
C3—C4—C5	120.2 (4)	N2—C13—C8	123.0 (3)
C3—C4—H4	119.9	N2—C13—C14	116.9 (3)
C5—C4—H4	119.9	C8—C13—C14	120.1 (3)
C4—C5—C14	116.6 (3)	N1—C14—C5	122.6 (3)
C4—C5—C6	124.3 (4)	N1—C14—C13	118.2 (3)
C14—C5—C6	119.1 (3)	C5—C14—C13	119.2 (3)
C7—C6—C5	121.6 (4)	C2—N1—C14	119.4 (3)
C7—C6—H6	119.2	C2—N1—Co1	129.5 (2)
C5—C6—H6	119.2	C14—N1—Co1	111.1 (2)
C6—C7—C8	120.6 (3)	C11—N2—C13	119.1 (3)
C6—C7—H7	119.7	C11—N2—Co1	129.6 (3)
C8—C7—H7	119.7	C13—N2—Co1	111.3 (2)
C13—C8—C9	116.9 (4)	N1—Co1—N2	82.44 (11)
C13—C8—C7	119.4 (3)	N1—Co1—Cl1	112.17 (4)
C9—C8—C7	123.7 (4)	N2—Co1—Cl1	113.31 (4)
C10—C9—C8	119.7 (4)	N1—Co1—Cl1ⁱ	112.17 (4)
C10—C9—H9	120.1	N2—Co1—Cl1ⁱ	113.34 (4)
C8—C9—H9	120.1	Cl1—Co1—Cl1ⁱ	118.12 (5)

N1—C2—C3—C4	0.000 (3)	C1—C2—N1—C14	180.000 (1)
C1—C2—C3—C4	180.000 (2)	C3—C2—N1—Co1	180.000 (1)
C2—C3—C4—C5	0.000 (3)	C1—C2—N1—Co1	0.000 (2)
C3—C4—C5—C14	0.000 (2)	C5—C14—N1—C2	0.000 (2)
C3—C4—C5—C6	180.000 (2)	C13—C14—N1—C2	180.000 (1)
C4—C5—C6—C7	180.000 (2)	C5—C14—N1—Co1	180.000 (1)
C14—C5—C6—C7	0.000 (3)	C13—C14—N1—Co1	0.000 (1)
C5—C6—C7—C8	0.000 (3)	C10—C11—N2—C13	0.000 (2)
C6—C7—C8—C13	0.000 (2)	C12—C11—N2—C13	180.000 (2)
C6—C7—C8—C9	180.000 (2)	C10—C11—N2—Co1	180.000 (1)
C13—C8—C9—C10	0.000 (2)	C12—C11—N2—Co1	0.000 (1)
C7—C8—C9—C10	180.000 (2)	C8—C13—N2—C11	0.000 (2)
C8—C9—C10—C11	0.000 (2)	C14—C13—N2—C11	180.000 (1)
C9—C10—C11—N2	0.000 (2)	C8—C13—N2—Co1	180.000 (1)
C9—C10—C11—C12	180.000 (2)	C14—C13—N2—Co1	0.000 (1)
C9—C8—C13—N2	0.000 (2)	C2—N1—Co1—N2	180.000 (1)
C7—C8—C13—N2	180.000 (2)	C14—N1—Co1—N2	0.000 (1)
C9—C8—C13—C14	180.000 (1)	C2—N1—Co1—Cl1	67.86 (4)
C7—C8—C13—C14	0.000 (2)	C14—N1—Co1—Cl1	−112.14 (4)
C4—C5—C14—N1	0.000 (2)	C2—N1—Co1—Cl1ⁱ	−67.82 (4)
C6—C5—C14—N1	180.000 (2)	C14—N1—Co1—Cl1ⁱ	112.18 (4)
C4—C5—C14—C13	180.000 (2)	C11—N2—Co1—N1	180.000 (1)
C6—C5—C14—C13	0.000 (2)	C13—N2—Co1—N1	0.000 (1)
N2—C13—C14—N1	0.000 (2)	C11—N2—Co1—Cl1	−69.07 (5)
C8—C13—C14—N1	180.000 (1)	C13—N2—Co1—Cl1	110.93 (5)
N2—C13—C14—C5	180.000 (2)	C11—N2—Co1—Cl1ⁱ	69.07 (5)
C8—C13—C14—C5	0.000 (2)	C13—N2—Co1—Cl1ⁱ	−110.93 (5)
C3—C2—N1—C14	0.000 (2)

Symmetry code: (i) x, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₁₄H₁₂N₂)]
M_r	338.09
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	298
a, b, c (Å)	11.2434 (12), 7.441 (1), 17.690 (3)
V (Å³)	1480.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.51
Crystal size (mm)	0.50 × 0.22 × 0.20

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED; Stoe & Cie, 2002)
T_min, T_max	0.681, 0.749
No. of measured, independent and observed [I > 2σ(I)] reflections	9742, 2124, 1871
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.139, 1.20
No. of reflections	2124
No. of parameters	114
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.55

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

N1—Co1	2.046 (3)	Cl1—Co1	2.2030 (9)
N2—Co1	2.046 (3)

Acknowledgements

We are grateful to the University of Sistan and Baluchestan, and Shahid Beheshti University for financial support.

References

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