Bis(2-amino-3-methyl-pyridine)-dichlorido-cobalt(II).

In the title compound, [CoCl(2)(C(6)H(8)N(2))(2)], the Co(II) ion is four-coordinated by two pyridine N atoms from the 2-amino-3-methyl-pyridine ligands and two chloride ions in a distorted tetra-hedral geometry. A weak intra-molecular N-H⋯Cl inter-action occurs. The crystal packing is stabilized by inter-molecular N-H⋯Cl and C-H⋯Cl hydrogen-bond inter-actions.

Related literature

2-Amino-3-methyl­pyridine (ampy) can potentially coordinate to metal centers through the N atom of the amino group (Chen et al., 2005 ▶) or the pyridyl nitro­gen atom (Amani Komaei et al., 1999 ▶; Ziegler et al., 2000 ▶; Castillo et al., 2001 ▶). For the structures of [(ampyH)2CoX 4] proton-transfer compounds (X = Cl, Br), see: Carnevale et al. (2010 ▶). Polar metal–halogen bonds are good hydrogen-bond acceptors, see: Aullón et al. (1998 ▶).

Experimental

Crystal data

[CoCl2(C6H8N2)2]

M = 346.12

Monoclinic,

a = 9.3768 (19) Å

b = 13.841 (3) Å

c = 12.175 (2) Å

β = 100.31 (3)°

V = 1554.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 1.44 mm−1

T = 298 K

0.50 × 0.38 × 0.30 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: numerical shape of crystal determined optically (XRED and XSHAPE; Stoe & Cie, 2005 ▶)T min = 0.517, T max = 0.642

11996 measured reflections

4174 independent reflections

2803 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.132

S = 1.07

4174 reflections

174 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.52 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036597/jj2058sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036597/jj2058Isup2.hkl

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

[CoCl2(C6H8N2)2]	F(000) = 708.0
Mr = 346.12	Dx = 1.479 Mg m−3
Monoclinic, P21/n	Melting point: 441 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.3768 (19) Å	Cell parameters from 4174 reflections
b = 13.841 (3) Å	θ = 2.3–29.2°
c = 12.175 (2) Å	µ = 1.44 mm−1
β = 100.31 (3)°	T = 298 K
V = 1554.6 (5) Å3	Block, blue
Z = 4	0.5 × 0.38 × 0.3 mm

Stoe IPDS II diffractometer	4174 independent reflections
Radiation source: fine-focus sealed tube	2803 reflections with I > 2σ(I)
graphite	Rint = 0.055
Detector resolution: 0.15 pixels mm-1	θmax = 29.2°, θmin = 2.3°
rotation method scans	h = −12→10
Absorption correction: numerical shape of crystal determined optically (X-RED and X-SHAPE; Stoe & Cie, 2005)	k = −18→18
Tmin = 0.517, Tmax = 0.642	l = −16→16
11996 measured reflections

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0528P)2 + 0.6654P] where P = (Fo2 + 2Fc2)/3
4174 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.52 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
Co1	0.14951 (4)	0.99824 (3)	0.31175 (3)	0.04765 (14)
Cl2	0.09365 (12)	1.14810 (7)	0.35642 (8)	0.0730 (3)
Cl1	0.24844 (11)	0.99925 (9)	0.15526 (7)	0.0738 (3)
N3	0.2899 (3)	0.93750 (18)	0.43978 (19)	0.0450 (6)
N1	−0.0296 (3)	0.9120 (2)	0.2839 (2)	0.0484 (6)
C5	−0.0369 (4)	0.8380 (3)	0.3553 (3)	0.0579 (8)
H5	0.0376	0.8310	0.4164	0.069*
C1	−0.1395 (3)	0.9237 (3)	0.1967 (2)	0.0509 (7)
C7	0.3589 (3)	0.8548 (2)	0.4302 (3)	0.0490 (7)
C2	−0.2593 (4)	0.8599 (3)	0.1783 (3)	0.0552 (8)
C9	0.4738 (4)	0.8617 (3)	0.6192 (3)	0.0641 (9)
H9	0.5363	0.8367	0.6805	0.077*
C11	0.3132 (4)	0.9843 (2)	0.5399 (3)	0.0541 (8)
H11	0.2654	1.0423	0.5464	0.065*
C6	−0.3807 (4)	0.8754 (4)	0.0808 (3)	0.0829 (13)
H6A	−0.4567	0.8296	0.0844	0.124*
H6B	−0.3449	0.8665	0.0124	0.124*
H6C	−0.4179	0.9398	0.0835	0.124*
C8	0.4538 (4)	0.8119 (3)	0.5215 (3)	0.0546 (8)
N2	−0.1321 (4)	0.9997 (2)	0.1281 (3)	0.0756 (10)
H2A	−0.0593	1.0385	0.1409	0.091*
H2B	−0.2003	1.0093	0.0718	0.091*
C10	0.4044 (4)	0.9485 (3)	0.6308 (3)	0.0664 (10)
H10	0.4195	0.9814	0.6985	0.080*
C3	−0.2594 (4)	0.7855 (3)	0.2517 (3)	0.0680 (10)
H3	−0.3359	0.7418	0.2410	0.082*
C4	−0.1470 (4)	0.7738 (3)	0.3422 (3)	0.0705 (10)
H4	−0.1477	0.7232	0.3923	0.085*
N4	0.3322 (4)	0.8108 (3)	0.3292 (3)	0.0793 (10)
H4A	0.2730	0.8365	0.2749	0.095*
H4B	0.3745	0.7572	0.3193	0.095*
C12	0.5285 (5)	0.7188 (3)	0.5056 (4)	0.0809 (12)
H12A	0.5894	0.7005	0.5744	0.121*
H12B	0.5866	0.7267	0.4488	0.121*
H12C	0.4574	0.6693	0.4833	0.121*

	U11	U22	U33	U12	U13	U23
Co1	0.0456 (2)	0.0545 (2)	0.0391 (2)	−0.0008 (2)	−0.00267 (15)	0.00612 (18)
Cl2	0.0862 (7)	0.0581 (5)	0.0698 (5)	0.0198 (5)	0.0008 (5)	0.0085 (4)
Cl1	0.0666 (5)	0.1115 (8)	0.0421 (4)	−0.0138 (6)	0.0066 (4)	0.0074 (5)
N3	0.0440 (13)	0.0488 (14)	0.0392 (12)	0.0019 (11)	−0.0004 (10)	0.0034 (10)
N1	0.0436 (14)	0.0585 (15)	0.0405 (12)	−0.0034 (11)	0.0005 (10)	0.0044 (11)
C5	0.0514 (18)	0.075 (2)	0.0442 (16)	−0.0008 (17)	0.0012 (14)	0.0128 (15)
C1	0.0452 (16)	0.0637 (19)	0.0419 (15)	−0.0024 (14)	0.0024 (13)	0.0021 (14)
C7	0.0448 (16)	0.0516 (17)	0.0499 (16)	−0.0021 (14)	0.0059 (13)	−0.0013 (14)
C2	0.0454 (16)	0.076 (2)	0.0431 (16)	−0.0095 (16)	0.0038 (13)	0.0002 (15)
C9	0.058 (2)	0.078 (2)	0.0525 (19)	0.0033 (18)	−0.0009 (16)	0.0191 (18)
C11	0.0531 (17)	0.060 (2)	0.0454 (15)	−0.0001 (15)	−0.0011 (13)	−0.0006 (14)
C6	0.057 (2)	0.121 (4)	0.062 (2)	−0.025 (2)	−0.0139 (18)	0.015 (2)
C8	0.0425 (15)	0.0540 (18)	0.066 (2)	−0.0001 (14)	0.0062 (14)	0.0155 (16)
N2	0.0690 (19)	0.082 (2)	0.0641 (18)	−0.0192 (17)	−0.0205 (15)	0.0253 (17)
C10	0.070 (2)	0.084 (3)	0.0393 (16)	−0.002 (2)	−0.0054 (15)	−0.0015 (17)
C3	0.056 (2)	0.086 (3)	0.061 (2)	−0.023 (2)	0.0079 (16)	0.0053 (19)
C4	0.059 (2)	0.085 (3)	0.065 (2)	−0.015 (2)	0.0053 (17)	0.024 (2)
N4	0.093 (2)	0.075 (2)	0.0648 (19)	0.0253 (19)	−0.0001 (17)	−0.0170 (16)
C12	0.074 (3)	0.067 (2)	0.102 (3)	0.019 (2)	0.016 (2)	0.019 (2)

Co1—N3	2.034 (2)	C9—H9	0.9300
Co1—N1	2.038 (3)	C11—C10	1.365 (5)
Co1—Cl2	2.2303 (11)	C11—H11	0.9300
Co1—Cl1	2.2635 (11)	C6—H6A	0.9600
N3—C7	1.330 (4)	C6—H6B	0.9600
N3—C11	1.363 (4)	C6—H6C	0.9600
N1—C1	1.350 (4)	C8—C12	1.495 (6)
N1—C5	1.353 (4)	N2—H2A	0.8600
C5—C4	1.349 (5)	N2—H2B	0.8600
C5—H5	0.9300	C10—H10	0.9300
C1—N2	1.352 (4)	C3—C4	1.391 (5)
C1—C2	1.415 (5)	C3—H3	0.9300
C7—N4	1.355 (4)	C4—H4	0.9300
C7—C8	1.424 (4)	N4—H4A	0.8600
C2—C3	1.363 (5)	N4—H4B	0.8600
C2—C6	1.506 (5)	C12—H12A	0.9600
C9—C8	1.358 (5)	C12—H12B	0.9600
C9—C10	1.385 (6)	C12—H12C	0.9600
N3—Co1—N1	106.66 (10)	C2—C6—H6A	109.5
N3—Co1—Cl2	110.23 (8)	C2—C6—H6B	109.5
N1—Co1—Cl2	111.26 (9)	H6A—C6—H6B	109.5
N3—Co1—Cl1	109.94 (8)	C2—C6—H6C	109.5
N1—Co1—Cl1	108.24 (8)	H6A—C6—H6C	109.5
Cl2—Co1—Cl1	110.42 (5)	H6B—C6—H6C	109.5
C7—N3—C11	119.0 (3)	C9—C8—C7	116.1 (3)
C7—N3—Co1	123.1 (2)	C9—C8—C12	123.8 (3)
C11—N3—Co1	117.8 (2)	C7—C8—C12	120.0 (3)
C1—N1—C5	118.5 (3)	C1—N2—H2A	120.0
C1—N1—Co1	123.4 (2)	C1—N2—H2B	120.0
C5—N1—Co1	118.1 (2)	H2A—N2—H2B	120.0
C4—C5—N1	123.2 (3)	C11—C10—C9	118.0 (3)
C4—C5—H5	118.4	C11—C10—H10	121.0
N1—C5—H5	118.4	C9—C10—H10	121.0
N1—C1—N2	117.6 (3)	C2—C3—C4	121.1 (3)
N1—C1—C2	121.4 (3)	C2—C3—H3	119.4
N2—C1—C2	121.0 (3)	C4—C3—H3	119.4
N3—C7—N4	117.0 (3)	C5—C4—C3	118.2 (3)
N3—C7—C8	122.4 (3)	C5—C4—H4	120.9
N4—C7—C8	120.6 (3)	C3—C4—H4	120.9
C3—C2—C1	117.5 (3)	C7—N4—H4A	120.0
C3—C2—C6	122.3 (3)	C7—N4—H4B	120.0
C1—C2—C6	120.2 (3)	H4A—N4—H4B	120.0
C8—C9—C10	122.4 (3)	C8—C12—H12A	109.5
C8—C9—H9	118.8	C8—C12—H12B	109.5
C10—C9—H9	118.8	H12A—C12—H12B	109.5
N3—C11—C10	122.0 (3)	C8—C12—H12C	109.5
N3—C11—H11	119.0	H12A—C12—H12C	109.5
C10—C11—H11	119.0	H12B—C12—H12C	109.5
N1—Co1—N3—C7	69.9 (3)	C11—N3—C7—C8	1.6 (5)
Cl2—Co1—N3—C7	−169.2 (2)	Co1—N3—C7—C8	−178.2 (2)
Cl1—Co1—N3—C7	−47.3 (3)	N1—C1—C2—C3	−0.4 (5)
N1—Co1—N3—C11	−109.9 (2)	N2—C1—C2—C3	−179.4 (4)
Cl2—Co1—N3—C11	11.0 (3)	N1—C1—C2—C6	179.5 (4)
Cl1—Co1—N3—C11	133.0 (2)	N2—C1—C2—C6	0.5 (6)
N3—Co1—N1—C1	−172.4 (3)	C7—N3—C11—C10	−0.4 (5)
Cl2—Co1—N1—C1	67.4 (3)	Co1—N3—C11—C10	179.3 (3)
Cl1—Co1—N1—C1	−54.1 (3)	C10—C9—C8—C7	1.1 (5)
N3—Co1—N1—C5	6.1 (3)	C10—C9—C8—C12	179.1 (4)
Cl2—Co1—N1—C5	−114.1 (2)	N3—C7—C8—C9	−1.9 (5)
Cl1—Co1—N1—C5	124.4 (2)	N4—C7—C8—C9	179.8 (4)
C1—N1—C5—C4	1.6 (5)	N3—C7—C8—C12	−180.0 (3)
Co1—N1—C5—C4	−176.9 (3)	N4—C7—C8—C12	1.8 (5)
C5—N1—C1—N2	178.2 (3)	N3—C11—C10—C9	−0.3 (6)
Co1—N1—C1—N2	−3.3 (4)	C8—C9—C10—C11	−0.1 (6)
C5—N1—C1—C2	−0.9 (5)	C1—C2—C3—C4	1.1 (6)
Co1—N1—C1—C2	177.6 (2)	C6—C2—C3—C4	−178.9 (4)
C11—N3—C7—N4	179.9 (3)	N1—C5—C4—C3	−1.0 (6)
Co1—N3—C7—N4	0.1 (4)	C2—C3—C4—C5	−0.4 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Cl1i	0.86	2.72	3.427 (4)	140
N4—H4A···Cl1	0.86	2.67	3.363 (4)	138
N4—H4B···Cl2ii	0.86	2.68	3.350 (4)	136
C3—H3···Cl2iii	0.93	2.81	3.701 (4)	161

Co1—N3	2.034 (2)
Co1—N1	2.038 (3)
Co1—Cl2	2.2303 (11)
Co1—Cl1	2.2635 (11)

N3—Co1—N1	106.66 (10)
N3—Co1—Cl2	110.23 (8)
N1—Co1—Cl2	111.26 (9)
N3—Co1—Cl1	109.94 (8)
N1—Co1—Cl1	108.24 (8)
Cl2—Co1—Cl1	110.42 (5)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯Cl1i	0.86	2.72	3.427 (4)	140
N4—H4A⋯Cl1	0.86	2.67	3.363 (4)	138
N4—H4B⋯Cl2ii	0.86	2.68	3.350 (4)	136
C3—H3⋯Cl2iii	0.93	2.81	3.701 (4)	161

Symmetry codes: (i) ; (ii) ; (iii) .