Bis(2-amino­pyridinium) tetra­chloro­cobalt(II)

Jebas, S.R.; Balasubramanian, T.; Light, M.E.

doi:10.1107/S1600536806026213

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 8| August 2006| Pages m1818-m1819

https://doi.org/10.1107/S1600536806026213

Bis(2-aminopyridinium) tetrachlorocobalt(II)¹ ¹

Samuel Robinson Jebas,^a Thailampillai Balasubramanian ^b ^* and Mark E Light ^c

^aDepartment of Electronics, St Joseph's College, Tiruchirappalli 620002, India, ^bDepartment of Physics, National Institute of Technology, Tiruchirappalli 620015, India, and ^cSchool of Chemistry, University of Southampton, Highfield, SO17 1BJ, England
^*Correspondence e-mail: bala@nitt.edu

(Received 1 July 2006; accepted 6 July 2006; online 14 July 2006)

In the crystal structure of the title compound, (C₅H₇N₂)₂[CoCl₄], the Co^II ion is coordinated by four chloride ions. The Co atom lies on a crystallographic twofold rotation axis. The structure is stabilized by an extensive network of N—H⋯Cl hydrogen bonds.

Comment

2-Aminopyridine is used in the manufacture of pharmaceuticals, especially antihistaminic drugs (Windholz, 1976 ). As part of our investigation of the reactions of 2-aminopyridine with metals, we report here the crystal structure of the title compound, (I).

The asymmetric unit of (I) contains a 2-aminopyridinium cation and half of a [CoCl₄]²⁻ anion. The Co atom lies on a crystallographic twofold rotation axis. Protonation of atom N1 of the 2-aminopyridine results in the widening of the C2—N1—C6 angle to 122.7 (2)°. This compares with 117.7 (1)° in neutral 2-aminopyridine (Chao et al., 1975 ). The bond lengths and angles in (I) are comparable to those in other 2-aminopyridinium complexes (Bis & Zaworotko, 2005 ; Smith et al., 2000 ; Jebas & Balasubramanian, 2006 ). The pyridinium ring deviates somewhat from planarity, with a maximum deviation from the mean plane of 0.026 (2) Å for atom C6.

The anion exhibits tetrahedral geometry, with the Co^II ion surrounded by four Cl atoms, with Cl—Co—Cl angles ranging from 109.85 (4) to 115.98 (3)°. The mean Co—Cl bond length, 2.27 (7) Å, is close to those observed in similar complexes (Zhang et al., 2005 ).

There are N—H⋯Cl hydrogen-bonding interactions between the cations and the anions (Table 2).

Figure 1
The structure of (I)

, showing the atom-numbering scheme, with 50% probability displacement ellipsoids. The suffix a indicates the symmetry position (−x, y, $[3\over2]$ − z).

Experimental

Solutions of 2-aminopyridine and CoCl₂·2H₂O in water were mixed in a 1:1 molar ratio and heated at 363 K for 2 h. Blue crystals of (I) were obtained by slow evaporation over a period of one week.

Crystal data

(C₅H₇N₂)₂[CoCl₄]
M_r = 390.98
Monoclinic, C 2/c
a = 8.2152 (3) Å
b = 14.0713 (5) Å
c = 13.5731 (5) Å
β = 95.190 (2)°
V = 1562.52 (10) Å³
Z = 4
D_x = 1.662 Mg m⁻³
Mo Kα radiation
μ = 1.77 mm⁻¹
T = 120 (2) K
Block, blue
0.4 × 0.25 × 0.2 mm

Data collection

Bruker–Nonius FR591 rotating-anode diffractometer
φ and ω scans
Absorption correction: multi-scan SADABS (Sheldrick, 2003 ) T_min = 0.595, T_max = 0.701
8864 measured reflections
1801 independent reflections
1488 reflections with I > 2σ(I)
R_int = 0.032
θ_max = 27.5°
3 standard reflections every 60 reflections intensity decay: none

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.119
S = 1.26
1801 reflections
87 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0653P)² + 0.2962P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co—Cl2	2.2724 (7)
Co—Cl1	2.2755 (7)

C2—N1—C6	122.7 (2)
Cl1—Co—Cl1ⁱ	109.37 (4)
Cl2—Co—Cl2ⁱ	109.85 (4)
Cl2—Co—Cl1	115.98 (3)
Symmetry code: (i) $[-x, y, -z+{\script{3\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H2A⋯Cl2ⁱⁱ	0.86	2.42	3.258 (2)	165
N7—H2B⋯Cl1ⁱⁱⁱ	0.86	2.44	3.286 (2)	169
N1—H1⋯Cl1^iv	0.86	2.58	3.275 (2)	139
Symmetry codes: (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[x, -y, z-{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

H atoms were placed in calculated positions, with C—H = 0.93 Å and N—H = 0.86 Å, and refined using a riding model, with U_iso(H) = 1.2U_eq(C,N).

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536806026213/ez2012sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806026213/ez2012Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) & COLLECT; data reduction: DENZO & COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

(I) top

Crystal data top

(C₅H₇N₂)₂[CoCl₄]	F(000) = 788
M_r = 390.98	D_x = 1.662 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 8.2152 (3) Å	θ = 2.9–27.5°
b = 14.0713 (5) Å	µ = 1.77 mm⁻¹
c = 13.5731 (5) Å	T = 120 K
β = 95.190 (2)°	Block, blue
V = 1562.52 (10) Å³	0.4 × 0.25 × 0.2 mm
Z = 4

Data collection top

Bruker–Nonius FR591 rotating anode diffractometer	R_int = 0.032
φ and ω scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan SADABS (Sheldrick, 2003)	h = −10→10
T_min = 0.595, T_max = 0.701	k = −18→17
8864 measured reflections	l = −17→17
1801 independent reflections	3 standard reflections every 60 reflections
1488 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0653P)² + 0.2962P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.119	(Δ/σ)_max < 0.001
S = 1.26	Δρ_max = 0.57 e Å⁻³
1801 reflections	Δρ_min = −0.67 e Å⁻³
87 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C2	0.0862 (3)	0.30455 (18)	0.44634 (18)	0.0176 (6)
H2	−0.0701	0.3131	0.6568	0.028*
C3	−0.0066 (3)	0.27692 (19)	0.5235 (2)	0.0208 (6)
H3	−0.0671	0.221	0.5182	0.025*
C4	−0.0082 (3)	0.33173 (19)	0.6060 (2)	0.0236 (6)
C5	0.0835 (3)	0.41657 (19)	0.6152 (2)	0.0240 (6)
C6	0.1703 (3)	0.44272 (18)	0.5399 (2)	0.0226 (6)
H6	0.2305	0.4987	0.5444	0.027*
N1	0.1702 (3)	0.38769 (15)	0.45715 (17)	0.0200 (5)
H1	0.2256	0.4063	0.4099	0.024*
N7	0.0986 (3)	0.25322 (16)	0.36481 (16)	0.0227 (5)
H2A	0.1588	0.2729	0.3204	0.027*
H2B	0.0463	0.2004	0.3567	0.027*
H1A	0.0841	0.4537	0.672	0.029*
Co	0	0.04217 (3)	0.75	0.01744 (19)
Cl1	−0.10210 (9)	−0.05131 (4)	0.86658 (5)	0.0261 (2)
Cl2	0.21666 (8)	0.13498 (5)	0.80332 (5)	0.0234 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0140 (11)	0.0201 (13)	0.0182 (13)	0.0030 (10)	−0.0014 (10)	0.0034 (10)
C3	0.0179 (13)	0.0225 (14)	0.0217 (13)	−0.0022 (11)	0.0005 (11)	0.0038 (11)
C4	0.0199 (14)	0.0295 (14)	0.0219 (14)	0.0007 (11)	0.0051 (11)	0.0037 (12)
C5	0.0240 (14)	0.0233 (14)	0.0245 (15)	0.0017 (11)	0.0018 (11)	−0.0027 (12)
C6	0.0194 (14)	0.0202 (13)	0.0280 (15)	0.0007 (10)	0.0008 (11)	0.0000 (11)
N1	0.0183 (11)	0.0204 (11)	0.0219 (12)	0.0006 (9)	0.0048 (9)	0.0062 (9)
N7	0.0229 (12)	0.0240 (11)	0.0215 (12)	−0.0012 (9)	0.0043 (9)	0.0016 (10)
Co	0.0164 (3)	0.0163 (3)	0.0202 (3)	0	0.0048 (2)	0
Cl1	0.0254 (4)	0.0240 (4)	0.0306 (4)	0.0031 (3)	0.0120 (3)	0.0083 (3)
Cl2	0.0218 (4)	0.0214 (4)	0.0270 (4)	−0.0053 (2)	0.0022 (3)	0.0001 (3)

Geometric parameters (Å, º) top

C3—C4	1.361 (4)	N1—C2	1.360 (3)
C3—C2	1.405 (4)	N1—H1	0.86
C3—H3	0.93	N7—C2	1.333 (3)
C4—H2	0.93	N7—H2A	0.86
C5—C4	1.411 (4)	N7—H2B	0.86
C5—H1A	0.93	Co—Cl2	2.2724 (7)
C6—C5	1.350 (4)	Co—Cl2ⁱ	2.2724 (7)
C6—N1	1.364 (4)	Co—Cl1	2.2755 (7)
C6—H6	0.93	Co—Cl1ⁱ	2.2755 (7)

C2—N7—H2A	120	C6—N1—H1	118.7
C2—N7—H2B	120	C6—C5—C4	118.5 (3)
H2A—N7—H2B	120	C6—C5—H1A	120.7
C2—N1—C6	122.7 (2)	N1—C6—H6	119.7
C2—N1—H1	118.7	N1—C2—C3	117.5 (2)
C2—C3—H3	119.9	N7—C2—N1	118.7 (2)
C3—C4—C5	120.5 (3)	N7—C2—C3	123.8 (2)
C3—C4—H2	119.8	Cl1—Co—Cl1ⁱ	109.37 (4)
C4—C3—C2	120.2 (2)	Cl2—Co—Cl2ⁱ	109.85 (4)
C4—C3—H3	119.9	Cl2—Co—Cl1	115.98 (3)
C4—C5—H1A	120.7	Cl2ⁱ—Co—Cl1	103.08 (2)
C5—C4—H2	119.8	Cl2—Co—Cl1ⁱ	103.08 (2)
C5—C6—N1	120.6 (3)	Cl2ⁱ—Co—Cl1ⁱ	115.98 (3)
C5—C6—H6	119.7

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H2A···Cl2ⁱⁱ	0.86	2.42	3.258 (2)	165
N7—H2B···Cl1ⁱⁱⁱ	0.86	2.44	3.286 (2)	169
N1—H1···Cl1^iv	0.86	2.58	3.275 (2)	139

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

Footnotes

¹.

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