2-Acetyl-pyridinium 3-amino-2-chloro-pyridinium tetra-chloridocobaltate(II).

In the title complex, (C(5)H(6)ClN(2))(C(7)H(8)NO)[CoCl(4)], the Co(II) ions are tetra-hedrally coordinated. The crystal structure is built from hydrogen-bonded centrosymmetric tetra-mers of tetra-chloridocobaltate(II) dianions and 3-amino-2-chloro-pyridinium cations, additionally strengthened by significant π-π stacking of pyridinium rings [interplanar distance 3.389 (3) Å]. The tetra-mers are linked by N-H⋯Cl hydrogen bonds into chains; the second kind of cations, viz. 2-acetyl-pyridinium, are connected by N-H⋯Cl hydrogen bonds to both sides of the chain. The Co-Cl bond lengths in the dianion correlate with the number of hydrogen bonds accepted by the Cl atom. An intramolecular C-H⋯Cl interaction is also present.

Related literature

There are only few examples of structures involving the ligands present in the title structure. For related structures, see: 2-acetyl­pyridine itself (Laurent, 1966 ▶) and its cation in perchlorate (Husak, 1996 ▶) and in the complex with n class="Species">tetra­phenyl­porphyrin-zinc(II) (Byrn et al., 1993 ▶), and a free base 3-amino-2-chloro­pyridine (Saha et al., 2006 ▶), and the latter as the dihydrogenphosphate (Hamed et al., 2007 ▶) and as the silver complexes (Tong et al., 2002 ▶; Li et al., 2002 ▶). For literature on the Schiff base complexes, see Häner & Hall (1999 ▶); Mukherjee et al. (2005 ▶); Radecka-Paryzek et al. (2005 ▶); Yam & Lo (1999 ▶).

Experimental

Crystal data

(C5H6ClN2)(C7H8n class="Chemical">NO)[CoCl4]

M = 452.44

Triclinic,

a = 7.3255 (5) Å

b = 8.3188 (5) Å

c = 16.2657 (11) Å

α = 89.114 (5)°

β = 82.806 (5)°

γ = 64.145 (6)°

V = 884.13 (10) Å3

Z = 2

Mo Kα radiation

μ = 1.73 mm−1

T = 100 (1) K

0.4 × 0.15 × 0.1 mm

Data collection

Kuma KM-4-CCD four-circle diffractometer

Absorption correction: multi-scan (CrysAlis n class="Disease">RED; Oxford Diffraction, 2007 ▶) T min = 0.616, T max = 0.841

10954 measured reflections

3798 independent reflections

3470 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.065

S = 1.24

3798 reflections

216 parameters

H atoms treated by a mixture of independent and n class="Chemical">constrained refinement

Δρmax = 0.70 e Å−3

Δρmin = −0.36 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis n class="Disease">RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000713/lx2085sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000713/lx2085Isup2.hkl

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

(C5H6ClN2)(C7H8NO)[CoCl4]	Z = 2
Mr = 452.44	F(000) = 454
Triclinic, P1	Dx = 1.700 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3255 (5) Å	Cell parameters from 7316 reflections
b = 8.3188 (5) Å	θ = 3–25°
c = 16.2657 (11) Å	µ = 1.73 mm−1
α = 89.114 (5)°	T = 100 K
β = 82.806 (5)°	Plate, blue
γ = 64.145 (6)°	0.4 × 0.15 × 0.1 mm
V = 884.13 (10) Å3

Kuma KM-4-CCD four-circle diffractometer	3798 independent reflections
Radiation source: fine-focus sealed tube	3470 reflections with I > 2σ(I)
graphite	Rint = 0.019
Detector resolution: 8.1929 pixels mm-1	θmax = 27.0°, θmin = 2.7°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −10→10
Tmin = 0.616, Tmax = 0.841	l = −20→19
10954 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)] = 0.031	Hydrogen site location: difference Fourier map
wR(F2) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.24	w = 1/[σ2(Fo2) + (0.0083P)2 + 1.4737P] where P = (Fo2 + 2Fc2)/3
3798 reflections	(Δ/σ)max < 0.001
216 parameters	Δρmax = 0.70 e Å−3
0 restraints	Δρmin = −0.36 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	0.88393 (5)	0.59259 (4)	0.24288 (2)	0.01220 (9)
Cl1	1.00305 (9)	0.37850 (8)	0.33709 (4)	0.01584 (13)
Cl2	0.70499 (9)	0.51487 (8)	0.15843 (4)	0.01614 (13)
Cl3	1.15608 (9)	0.60998 (8)	0.16588 (4)	0.01751 (13)
Cl4	0.66564 (10)	0.86213 (8)	0.30354 (4)	0.01991 (14)
N1A	0.5900 (3)	1.1877 (3)	−0.05439 (15)	0.0177 (5)
H1A	0.542 (5)	1.229 (4)	−0.098 (2)	0.026 (9)*
C2A	0.7364 (4)	1.0189 (3)	−0.06482 (16)	0.0175 (5)
Cl2A	0.82058 (10)	0.92797 (9)	−0.16337 (4)	0.02218 (15)
C3A	0.8134 (4)	0.9213 (3)	0.00390 (16)	0.0161 (5)
N31A	0.9566 (4)	0.7490 (3)	−0.00534 (16)	0.0236 (5)
H31A	1.011 (5)	0.705 (4)	−0.058 (2)	0.033 (9)*
H31B	1.015 (5)	0.690 (4)	0.042 (2)	0.032 (9)*
C4A	0.7311 (4)	1.0089 (4)	0.08237 (17)	0.0186 (5)
H4A	0.7798	0.9479	0.1307	0.022*
C5A	0.5794 (4)	1.1834 (4)	0.08995 (17)	0.0209 (6)
H5A	0.5254	1.2408	0.1434	0.025*
C6A	0.5065 (4)	1.2742 (4)	0.02109 (18)	0.0198 (6)
H6A	0.4014	1.3933	0.0259	0.024*
N1B	0.7520 (3)	0.5002 (3)	0.51335 (13)	0.0148 (4)
H1B	0.844 (5)	0.447 (4)	0.470 (2)	0.032 (9)*
C2B	0.7401 (4)	0.4099 (3)	0.58207 (15)	0.0148 (5)
C21B	0.9013 (4)	0.2182 (3)	0.57886 (16)	0.0162 (5)
O21B	1.0417 (3)	0.1707 (3)	0.52259 (12)	0.0222 (4)
C22B	0.8761 (4)	0.1020 (4)	0.64563 (17)	0.0210 (6)
H22A	0.9764	−0.0222	0.6320	0.029*
H22B	0.7376	0.1102	0.6503	0.029*
H22C	0.8978	0.1416	0.6985	0.029*
C3B	0.5901 (4)	0.4969 (4)	0.64742 (16)	0.0176 (5)
H3B	0.5773	0.4356	0.6959	0.021*
C4B	0.4563 (4)	0.6782 (4)	0.64097 (17)	0.0201 (6)
H4B	0.3530	0.7407	0.6857	0.024*
C5B	0.4745 (4)	0.7655 (4)	0.56984 (17)	0.0198 (6)
H5B	0.3839	0.8878	0.5653	0.024*
C6B	0.6263 (4)	0.6729 (3)	0.50503 (17)	0.0179 (5)
H6B	0.6410	0.7308	0.4556	0.022*

	U11	U22	U33	U12	U13	U23
Co1	0.01261 (16)	0.01326 (16)	0.01084 (17)	−0.00584 (13)	−0.00127 (12)	0.00103 (13)
Cl1	0.0180 (3)	0.0160 (3)	0.0126 (3)	−0.0066 (2)	−0.0024 (2)	0.0034 (2)
Cl2	0.0149 (3)	0.0185 (3)	0.0152 (3)	−0.0069 (2)	−0.0039 (2)	−0.0007 (2)
Cl3	0.0151 (3)	0.0224 (3)	0.0162 (3)	−0.0097 (2)	−0.0007 (2)	0.0032 (2)
Cl4	0.0213 (3)	0.0151 (3)	0.0190 (3)	−0.0047 (2)	0.0003 (2)	−0.0023 (2)
N1A	0.0163 (11)	0.0158 (11)	0.0217 (12)	−0.0073 (9)	−0.0041 (9)	0.0036 (9)
C2A	0.0176 (12)	0.0193 (13)	0.0167 (13)	−0.0099 (10)	0.0010 (10)	0.0011 (10)
Cl2A	0.0260 (3)	0.0232 (3)	0.0140 (3)	−0.0083 (3)	−0.0004 (2)	0.0017 (2)
C3A	0.0156 (12)	0.0185 (13)	0.0174 (13)	−0.0105 (10)	−0.0020 (10)	0.0037 (10)
N31A	0.0246 (12)	0.0212 (12)	0.0157 (12)	−0.0018 (10)	−0.0010 (10)	0.0022 (10)
C4A	0.0201 (13)	0.0201 (13)	0.0172 (13)	−0.0106 (11)	−0.0019 (10)	0.0023 (11)
C5A	0.0221 (13)	0.0223 (14)	0.0211 (14)	−0.0132 (11)	0.0012 (11)	−0.0038 (11)
C6A	0.0190 (13)	0.0161 (13)	0.0300 (15)	−0.0122 (11)	−0.0072 (11)	0.0051 (11)
N1B	0.0162 (10)	0.0166 (11)	0.0122 (10)	−0.0077 (9)	−0.0016 (8)	−0.0002 (9)
C2B	0.0160 (12)	0.0197 (13)	0.0131 (12)	−0.0114 (10)	−0.0038 (10)	0.0004 (10)
C21B	0.0184 (12)	0.0193 (13)	0.0140 (13)	−0.0102 (10)	−0.0051 (10)	0.0014 (10)
O21B	0.0212 (10)	0.0225 (10)	0.0173 (10)	−0.0051 (8)	−0.0007 (8)	0.0025 (8)
C22B	0.0244 (14)	0.0222 (14)	0.0183 (13)	−0.0117 (11)	−0.0048 (11)	0.0063 (11)
C3B	0.0177 (12)	0.0256 (14)	0.0138 (12)	−0.0133 (11)	−0.0021 (10)	0.0009 (11)
C4B	0.0167 (12)	0.0237 (14)	0.0195 (14)	−0.0088 (11)	0.0001 (10)	−0.0066 (11)
C5B	0.0196 (13)	0.0175 (13)	0.0231 (14)	−0.0083 (11)	−0.0046 (11)	−0.0021 (11)
C6B	0.0221 (13)	0.0176 (13)	0.0175 (13)	−0.0112 (11)	−0.0056 (10)	0.0039 (10)

Co1—Cl4	2.2593 (7)	N1B—C6B	1.342 (3)
Co1—Cl1	2.2751 (7)	N1B—C2B	1.352 (3)
Co1—Cl3	2.2771 (7)	N1B—H1B	0.88 (3)
Co1—Cl2	2.2893 (7)	C2B—C3B	1.378 (4)
N1A—C2A	1.341 (3)	C2B—C21B	1.512 (4)
N1A—C6A	1.362 (4)	C21B—O21B	1.214 (3)
N1A—H1A	0.84 (3)	C21B—C22B	1.490 (4)
C2A—C3A	1.399 (4)	C22B—H22A	0.9800
C2A—Cl2A	1.705 (3)	C22B—H22B	0.9800
C3A—N31A	1.354 (3)	C22B—H22C	0.9800
C3A—C4A	1.406 (4)	C3B—C4B	1.406 (4)
N31A—H31A	0.90 (4)	C3B—H3B	0.9500
N31A—H31B	0.96 (4)	C4B—C5B	1.379 (4)
C4A—C5A	1.386 (4)	C4B—H4B	0.9500
C4A—H4A	0.9500	C5B—C6B	1.388 (4)
C5A—C6A	1.372 (4)	C5B—H5B	0.9500
C5A—H5A	0.9500	C6B—H6B	0.9500
C6A—H6A	0.9500
Cl4—Co1—Cl1	112.35 (3)	C6B—N1B—C2B	123.6 (2)
Cl4—Co1—Cl3	110.42 (3)	C6B—N1B—H1B	116 (2)
Cl1—Co1—Cl3	108.54 (3)	C2B—N1B—H1B	121 (2)
Cl4—Co1—Cl2	106.68 (3)	N1B—C2B—C3B	119.1 (2)
Cl1—Co1—Cl2	109.10 (3)	N1B—C2B—C21B	114.6 (2)
Cl3—Co1—Cl2	109.72 (3)	C3B—C2B—C21B	126.3 (2)
C2A—N1A—C6A	123.7 (2)	O21B—C21B—C22B	124.9 (2)
C2A—N1A—H1A	113 (2)	O21B—C21B—C2B	117.8 (2)
C6A—N1A—H1A	123 (2)	C22B—C21B—C2B	117.3 (2)
N1A—C2A—C3A	120.3 (2)	C21B—C22B—H22A	109.5
N1A—C2A—Cl2A	118.0 (2)	C21B—C22B—H22B	109.5
C3A—C2A—Cl2A	121.7 (2)	H22A—C22B—H22B	109.5
N31A—C3A—C2A	121.0 (2)	C21B—C22B—H22C	109.5
N31A—C3A—C4A	122.0 (2)	H22A—C22B—H22C	109.5
C2A—C3A—C4A	116.9 (2)	H22B—C22B—H22C	109.5
C3A—N31A—H31A	117 (2)	C2B—C3B—C4B	118.8 (2)
C3A—N31A—H31B	119 (2)	C2B—C3B—H3B	120.6
H31A—N31A—H31B	123 (3)	C4B—C3B—H3B	120.6
C5A—C4A—C3A	120.7 (2)	C5B—C4B—C3B	120.2 (2)
C5A—C4A—H4A	119.7	C5B—C4B—H4B	119.9
C3A—C4A—H4A	119.7	C3B—C4B—H4B	119.9
C6A—C5A—C4A	120.7 (3)	C4B—C5B—C6B	119.4 (2)
C6A—C5A—H5A	119.6	C4B—C5B—H5B	120.3
C4A—C5A—H5A	119.6	C6B—C5B—H5B	120.3
N1A—C6A—C5A	117.7 (2)	N1B—C6B—C5B	118.9 (2)
N1A—C6A—H6A	121.2	N1B—C6B—H6B	120.5
C5A—C6A—H6A	121.2	C5B—C6B—H6B	120.5
C6A—N1A—C2A—C3A	−0.5 (4)	C6B—N1B—C2B—C21B	−178.2 (2)
C6A—N1A—C2A—Cl2A	178.5 (2)	N1B—C2B—C21B—O21B	10.7 (3)
N1A—C2A—C3A—N31A	177.9 (2)	C3B—C2B—C21B—O21B	−168.3 (2)
Cl2A—C2A—C3A—N31A	−1.0 (4)	N1B—C2B—C21B—C22B	−169.7 (2)
N1A—C2A—C3A—C4A	−0.3 (4)	C3B—C2B—C21B—C22B	11.3 (4)
Cl2A—C2A—C3A—C4A	−179.19 (19)	N1B—C2B—C3B—C4B	−1.1 (4)
N31A—C3A—C4A—C5A	−177.7 (3)	C21B—C2B—C3B—C4B	177.9 (2)
C2A—C3A—C4A—C5A	0.5 (4)	C2B—C3B—C4B—C5B	0.8 (4)
C3A—C4A—C5A—C6A	0.0 (4)	C3B—C4B—C5B—C6B	−0.2 (4)
C2A—N1A—C6A—C5A	1.0 (4)	C2B—N1B—C6B—C5B	−0.3 (4)
C4A—C5A—C6A—N1A	−0.8 (4)	C4B—C5B—C6B—N1B	−0.1 (4)
C6B—N1B—C2B—C3B	0.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1B—H1B···Cl1	0.88 (3)	2.28 (4)	3.126 (2)	161 (3)
N1A—H1A···Cl2i	0.84 (3)	2.41 (3)	3.127 (2)	145 (3)
N31A—H31A···Cl2ii	0.90 (4)	2.51 (4)	3.323 (3)	151 (3)
N31A—H31B···Cl3	0.96 (4)	2.33 (4)	3.267 (3)	167 (3)
C6B—H6B···Cl4	0.95	2.71	3.647 (3)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1B—H1B⋯Cl1	0.88 (3)	2.28 (4)	3.126 (2)	161 (3)
N1A—H1A⋯Cl2i	0.84 (3)	2.41 (3)	3.127 (2)	145 (3)
N31A—H31A⋯Cl2ii	0.90 (4)	2.51 (4)	3.323 (3)	151 (3)
N31A—H31B⋯Cl3	0.96 (4)	2.33 (4)	3.267 (3)	167 (3)
C6B—H6B⋯Cl4	0.95	2.71	3.647 (3)	171

Symmetry codes: (i) ; (ii) .