Bis(3-methyl­pyridinium) tetra­chlorido­cuprate(II)

Sengottvelan, N.; Lee, Y.-S.; Lim, H.-S.; Kim, Y.-I.; Kang, S.K.

doi:10.1107/S1600536809007818

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page m384

doi:10.1107/S1600536809007818

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Bis(3-methylpyridinium) tetrachloridocuprate(II)

Nallathambi Sengottvelan,^a You-Soon Lee,^b Hyun-Soo Lim,^a Young-Inn Kim ^a and Sung Kwon Kang ^b ^*

^aDepartment of Chemistry Education and Center for Plastic Information Systems, Pusan National University, Pusan 609-735, Republic of Korea, and ^bDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
^*Correspondence e-mail: skkang@cnu.ac.kr

(Received 19 February 2009; accepted 4 March 2009; online 11 March 2009)

The title compound, (C₆H₈N)₂[CuCl₄], is composed of two 3-methylpyridinium cation and one tetrachloridocuprate(II) anion. The geometry around the copper(II) ion is that of a distorted tetrahedron. In the crystal structure, the anions and cations are linked by three different N—H⋯Cl hydrogen bonds. In addition, the crystal structure exhibits aromatic π–π interactions between the pyridinium rings of two discrete units [centroid–centroid distance = 3.704 (2) Å].

Related literature

For general background on the influence of crystal-packing forces on the geometry of the tetrahalogenidocuprate(II) species, see: Schneider et al. (2007 ); Parent et al. (2007 ); Haddad et al. (2006 ); Marzotto et al. (2001 ); Choi et al. (2002 ); Awwadi et al. (2007 ). For the electronic spectrum in DMF solution, see Lee et al. (2002 ). For related literature, see: Lee et al. (2008 ).

Experimental

Crystal data

(C₆H₈N)₂[CuCl₄]
M_r = 393.61
Monoclinic, P 2₁ /n
a = 9.0438 (3) Å
b = 13.0530 (4) Å
c = 13.7391 (5) Å
β = 103.541 (2)°
V = 1576.80 (9) Å³
Z = 4
Mo Kα radiation
μ = 2.05 mm⁻¹
T = 123 K
0.25 × 0.24 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.603, T_max = 0.62
16009 measured reflections
3899 independent reflections
3429 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.062
S = 1.04
3899 reflections
182 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.80 (2)	2.44 (2)	3.136 (2)	146 (2)
N2—H2⋯Cl1	0.81 (2)	2.66 (2)	3.270 (2)	134 (2)
N2—H2⋯Cl2	0.81 (2)	2.50 (2)	3.196 (2)	145 (2)

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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 ) and DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809007818/lx2094sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007818/lx2094Isup2.hkl

checkCIF report

Comment top

The four–coordinated tetrahalocuprate (II) ions, [CuCl₄]^2- possess a variety of geometries from square planar to near tetrahedral symmetry, and the geometry of tetrahalocuprate (II) species is influenced by the crystal-packing forces resulted from the size and shape of counter cations (Schneider et al., 2007; Parent et al., 2007), hydrogen bonding to cations (Haddad et al., 2006; Marzotto et al., 2001; Choi et al., 2002), and halide-halide interactions in solid (Awwadi et al., 2007). Herein, we report the crystal structure of the title compound, bis(3-methylpyridinium)tetrachloridocuprate(II) (Fig. 1).

The [CuCl₄]^2- anion in the title compound is distorted to be approximately D_2d, somewhat distorted from tetrahedral as a result of hydrogen bonding interactions with two 3-methylpyridinium cations. The range of Cl—Cu—Cl angles is 99.28 (2)–137.32 (2)°, which is far away from tetrahedral geometry. The Cl1 atom of [CuCl₄]^2- anion forms a three-center hydrogen bond with two protonated pyridinium N atoms (Fig. 2 & Table 1). On the other hand, the Cl2 atom forms a common two–center hydrogen bond with nicotinium cations. As shown in Fig. 2, there are weak π—π interactions between pyridinium rings of two discrete units. The Cg1···Cg2ⁱ distance is 3.704 (2) Å (Cg1 and Cg2 are the centroids of the C1–C5/N1 pyridinium ring and the C7–C11/N2 pyridinium ring, respectively; symmetry code as in Fig.2 & Table 1).

Related literature top

For general background on the influence of crystal-packing forces on the geometry of the tetrahalocuprate(II) species, see: Schneider et al. (2007); Parent et al. (2007); Haddad et al. (2006); Marzotto et al. (2001); Choi et al. (2002); Awwadi et al. (2007). For the electronic spectrum in DMF solution, see Lee et al. (2002). For related literature, see: Lee et al. (2008).

Experimental top

A total 1 mmol (0.093 g) of 3-methylpyridine and 1 mmol (0.170 g) of CuCl₂.2H₂O were dissolved in 10 mL of ethanol acidified with 5 mL of concentrated HCl. The mixture solution was heated and refluxed for 1 hr. The single crystals were obtained by slow evaporation in ethanol solution for 7 days. Elemental analysis was performed at the Korean Basic Science Center. Anal. (%) calculated for C₁₂H₁₆Cl₄CuN₂: C, 36.62; H, 4.10; N, 7.12; found: C, 37.23; H, 4.33; N, 7.17. Spectroscopic analysis: The electronic spectrum in DMF solution: ν₁; 874 nm (ε = 20M^-1cm^-1), ν₂; 1038 (71), ν₃; 1326 (62). The peak was analyzed into three peaks based on the distorted tetrahedral structure around copper(II) metal ion (Lee et al., 2002). These bands are tentatively assigned to d_x²_-_y²(²B₂) —> d_xz, d_yz(²E), d_x²_-_y² —> d_xy(²B₁), d_x²_-_y² —> d_z²(²A₁), respectively.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. N—H···Cl and π—π interactions (dotted lines) in the title compound. Cg denotes the ring centroid. [Symmetry code: (i) -x+1, -y+1, -z+1]

Bis(3-methylpyridinium) tetrachloridocuprate(II) top

Crystal data top

(C₆H₈N)₂[CuCl₄]	F(000) = 796
M_r = 393.61	D_x = 1.658 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7316 reflections
a = 9.0438 (3) Å	θ = 2.8–28.3°
b = 13.0530 (4) Å	µ = 2.05 mm⁻¹
c = 13.7391 (5) Å	T = 123 K
β = 103.541 (2)°	Block, orange
V = 1576.80 (9) Å³	0.25 × 0.24 × 0.23 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3429 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.036
Absorption correction: multi-scan (SADABS; Bruker, 2002)	θ_max = 28.3°, θ_min = 2.2°
T_min = 0.603, T_max = 0.62	h = −11→12
16009 measured reflections	k = −17→17
3899 independent reflections	l = −17→18

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.024	w = 1/[σ²(F_o²) + (0.0228P)² + 0.7012P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.062	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.36 e Å⁻³
3899 reflections	Δρ_min = −0.35 e Å⁻³
182 parameters

Crystal data top

(C₆H₈N)₂[CuCl₄]	V = 1576.80 (9) Å³
M_r = 393.61	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.0438 (3) Å	µ = 2.05 mm⁻¹
b = 13.0530 (4) Å	T = 123 K
c = 13.7391 (5) Å	0.25 × 0.24 × 0.23 mm
β = 103.541 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3899 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	3429 reflections with I > 2σ(I)
T_min = 0.603, T_max = 0.62	R_int = 0.036
16009 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.062	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.36 e Å⁻³
3899 reflections	Δρ_min = −0.35 e Å⁻³
182 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Cu	0.55797 (2)	0.545725 (15)	0.703075 (14)	0.01588 (6)
Cl1	0.65531 (4)	0.43858 (3)	0.60513 (3)	0.02068 (9)
Cl2	0.75323 (4)	0.65743 (3)	0.73115 (3)	0.02099 (9)
Cl3	0.36357 (4)	0.65699 (3)	0.68081 (3)	0.01929 (9)
Cl4	0.46771 (5)	0.42349 (3)	0.78922 (3)	0.02114 (9)
N1	0.44305 (15)	0.24760 (11)	0.59904 (10)	0.0181 (3)
H1	0.486 (2)	0.2980 (17)	0.6238 (15)	0.031 (6)*
C1	0.46256 (17)	0.21958 (12)	0.50880 (11)	0.0172 (3)
H1A	0.5226	0.2594	0.4771	0.021*
C2	0.39398 (17)	0.13197 (12)	0.46271 (11)	0.0175 (3)
C3	0.30426 (18)	0.07611 (13)	0.51325 (12)	0.0207 (3)
H3	0.2563	0.0168	0.4843	0.025*
C4	0.28506 (18)	0.10739 (13)	0.60617 (12)	0.0214 (3)
H4	0.2243	0.0698	0.6392	0.026*
C5	0.35733 (18)	0.19485 (13)	0.64851 (12)	0.0198 (3)
H5	0.3467	0.217	0.7108	0.024*
C6	0.4135 (2)	0.10069 (14)	0.36131 (12)	0.0244 (4)
H6A	0.3316	0.1282	0.3106	0.037*
H6B	0.413	0.0273	0.3567	0.037*
H6C	0.5086	0.1266	0.3519	0.037*
N2	0.85716 (15)	0.61542 (11)	0.52789 (10)	0.0188 (3)
H2	0.820 (3)	0.5984 (19)	0.5735 (17)	0.044 (7)*
C7	0.94635 (17)	0.69916 (13)	0.54089 (11)	0.0182 (3)
H7	0.9581	0.7377	0.5992	0.022*
C8	1.02028 (17)	0.72809 (12)	0.46826 (11)	0.0178 (3)
C9	0.99762 (18)	0.66842 (13)	0.38198 (12)	0.0197 (3)
H9	1.0457	0.6861	0.3315	0.024*
C10	0.90430 (19)	0.58299 (13)	0.37064 (12)	0.0223 (3)
H10	0.8895	0.5436	0.3128	0.027*
C11	0.83398 (19)	0.55690 (13)	0.44509 (12)	0.0214 (3)
H11	0.7712	0.4997	0.4386	0.026*
C12	1.1178 (2)	0.82208 (13)	0.48099 (13)	0.0253 (4)
H12A	1.0547	0.8815	0.4636	0.038*
H12B	1.1875	0.8177	0.4381	0.038*
H12C	1.1738	0.8273	0.5494	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.01598 (11)	0.01411 (10)	0.01823 (11)	−0.00095 (7)	0.00540 (8)	−0.00009 (7)
Cl1	0.0225 (2)	0.01704 (18)	0.0254 (2)	−0.00297 (15)	0.01148 (16)	−0.00423 (14)
Cl2	0.02040 (19)	0.02015 (19)	0.02291 (19)	−0.00627 (15)	0.00604 (15)	−0.00435 (15)
Cl3	0.02013 (19)	0.01763 (18)	0.02150 (19)	0.00232 (14)	0.00768 (15)	0.00053 (14)
Cl4	0.0242 (2)	0.01839 (19)	0.02248 (19)	−0.00029 (15)	0.00882 (15)	0.00461 (14)
N1	0.0172 (6)	0.0156 (7)	0.0202 (7)	−0.0019 (5)	0.0016 (5)	−0.0005 (5)
C1	0.0163 (7)	0.0172 (7)	0.0186 (7)	0.0000 (6)	0.0048 (6)	0.0028 (6)
C2	0.0168 (7)	0.0177 (7)	0.0174 (7)	0.0020 (6)	0.0028 (6)	0.0017 (6)
C3	0.0197 (8)	0.0171 (8)	0.0243 (8)	−0.0027 (6)	0.0029 (6)	0.0012 (6)
C4	0.0189 (8)	0.0215 (8)	0.0245 (8)	−0.0009 (6)	0.0066 (6)	0.0061 (7)
C5	0.0184 (7)	0.0233 (8)	0.0177 (7)	0.0030 (6)	0.0042 (6)	0.0025 (6)
C6	0.0300 (9)	0.0238 (9)	0.0192 (8)	0.0011 (7)	0.0053 (7)	−0.0024 (7)
N2	0.0180 (7)	0.0204 (7)	0.0185 (7)	−0.0002 (5)	0.0056 (5)	0.0027 (5)
C7	0.0186 (8)	0.0183 (8)	0.0173 (7)	0.0003 (6)	0.0034 (6)	−0.0004 (6)
C8	0.0157 (7)	0.0185 (8)	0.0191 (7)	0.0030 (6)	0.0039 (6)	0.0029 (6)
C9	0.0206 (8)	0.0228 (8)	0.0162 (7)	0.0069 (6)	0.0056 (6)	0.0042 (6)
C10	0.0254 (8)	0.0225 (8)	0.0172 (7)	0.0039 (7)	0.0015 (6)	−0.0035 (6)
C11	0.0196 (8)	0.0186 (8)	0.0238 (8)	−0.0006 (6)	0.0005 (6)	0.0001 (6)
C12	0.0263 (9)	0.0237 (9)	0.0272 (9)	−0.0058 (7)	0.0089 (7)	0.0020 (7)

Geometric parameters (Å, º) top

Cu—Cl3	2.2455 (4)	C6—H6B	0.96
Cu—Cl4	2.2506 (4)	C6—H6C	0.96
Cu—Cl2	2.2526 (4)	N2—C7	1.345 (2)
Cu—Cl1	2.2576 (4)	N2—C11	1.345 (2)
N1—C5	1.336 (2)	N2—H2	0.81 (2)
N1—C1	1.343 (2)	C7—C8	1.378 (2)
N1—H1	0.80 (2)	C7—H7	0.93
C1—C2	1.382 (2)	C8—C9	1.393 (2)
C1—H1A	0.93	C8—C12	1.497 (2)
C2—C3	1.391 (2)	C9—C10	1.385 (2)
C2—C6	1.501 (2)	C9—H9	0.93
C3—C4	1.389 (2)	C10—C11	1.368 (2)
C3—H3	0.93	C10—H10	0.93
C4—C5	1.375 (2)	C11—H11	0.93
C4—H4	0.93	C12—H12A	0.96
C5—H5	0.93	C12—H12B	0.96
C6—H6A	0.96	C12—H12C	0.96

Cl3—Cu—Cl4	99.283 (16)	C2—C6—H6C	109.5
Cl3—Cu—Cl2	99.327 (17)	H6A—C6—H6C	109.5
Cl4—Cu—Cl2	137.322 (16)	H6B—C6—H6C	109.5
Cl3—Cu—Cl1	136.189 (16)	C7—N2—C11	122.92 (15)
Cl4—Cu—Cl1	96.568 (17)	C7—N2—H2	117.7 (17)
Cl2—Cu—Cl1	95.946 (16)	C11—N2—H2	119.3 (17)
C5—N1—C1	123.14 (15)	N2—C7—C8	120.27 (15)
C5—N1—H1	119.2 (15)	N2—C7—H7	119.9
C1—N1—H1	117.7 (15)	C8—C7—H7	119.9
N1—C1—C2	120.43 (15)	C7—C8—C9	117.62 (15)
N1—C1—H1A	119.8	C7—C8—C12	120.84 (15)
C2—C1—H1A	119.8	C9—C8—C12	121.53 (15)
C1—C2—C3	117.17 (15)	C10—C9—C8	120.68 (15)
C1—C2—C6	120.83 (15)	C10—C9—H9	119.7
C3—C2—C6	121.98 (15)	C8—C9—H9	119.7
C4—C3—C2	121.16 (15)	C11—C10—C9	119.60 (15)
C4—C3—H3	119.4	C11—C10—H10	120.2
C2—C3—H3	119.4	C9—C10—H10	120.2
C5—C4—C3	118.91 (16)	N2—C11—C10	118.90 (16)
C5—C4—H4	120.5	N2—C11—H11	120.5
C3—C4—H4	120.5	C10—C11—H11	120.5
N1—C5—C4	119.19 (16)	C8—C12—H12A	109.5
N1—C5—H5	120.4	C8—C12—H12B	109.5
C4—C5—H5	120.4	H12A—C12—H12B	109.5
C2—C6—H6A	109.5	C8—C12—H12C	109.5
C2—C6—H6B	109.5	H12A—C12—H12C	109.5
H6A—C6—H6B	109.5	H12B—C12—H12C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.80 (2)	2.44 (2)	3.136 (2)	146 (2)
N2—H2···Cl1	0.81 (2)	2.66 (2)	3.270 (2)	134 (2)
N2—H2···Cl2	0.81 (2)	2.50 (2)	3.196 (2)	145 (2)

Experimental details

Crystal data
Chemical formula	(C₆H₈N)₂[CuCl₄]
M_r	393.61
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	123
a, b, c (Å)	9.0438 (3), 13.0530 (4), 13.7391 (5)
β (°)	103.541 (2)
V (Å³)	1576.80 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.05
Crystal size (mm)	0.25 × 0.24 × 0.23

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.603, 0.62
No. of measured, independent and observed [I > 2σ(I)] reflections	16009, 3899, 3429
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.062, 1.04
No. of reflections	3899
No. of parameters	182
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.35

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1998), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.80 (2)	2.44 (2)	3.136 (2)	146 (2)
N2—H2···Cl1	0.81 (2)	2.66 (2)	3.270 (2)	134 (2)
N2—H2···Cl2	0.81 (2)	2.50 (2)	3.196 (2)	145 (2)

Acknowledgements

This study was supported financially by the Research Fund of Chungnam National University in 2008.

References

Awwadi, F. F., Willett, R. D. & Twamly, B. (2007). Cryst. Growth Des. 7, 624–632. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choi, S.-N., Lee, Y.-M., Lee, H.-W., Kang, S. K. & Kim, Y.-I. (2002). Acta Cryst. E58, m583–m585. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Haddad, S. F., Aidamen, M. A. & Willett, R. D. (2006). Inorg. Chim. Acta, 359, 424–432. Web of Science CrossRef CAS Google Scholar
Lee, Y. M., Kim, Y. K., Jung, H. C., Kim, Y. I. & Choi, S. N. (2002). Bull. Korean Chem. Soc. 23, 404–412. CAS Google Scholar
Lee, H. W., Sengottuvelan, N., Seo, H. J., Choi, J. S., Kang, S. K. & Kim, Y. I. (2008). Bull. Korean Chem. Soc. 29, 1711–1716. CAS Google Scholar
Marzotto, A., Clemente, D. A., Benetollo, F. & Valle, G. (2001). Polyhedron, 20, 171–177. Web of Science CSD CrossRef CAS Google Scholar
Parent, A. R., Landee, C. P. & Turnbull, M. M. (2007). Inorg. Chim. Acta, 360, 1943–1953. Web of Science CSD CrossRef CAS Google Scholar
Schneider, T. T., Landee, C. P., Turnbull, M. M., Awwadi, F. F. & Twamley, B. (2007). Polyhedron, 26, 1849–1858. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar