Bis(2-amino-6-methyl-pyridinium) tetra-chloridocuprate(II).

The title compound, (C(6)H(9)N(2))(2)[CuCl(4)], contains a distorted tetra-hedral [CuCl(4)](2-) anion and two protonated amino-pyridinium cations. The geometries of the protonated amino-pyridinium cations reveal amine-imine tautomerism. The crystal packing is influenced by N-H⋯Cl and C-H⋯Cl hydrogen bonds and π-π stacking inter-actions [centroid-centroid distances = 3.635 (4) and 3.642 (4)°].

Related literature

For a series of compounds with formula A2[MX 4], where A is an organic cation, usually a protonted base, M is a divalent transition metal ion and X is a halide (Cl, Br), see: Hammar et al. (1997 ▶). For complexes in which A is a protonated alkyl­amine, see: Zhou & Drumheller (1990 ▶), a heterocycle such as pyridine, see: Place & Willett (1987 ▶), 2-amino­pyrimidine, see: Zanchini & Willett (1990 ▶) and 2-amino-3-methyl­pridine, see: Coffey et al. (2000 ▶). For bond lengths and angles in related structures, see: Antolini et al. (1988 ▶); Zhang et al. (2005 ▶); Jin, Shun et al. (2005 ▶); Feng et al. (2007 ▶); Nahringbauer & Kvick (1977 ▶). For other 2-amino­pyridinium structures, see: Luque et al. (1997 ▶); Jin et al. (2000 ▶, 2001 ▶); Jin, Tu et al. (2005 ▶). For studies on the tautomeric forms of 2-aminopyridine systems, see: Inuzuka & Fujimoto (1986 ▶, 1990 ▶); Ishikawa et al. (2002 ▶).

Experimental

Crystal data

(C6H9N2)2[CuCl4]

M = 423.65

Triclinic,

a = 7.7466 (17) Å

b = 8.0372 (18) Å

c = 14.969 (3) Å

α = 78.922 (4)°

β = 82.154 (4)°

γ = 89.911 (4)°

V = 905.8 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.79 mm−1

T = 273 K

0.35 × 0.34 × 0.30 mm

Data collection

Bruker SMART APEX area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.549, T max = 0.578

4783 measured reflections

3161 independent reflections

2874 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.090

S = 1.05

3161 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.55 e Å−3

Δρmin = −0.33 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904923X/kp2235sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680904923X/kp2235Isup2.hkl

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

(C6H9N2)2[CuCl4]	Z = 2
Mr = 423.65	F(000) = 430.0
Triclinic, P1	Dx = 1.553 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7466 (17) Å	Cell parameters from 2451 reflections
b = 8.0372 (18) Å	θ = 2.2–24.3°
c = 14.969 (3) Å	µ = 1.79 mm−1
α = 78.922 (4)°	T = 273 K
β = 82.154 (4)°	Prism, blue
γ = 89.911 (4)°	0.35 × 0.34 × 0.30 mm
V = 905.8 (3) Å3

Bruker SMART APEX area-detector diffractometer	3206 independent reflections
Radiation source: fine-focus sealed tube	3161 reflections with I > 2σ(I)
graphite	Rint = 0.013
φ and ω scan	θmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→9
Tmin = 0.549, Tmax = 0.578	k = −9→9
4783 measured reflections	l = −12→17

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0481P)2 + 0.406P] where P = (Fo2 + 2Fc2)/3
3161 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.55 e Å−3
0 restraints	Δρmin = −0.33 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
cu1	0.18139 (4)	0.80739 (4)	0.75385 (2)	0.04615 (13)
cl4	0.31507 (11)	0.56448 (9)	0.80270 (5)	0.0630 (2)
cl1	0.04761 (10)	0.98881 (10)	0.83451 (6)	0.0677 (2)
cl3	0.41383 (10)	0.96162 (10)	0.68092 (7)	0.0757 (3)
cl2	−0.04646 (10)	0.69927 (13)	0.70434 (6)	0.0734 (3)
n4	0.4134 (3)	0.7120 (3)	0.97401 (16)	0.0498 (5)
h4	0.3725	0.6715	0.9318	0.060*
c8	0.6468 (4)	0.8324 (4)	1.0262 (2)	0.0575 (7)
h8	0.7613	0.8733	1.0172	0.069*
c1	0.2333 (4)	0.4070 (3)	0.56633 (19)	0.0506 (6)
n2	0.1895 (3)	0.5691 (3)	0.54343 (16)	0.0506 (5)
h2	0.1328	0.6149	0.5855	0.061*
c11	0.3066 (4)	0.7100 (4)	1.0545 (2)	0.0532 (7)
c9	0.5450 (5)	0.8298 (4)	1.1068 (2)	0.0646 (8)
h9	0.5906	0.8679	1.1538	0.077*
c10	0.3717 (4)	0.7707 (4)	1.1212 (2)	0.0641 (8)
h10	0.3017	0.7733	1.1766	0.077*
c5	0.2289 (4)	0.6664 (4)	0.4578 (2)	0.0574 (7)
n1	0.1881 (4)	0.3267 (3)	0.65263 (19)	0.0753 (8)
h1a	0.1321	0.3790	0.6922	0.090*
h1b	0.2148	0.2224	0.6690	0.090*
c2	0.3220 (4)	0.3304 (4)	0.4975 (2)	0.0610 (8)
h2a	0.3539	0.2177	0.5104	0.073*
c3	0.3598 (4)	0.4236 (5)	0.4123 (2)	0.0720 (10)
h3	0.4166	0.3735	0.3658	0.086*
c12	0.1255 (4)	0.6423 (5)	1.0599 (3)	0.0741 (9)
h12a	0.1120	0.6067	1.0035	0.111*
h12b	0.0440	0.7294	1.0696	0.111*
h12c	0.1038	0.5474	1.1102	0.111*
n3	0.6670 (4)	0.7728 (4)	0.8737 (2)	0.0784 (8)
h3a	0.6183	0.7342	0.8333	0.094*
h3b	0.7728	0.8112	0.8607	0.094*
c4	0.3162 (4)	0.5927 (5)	0.3920 (2)	0.0704 (9)
h4a	0.3471	0.6554	0.3329	0.084*
c6	0.1734 (5)	0.8456 (4)	0.4464 (3)	0.0841 (11)
h6a	0.1139	0.8658	0.5037	0.126*
h6b	0.0965	0.8668	0.4005	0.126*
h6c	0.2741	0.9200	0.4274	0.126*
c7	0.5786 (3)	0.7731 (3)	0.9564 (2)	0.0513 (6)

	U11	U22	U33	U12	U13	U23
cu1	0.04167 (19)	0.0479 (2)	0.0488 (2)	0.00113 (13)	0.00015 (14)	−0.01383 (14)
cl4	0.0799 (5)	0.0468 (4)	0.0649 (5)	0.0114 (3)	−0.0143 (4)	−0.0143 (3)
cl1	0.0553 (4)	0.0672 (5)	0.0843 (6)	−0.0018 (3)	0.0113 (4)	−0.0387 (4)
cl3	0.0564 (4)	0.0628 (5)	0.0938 (6)	−0.0028 (3)	0.0196 (4)	−0.0012 (4)
cl2	0.0468 (4)	0.1114 (7)	0.0754 (5)	−0.0016 (4)	−0.0041 (4)	−0.0547 (5)
n4	0.0454 (12)	0.0522 (13)	0.0532 (13)	0.0017 (10)	−0.0052 (10)	−0.0151 (10)
c8	0.0479 (15)	0.0499 (15)	0.075 (2)	0.0064 (12)	−0.0217 (15)	−0.0052 (14)
c1	0.0541 (15)	0.0491 (15)	0.0523 (16)	−0.0018 (12)	−0.0095 (12)	−0.0177 (12)
n2	0.0494 (13)	0.0517 (13)	0.0511 (13)	−0.0010 (10)	0.0017 (10)	−0.0171 (10)
c11	0.0483 (15)	0.0512 (15)	0.0540 (16)	0.0060 (12)	−0.0003 (13)	0.0003 (13)
c9	0.078 (2)	0.0630 (19)	0.0567 (18)	0.0104 (16)	−0.0305 (17)	−0.0069 (15)
c10	0.071 (2)	0.074 (2)	0.0435 (15)	0.0107 (16)	−0.0065 (14)	−0.0028 (14)
c5	0.0474 (15)	0.0672 (18)	0.0556 (17)	−0.0057 (13)	−0.0081 (13)	−0.0059 (14)
n1	0.106 (2)	0.0559 (15)	0.0605 (17)	0.0022 (14)	−0.0031 (15)	−0.0076 (13)
c2	0.0581 (17)	0.0664 (18)	0.071 (2)	0.0108 (14)	−0.0178 (15)	−0.0373 (16)
c3	0.0570 (18)	0.110 (3)	0.060 (2)	0.0061 (18)	−0.0058 (15)	−0.045 (2)
c12	0.0543 (18)	0.081 (2)	0.079 (2)	−0.0058 (16)	0.0037 (16)	−0.0056 (18)
n3	0.0528 (15)	0.102 (2)	0.082 (2)	−0.0050 (14)	0.0126 (14)	−0.0362 (17)
c4	0.0624 (19)	0.100 (3)	0.0455 (17)	−0.0032 (18)	−0.0046 (14)	−0.0077 (17)
c6	0.078 (2)	0.065 (2)	0.097 (3)	−0.0018 (18)	−0.004 (2)	0.007 (2)
c7	0.0410 (14)	0.0475 (14)	0.0647 (18)	0.0082 (11)	−0.0025 (13)	−0.0124 (13)

Cu1—Cl3	2.2183 (9)	c10—h10	0.9300
Cu1—Cl1	2.2333 (8)	c5—c4	1.348 (5)
Cu1—Cl2	2.2426 (9)	c5—c6	1.488 (5)
Cu1—Cl4	2.2517 (9)	n1—h1a	0.8600
N4—C7	1.345 (4)	n1—h1b	0.8600
N4—C11	1.362 (4)	c2—c3	1.343 (5)
n4—h4	0.8600	c2—h2a	0.9300
c8—c9	1.345 (5)	c3—c4	1.386 (5)
c8—c7	1.394 (4)	c3—h3	0.9300
c8—h8	0.9300	c12—h12a	0.9600
C1—N1	1.328 (4)	c12—h12b	0.9600
C1—N2	1.337 (4)	c12—h12c	0.9600
c1—c2	1.401 (4)	N3—C7	1.330 (4)
N2—C5	1.363 (4)	n3—h3a	0.8600
n2—h2	0.8600	n3—h3b	0.8600
c11—c10	1.348 (4)	c4—h4a	0.9300
c11—c12	1.492 (4)	c6—h6a	0.9600
c9—c10	1.399 (5)	c6—h6b	0.9600
c9—h9	0.9300	c6—h6c	0.9600
cl3—cu1—cl1	100.96 (4)	c1—n1—h1a	120.0
cl3—cu1—cl2	132.57 (4)	c1—n1—h1b	120.0
cl1—cu1—cl2	100.71 (3)	h1a—n1—h1b	120.0
cl3—cu1—cl4	98.61 (4)	c3—c2—c1	118.4 (3)
cl1—cu1—cl4	129.70 (4)	c3—c2—h2a	120.8
cl2—cu1—cl4	99.05 (4)	c1—c2—h2a	120.8
c7—n4—c11	124.2 (3)	c2—c3—c4	121.6 (3)
c7—n4—h4	117.9	c2—c3—h3	119.2
c11—n4—h4	117.9	c4—c3—h3	119.2
c9—c8—c7	119.2 (3)	c11—c12—h12a	109.5
c9—c8—h8	120.4	c11—c12—h12b	109.5
c7—c8—h8	120.4	h12a—c12—h12b	109.5
n1—c1—n2	118.3 (3)	c11—c12—h12c	109.5
n1—c1—c2	123.6 (3)	h12a—c12—h12c	109.5
n2—c1—c2	118.1 (3)	h12b—c12—h12c	109.5
c1—n2—c5	124.3 (2)	c7—n3—h3a	120.0
c1—n2—h2	117.8	c7—n3—h3b	120.0
c5—n2—h2	117.8	h3a—n3—h3b	120.0
c10—c11—n4	117.9 (3)	c5—c4—c3	120.1 (3)
c10—c11—c12	125.8 (3)	c5—c4—h4a	119.9
n4—c11—c12	116.4 (3)	c3—c4—h4a	119.9
c8—c9—c10	121.2 (3)	c5—c6—h6a	109.5
c8—c9—h9	119.4	c5—c6—h6b	109.5
c10—c9—h9	119.4	h6a—c6—h6b	109.5
c11—c10—c9	119.7 (3)	c5—c6—h6c	109.5
c11—c10—h10	120.2	h6a—c6—h6c	109.5
c9—c10—h10	120.2	h6b—c6—h6c	109.5
c4—c5—n2	117.3 (3)	n3—c7—n4	118.2 (3)
c4—c5—c6	126.2 (3)	n3—c7—c8	124.0 (3)
n2—c5—c6	116.4 (3)	n4—c7—c8	117.8 (3)
n1—c1—n2—c5	179.5 (3)	n1—c1—c2—c3	179.5 (3)
c2—c1—n2—c5	−1.6 (4)	n2—c1—c2—c3	0.5 (4)
c7—n4—c11—c10	−1.1 (4)	c1—c2—c3—c4	1.2 (5)
c7—n4—c11—c12	178.0 (3)	n2—c5—c4—c3	1.0 (5)
c7—c8—c9—c10	−0.8 (4)	c6—c5—c4—c3	−180.0 (3)
n4—c11—c10—c9	−1.3 (4)	c2—c3—c4—c5	−2.1 (5)
c12—c11—c10—c9	179.8 (3)	c11—n4—c7—n3	−177.7 (3)
c8—c9—c10—c11	2.2 (5)	c11—n4—c7—c8	2.5 (4)
c1—n2—c5—c4	0.8 (4)	c9—c8—c7—n3	178.8 (3)
c1—n2—c5—c6	−178.3 (3)	c9—c8—c7—n4	−1.4 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl4	0.86	2.93	3.453 (4)	121.4
N1—H1A···Cl2	0.86	2.95	3.655 (4)	141.1
N1—H1B···Cl3i	0.86	2.60	3.399 (4)	156.6
N1—H1B···Cl1i	0.86	2.95	3.511 (4)	125.0
N3—H3B···Cl1ii	0.86	2.51	3.347 (4)	165.5
N3—H3B···Cl2ii	0.86	2.86	3.277 (4)	112.0
N2—H2···Cl2	0.86	2.31	3.162 (4)	171.0
N3—H3A···Cl4	0.86	2.85	3.585 (4)	144.3
N4—H4···Cl4	0.86	2.36	3.204 (4)	169.3
C6—H6C···Cl3iii	0.96	2.78	3.670 (4)	154.7
C12—H12B···Cl1iv	0.96	2.94	3.781 (4)	146.5

Table 1

Selected bond lengths (Å)

Cu1—Cl3	2.2183 (9)
Cu1—Cl1	2.2333 (8)
Cu1—Cl2	2.2426 (9)
Cu1—Cl4	2.2517 (9)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl4	0.86	2.93	3.453 (4)	121
N1—H1A⋯Cl2	0.86	2.95	3.655 (4)	141
N1—H1B⋯Cl3i	0.86	2.60	3.399 (4)	157
N1—H1B⋯Cl1i	0.86	2.95	3.511 (4)	125
N3—H3B⋯Cl1ii	0.86	2.51	3.347 (4)	166
N3—H3B⋯Cl2ii	0.86	2.86	3.277 (4)	112
N2—H2⋯Cl2	0.86	2.31	3.162 (4)	171
N3—H3A⋯Cl4	0.86	2.85	3.585 (4)	144
N4—H4⋯Cl4	0.86	2.36	3.204 (4)	169
C6—H6C⋯Cl3iii	0.96	2.78	3.670 (4)	155
C12—H12B⋯Cl1iv	0.96	2.94	3.781 (4)	147

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