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Acta Cryst. (2009). E65, m1661-m1662    [ doi:10.1107/S160053680904923X ]

Bis(2-amino-6-methylpyridinium) tetrachloridocuprate(II)

J. Gong, G. Chen, S.-F. Ni, Y.-Y. Zhang and H.-B. Wang

Abstract top

The title compound, (C6H9N2)2[CuCl4], contains a distorted tetrahedral [CuCl4]2- anion and two protonated aminopyridinium cations. The geometries of the protonated aminopyridinium cations reveal amine-imine tautomerism. The crystal packing is influenced by N-H...Cl and C-H...Cl hydrogen bonds and [pi]-[pi] stacking interactions [centroid-centroid distances = 3.635 (4) and 3.642 (4)°].

Comment top

There are a series of compounds of the formula A2[MX4], where A is an organic cation, usually a protonted base, M is a divalent transition metal ion and X is a halide (Cl, Br) (Hammar et al., 1997). A wide variety of these complexes are known where the A-group is a protonated alkylamine (Zhou et al., 1990), heterocycle such as pyridine (Place et al., 1987), 2-aminopyrimidine (Zanchini et al., 1990), or 2-amino-3-methylpridine (Coffey et al., 2000). The crystal structure of the title compound, (I), is now subjected to X-ray structure analysis.

The asymmetric unit comprises the two protonated, 2-amino-6-methyl-pyridinium cations (HAMP) and [CuCl4]2- anion (Fig. 1, Table1). The dihedral angle of the two HAMP cations is of 97.0 (3)°. The [CuCl4]2- anion assumes a distorted tetrahedral geometry consistent with the anticipated by Jahn–Teller effect documented by the value of the trans Cl—Cu—Cl angle and also by the dihedral angle between CuCl2 planes. In the present structure, the two independent trans angles are 132.57 (4)° and 129.70 (4)° and the dihedral angle between the CuCl2 planes is 65.4°. The average value of 2.2365Å observed in the [CuCl4]2- anion is shorter than the average value of 2.270Å (Antolini et al., 1988) or 2.260Å (Zhang et al., 2005) of square planar [CuCl4]2-anion. In the cation, the N3—C7 bond [1.330 (4) Å] is shorter than the N4—C7 [1.345 (4) Å] and N4—C11 [1.362 (4) Å] bonds, and the C7—C8 [1.394 (4) Å] and C(9)—C(10) [1.399 (5) Å] bonds are significantly longer than C8—C9 [1.345 (5) Å] and C10—C11 [1.348 (4) Å] bonds, this are similar to those in the HAMP cation of (C6H9N2)[ZnCl3(C6H8N2)] (Jin et al., 2005) and (C6H9N2)2[Sb2Cl6O] (Feng et al., 2007). In contrast, in the solid state structure of AMP, the N—C bond out of ring is clearly longer than that in the ring (Nahringbauer et al., 1997). The geometric features of HAMP cation (N1/N2/C1/C6) resemble those observed in other 2-aminopyridinium structures (Luque et al., 1997; Jin et al., 2000; Jin et al., 2001; Jin et al., 2005) that are believed to be involved in amine-imine tautomerism (Inuzuka et al., 1986; Inuzuka et al., 1990; Ishikawa et al., 2002). Similar features are also provided by cation HAMP (N3/N4/C7/C12). The crystal packing is determined by hydrogen bonds (Fig. 2 and Table 2) and π–π stacking interactions. The X1A···X1Ai separation (X1A is the centroid of the C1C5 ring, symmetry code: 1 - x, 1 - y, 1 - z) is of 3.635 (4)°, and the X1B···X1Bi separation (X1B is the centroid of the C7C11 ring, symmetry code: 1 - x, 2 - y, 2 - z) is of 3.642 (4)°.

Related literature top

For a series of compounds with formula A2[MX4], where A is an organic cation, usually a protonted base, M is a 2+ 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); Inuzuka & Fujimoto (1986, 1990); Ishikawa et al. (2002).

Experimental top

2-Amino-6-methyl-pyridine, aqueous HCl and CuCl2.2H2O in a molar ratio of 2:2:1 were mixed and dissolved in sufficient water. It was kept stirring and heating till a clear solution was obtained. Crystals of (I) were formed by gradual evaporation of excess water over one week at 293 K. Analysis for (I) (%): C 34.06; H 4.25; N, 13.27; Found (%): C 34.02; H 4.28; N 13.22. IR Spectrum (KBr, cm-1): 3411 (s), 3295 (s), 3195 (m), 3090 (m), 1656 (versus), 1630 (w), 1565 (w), 1474 (w), 1392 (m), 1309 (m), 1174 (w), 1042 (w), 997 (w), 793 (m), 715 (w), 612 (w), 564 (w), 421 (m).

Refinement top

All the H atoms were placed in calculated positions and allowed to ride on their parent atoms at distances of 0.93 Å for aromatic group, 0.86 Å for amido and 0.96 Å for methyl with isotropic displacement parameters 1.2 times Ueq of the parent atoms.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of (I).
[Figure 2] Fig. 2. A packing diagram viewed down along the b axis. Hydrogen bonds are illustrated as thin lines.
Bis(2-amino-6-methylpyridinium) tetrachloridocuprate(II) top
Crystal data top
(C6H9N2)2[CuCl4]Z = 2
Mr = 423.65F(000) = 430.0
Triclinic, P1Dx = 1.553 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7466 (17) ÅCell parameters from 2451 reflections
b = 8.0372 (18) Åθ = 2.2–24.3°
c = 14.969 (3) ŵ = 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
Data collection top
Bruker SMART APEX area-detector
diffractometer		3206 independent reflections
Radiation source: fine-focus sealed tube3161 reflections with I > 2σ(I)
graphiteRint = 0.013
φ and ω scanθmax = 25.0°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −7→9
Tmin = 0.549, Tmax = 0.578k = −9→9
4783 measured reflectionsl = −12→17
Refinement top
Refinement on f2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.090H-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 parametersΔρmax = 0.55 e Å−3
0 restraintsΔρmin = −0.33 e Å−3
Crystal data top
(C6H9N2)2[CuCl4]γ = 89.911 (4)°
Mr = 423.65V = 905.8 (3) Å3
Triclinic, P1Z = 2
a = 7.7466 (17) ÅMo Kα radiation
b = 8.0372 (18) ŵ = 1.79 mm−1
c = 14.969 (3) ÅT = 273 K
α = 78.922 (4)°0.35 × 0.34 × 0.30 mm
β = 82.154 (4)°
Data collection top
Bruker SMART APEX area-detector
diffractometer		3206 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		3161 reflections with I > 2σ(I)
Tmin = 0.549, Tmax = 0.578Rint = 0.013
4783 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.090Δρmax = 0.55 e Å−3
S = 1.05Δρmin = −0.33 e Å−3
3161 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
cu10.18139 (4)0.80739 (4)0.75385 (2)0.04615 (13)
cl40.31507 (11)0.56448 (9)0.80270 (5)0.0630 (2)
cl10.04761 (10)0.98881 (10)0.83451 (6)0.0677 (2)
cl30.41383 (10)0.96162 (10)0.68092 (7)0.0757 (3)
cl2−0.04646 (10)0.69927 (13)0.70434 (6)0.0734 (3)
n40.4134 (3)0.7120 (3)0.97401 (16)0.0498 (5)
h40.37250.67150.93180.060*
c80.6468 (4)0.8324 (4)1.0262 (2)0.0575 (7)
h80.76130.87331.01720.069*
c10.2333 (4)0.4070 (3)0.56633 (19)0.0506 (6)
n20.1895 (3)0.5691 (3)0.54343 (16)0.0506 (5)
h20.13280.61490.58550.061*
c110.3066 (4)0.7100 (4)1.0545 (2)0.0532 (7)
c90.5450 (5)0.8298 (4)1.1068 (2)0.0646 (8)
h90.59060.86791.15380.077*
c100.3717 (4)0.7707 (4)1.1212 (2)0.0641 (8)
h100.30170.77331.17660.077*
c50.2289 (4)0.6664 (4)0.4578 (2)0.0574 (7)
n10.1881 (4)0.3267 (3)0.65263 (19)0.0753 (8)
h1a0.13210.37900.69220.090*
h1b0.21480.22240.66900.090*
c20.3220 (4)0.3304 (4)0.4975 (2)0.0610 (8)
h2a0.35390.21770.51040.073*
c30.3598 (4)0.4236 (5)0.4123 (2)0.0720 (10)
h30.41660.37350.36580.086*
c120.1255 (4)0.6423 (5)1.0599 (3)0.0741 (9)
h12a0.11200.60671.00350.111*
h12b0.04400.72941.06960.111*
h12c0.10380.54741.11020.111*
n30.6670 (4)0.7728 (4)0.8737 (2)0.0784 (8)
h3a0.61830.73420.83330.094*
h3b0.77280.81120.86070.094*
c40.3162 (4)0.5927 (5)0.3920 (2)0.0704 (9)
h4a0.34710.65540.33290.084*
c60.1734 (5)0.8456 (4)0.4464 (3)0.0841 (11)
h6a0.11390.86580.50370.126*
h6b0.09650.86680.40050.126*
h6c0.27410.92000.42740.126*
c70.5786 (3)0.7731 (3)0.9564 (2)0.0513 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
cu10.04167 (19)0.0479 (2)0.0488 (2)0.00113 (13)0.00015 (14)−0.01383 (14)
cl40.0799 (5)0.0468 (4)0.0649 (5)0.0114 (3)−0.0143 (4)−0.0143 (3)
cl10.0553 (4)0.0672 (5)0.0843 (6)−0.0018 (3)0.0113 (4)−0.0387 (4)
cl30.0564 (4)0.0628 (5)0.0938 (6)−0.0028 (3)0.0196 (4)−0.0012 (4)
cl20.0468 (4)0.1114 (7)0.0754 (5)−0.0016 (4)−0.0041 (4)−0.0547 (5)
n40.0454 (12)0.0522 (13)0.0532 (13)0.0017 (10)−0.0052 (10)−0.0151 (10)
c80.0479 (15)0.0499 (15)0.075 (2)0.0064 (12)−0.0217 (15)−0.0052 (14)
c10.0541 (15)0.0491 (15)0.0523 (16)−0.0018 (12)−0.0095 (12)−0.0177 (12)
n20.0494 (13)0.0517 (13)0.0511 (13)−0.0010 (10)0.0017 (10)−0.0171 (10)
c110.0483 (15)0.0512 (15)0.0540 (16)0.0060 (12)−0.0003 (13)0.0003 (13)
c90.078 (2)0.0630 (19)0.0567 (18)0.0104 (16)−0.0305 (17)−0.0069 (15)
c100.071 (2)0.074 (2)0.0435 (15)0.0107 (16)−0.0065 (14)−0.0028 (14)
c50.0474 (15)0.0672 (18)0.0556 (17)−0.0057 (13)−0.0081 (13)−0.0059 (14)
n10.106 (2)0.0559 (15)0.0605 (17)0.0022 (14)−0.0031 (15)−0.0076 (13)
c20.0581 (17)0.0664 (18)0.071 (2)0.0108 (14)−0.0178 (15)−0.0373 (16)
c30.0570 (18)0.110 (3)0.060 (2)0.0061 (18)−0.0058 (15)−0.045 (2)
c120.0543 (18)0.081 (2)0.079 (2)−0.0058 (16)0.0037 (16)−0.0056 (18)
n30.0528 (15)0.102 (2)0.082 (2)−0.0050 (14)0.0126 (14)−0.0362 (17)
c40.0624 (19)0.100 (3)0.0455 (17)−0.0032 (18)−0.0046 (14)−0.0077 (17)
c60.078 (2)0.065 (2)0.097 (3)−0.0018 (18)−0.004 (2)0.007 (2)
c70.0410 (14)0.0475 (14)0.0647 (18)0.0082 (11)−0.0025 (13)−0.0124 (13)
Geometric parameters (Å, °) top
Cu1—Cl32.2183 (9)c10—h100.9300
Cu1—Cl12.2333 (8)c5—c41.348 (5)
Cu1—Cl22.2426 (9)c5—c61.488 (5)
Cu1—Cl42.2517 (9)n1—h1a0.8600
N4—C71.345 (4)n1—h1b0.8600
N4—C111.362 (4)c2—c31.343 (5)
n4—h40.8600c2—h2a0.9300
c8—c91.345 (5)c3—c41.386 (5)
c8—c71.394 (4)c3—h30.9300
c8—h80.9300c12—h12a0.9600
C1—N11.328 (4)c12—h12b0.9600
C1—N21.337 (4)c12—h12c0.9600
c1—c21.401 (4)N3—C71.330 (4)
N2—C51.363 (4)n3—h3a0.8600
n2—h20.8600n3—h3b0.8600
c11—c101.348 (4)c4—h4a0.9300
c11—c121.492 (4)c6—h6a0.9600
c9—c101.399 (5)c6—h6b0.9600
c9—h90.9300c6—h6c0.9600
cl3—cu1—cl1100.96 (4)c1—n1—h1a120.0
cl3—cu1—cl2132.57 (4)c1—n1—h1b120.0
cl1—cu1—cl2100.71 (3)h1a—n1—h1b120.0
cl3—cu1—cl498.61 (4)c3—c2—c1118.4 (3)
cl1—cu1—cl4129.70 (4)c3—c2—h2a120.8
cl2—cu1—cl499.05 (4)c1—c2—h2a120.8
c7—n4—c11124.2 (3)c2—c3—c4121.6 (3)
c7—n4—h4117.9c2—c3—h3119.2
c11—n4—h4117.9c4—c3—h3119.2
c9—c8—c7119.2 (3)c11—c12—h12a109.5
c9—c8—h8120.4c11—c12—h12b109.5
c7—c8—h8120.4h12a—c12—h12b109.5
n1—c1—n2118.3 (3)c11—c12—h12c109.5
n1—c1—c2123.6 (3)h12a—c12—h12c109.5
n2—c1—c2118.1 (3)h12b—c12—h12c109.5
c1—n2—c5124.3 (2)c7—n3—h3a120.0
c1—n2—h2117.8c7—n3—h3b120.0
c5—n2—h2117.8h3a—n3—h3b120.0
c10—c11—n4117.9 (3)c5—c4—c3120.1 (3)
c10—c11—c12125.8 (3)c5—c4—h4a119.9
n4—c11—c12116.4 (3)c3—c4—h4a119.9
c8—c9—c10121.2 (3)c5—c6—h6a109.5
c8—c9—h9119.4c5—c6—h6b109.5
c10—c9—h9119.4h6a—c6—h6b109.5
c11—c10—c9119.7 (3)c5—c6—h6c109.5
c11—c10—h10120.2h6a—c6—h6c109.5
c9—c10—h10120.2h6b—c6—h6c109.5
c4—c5—n2117.3 (3)n3—c7—n4118.2 (3)
c4—c5—c6126.2 (3)n3—c7—c8124.0 (3)
n2—c5—c6116.4 (3)n4—c7—c8117.8 (3)
n1—c1—n2—c5179.5 (3)n1—c1—c2—c3179.5 (3)
c2—c1—n2—c5−1.6 (4)n2—c1—c2—c30.5 (4)
c7—n4—c11—c10−1.1 (4)c1—c2—c3—c41.2 (5)
c7—n4—c11—c12178.0 (3)n2—c5—c4—c31.0 (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—c9179.8 (3)c11—n4—c7—n3−177.7 (3)
c8—c9—c10—c112.2 (5)c11—n4—c7—c82.5 (4)
c1—n2—c5—c40.8 (4)c9—c8—c7—n3178.8 (3)
c1—n2—c5—c6−178.3 (3)c9—c8—c7—n4−1.4 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl40.862.933.453 (4)121.4
N1—H1A···Cl20.862.953.655 (4)141.1
N1—H1B···Cl3i0.862.603.399 (4)156.6
N1—H1B···Cl1i0.862.953.511 (4)125.0
N3—H3B···Cl1ii0.862.513.347 (4)165.5
N3—H3B···Cl2ii0.862.863.277 (4)112.0
N2—H2···Cl20.862.313.162 (4)171.0
N3—H3A···Cl40.862.853.585 (4)144.3
N4—H4···Cl40.862.363.204 (4)169.3
C6—H6C···Cl3iii0.962.783.670 (4)154.7
C12—H12B···Cl1iv0.962.943.781 (4)146.5
Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1; (iv) −x, −y+2, −z+2.
Table 1
Selected geometric parameters (Å) top
Cu1—Cl32.2183 (9)N4—C111.362 (4)
Cu1—Cl12.2333 (8)C1—N11.328 (4)
Cu1—Cl22.2426 (9)C1—N21.337 (4)
Cu1—Cl42.2517 (9)N2—C51.363 (4)
N4—C71.345 (4)N3—C71.330 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl40.862.933.453 (4)121.4
N1—H1A···Cl20.862.953.655 (4)141.1
N1—H1B···Cl3i0.862.603.399 (4)156.6
N1—H1B···Cl1i0.862.953.511 (4)125.0
N3—H3B···Cl1ii0.862.513.347 (4)165.5
N3—H3B···Cl2ii0.862.863.277 (4)112.0
N2—H2···Cl20.862.313.162 (4)171.0
N3—H3A···Cl40.862.853.585 (4)144.3
N4—H4···Cl40.862.363.204 (4)169.3
C6—H6C···Cl3iii0.962.783.670 (4)154.7
C12—H12B···Cl1iv0.962.943.781 (4)146.5
Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) −x+1, −y+2, −z+1; (iv) −x, −y+2, −z+2.
references
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