Bis(2-aminopyridinium) tetra­chloridozincate(II)

Cai, H.; Fu, X.

doi:10.1107/S1600536810046817

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page m1596

https://doi.org/10.1107/S1600536810046817

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Bis(2-aminopyridinium) tetrachloridozincate(II)

Hong-ling Cai ^a and Xue-qun Fu ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fuxuequn222@163.com

(Received 6 November 2010; accepted 12 November 2010; online 17 November 2010)

In the title compound, (C₅H₇N₂)₂[ZnCl₄], the pyridine N atoms are protonated and the [ZnCl₄]²⁻ anions adopt a slightly distorted tetrahedral configuration. In the crystal, weak N—H⋯Cl hydrogen bonds link the molecules into layers, while weak π–π interactions [centroid–centroid distance = 4.2758 (18) Å] also help to stabilize the packing.

Related literature

For background to phase transition materials, see: Li et al. (2008 ); Ye et al. (2009 ); Zhang et al. (2010 )

Experimental

Crystal data

(C₅H₇N₂)₂[ZnCl₄]
M_r = 397.42
Monoclinic, C 2/c
a = 8.3520 (17) Å
b = 14.198 (3) Å
c = 13.913 (3) Å
β = 93.70 (3)°
V = 1646.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.13 mm⁻¹
T = 298 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.653, T_max = 0.659
8175 measured reflections
1870 independent reflections
1612 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.103
S = 1.21
1870 reflections
99 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.94 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Cl1	0.90 (4)	2.44 (4)	3.335 (3)	170 (3)
N1—H1A⋯Cl2ⁱ	0.88 (4)	2.42 (4)	3.291 (3)	168 (4)
N2—H2A⋯Cl1ⁱⁱ	0.87 (3)	2.61 (3)	3.325 (2)	140 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046817/jh2229sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046817/jh2229Isup2.hkl

checkCIF report

Comment top

The asymmetric unit of the title compound is built up from one protonated 2-amino-pyridinium cation where the non-hydrogen atoms are practically co-planar with a mean deviation of 0.0101 (3)Å and a half of [ZnCl₄]^2- anion (Fig. 1). The [ZnCl₄]^2- anion is slightly distorted with the Zn—Cl distances and Cl—Zn—Cl angles of 2.2800 (8)Å to 2.2819 (8)Å and 104.40 (3)° to 114.65 (4)°, respectively. In the crystal structure (Fig. 2), π-π packing interactions of adjacent pyridine rings with a Cg1—Cg2 distance of 4.2758 (18)Å link the cations chains along b axis. The N—H···Cl hydrogen bonds with the average N—Cl distances of 3.317 A link the cations and anions into plan parallel to [1 1 0].

Related literature top

For background to phase transition materials, see: Li et al. (2008); Ye et al. (2009); Zhang et al. (2010)

Experimental top

As a continuation of our study of phase transition materials (Li et al., 2008, Ye et al., 2009, Zhang et al., 2010,), we performed dielectric studies (capacitance and dielectric loss measurements) using an automatic impedance TongHui2828 Analyzer on samples that were pressed into tablets on the surfaces of which a conducting carbon glue was deposited. Unfortunately, there was no distinct anomaly observed from 93 K to 420 K, (m.p. 438–440 K), suggesting that this compound should be not a real ferroelectrics or there may be no distinct phase transition occurred within the measured temperature range.

1.36 g (10 mmol)ZnCl₂ was firstly dissolved in 20 ml 1M HCl solution, to which 0.94 g (10 mmol) 2-amino-pyridine ethanol solution was then added under stirring. Ethanol was added until the precipitated substrates disappeared, then the solution was allowed to slowly evaporate at room temperature until prisms of the title were grown.

Structure description top

For background to phase transition materials, see: Li et al. (2008); Ye et al. (2009); Zhang et al. (2010)

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds and π-π packing interactions.

Bis(2-aminopyridinium) tetrachloridozincate(II) top

Crystal data top

(C₅H₇N₂)₂[ZnCl₄]	F(000) = 800
M_r = 397.42	D_x = 1.603 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3679 reflections
a = 8.3520 (17) Å	θ = 3.1–27.4°
b = 14.198 (3) Å	µ = 2.13 mm⁻¹
c = 13.913 (3) Å	T = 298 K
β = 93.70 (3)°	Prism, colourless
V = 1646.5 (6) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Rigaku SCXmini diffractometer	1870 independent reflections
Radiation source: fine-focus sealed tube	1612 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −18→18
T_min = 0.653, T_max = 0.659	l = −17→17
8175 measured reflections

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	w = 1/[σ²(F_o²) + (0.0494P)² + 0.9383P] where P = (F_o² + 2F_c²)/3
1870 reflections	(Δ/σ)_max = 0.001
99 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.94 e Å⁻³

Crystal data top

(C₅H₇N₂)₂[ZnCl₄]	V = 1646.5 (6) Å³
M_r = 397.42	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 8.3520 (17) Å	µ = 2.13 mm⁻¹
b = 14.198 (3) Å	T = 298 K
c = 13.913 (3) Å	0.20 × 0.20 × 0.20 mm
β = 93.70 (3)°

Data collection top

Rigaku SCXmini diffractometer	1870 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1612 reflections with I > 2σ(I)
T_min = 0.653, T_max = 0.659	R_int = 0.036
8175 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.21	Δρ_max = 0.39 e Å⁻³
1870 reflections	Δρ_min = −0.94 e Å⁻³
99 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.

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

	x	y	z	U_iso*/U_eq
Zn1	0.5000	0.53941 (3)	0.2500	0.04169 (16)
Cl1	0.40003 (10)	0.44657 (6)	0.36567 (7)	0.0650 (3)
Cl2	0.71122 (9)	0.63194 (5)	0.30264 (6)	0.0577 (2)
N1	0.5979 (3)	0.2427 (2)	0.3635 (2)	0.0569 (6)
H1B	0.543 (4)	0.297 (3)	0.356 (3)	0.071 (11)*
H1A	0.655 (5)	0.222 (3)	0.317 (3)	0.083 (12)*
N2	0.6702 (3)	0.11162 (17)	0.45575 (19)	0.0495 (6)
H2A	0.728 (4)	0.092 (2)	0.410 (2)	0.055 (9)*
C1	0.5877 (3)	0.19378 (19)	0.44405 (19)	0.0432 (6)
C2	0.4952 (3)	0.2225 (2)	0.5209 (2)	0.0510 (6)
H2B	0.4328	0.2793	0.5154	0.061*
C3	0.4951 (4)	0.1691 (2)	0.6022 (2)	0.0586 (7)
H3A	0.4330	0.1893	0.6541	0.070*
C4	0.5850 (4)	0.0851 (2)	0.6126 (2)	0.0606 (8)
H4A	0.5839	0.0479	0.6702	0.073*
C5	0.6707 (4)	0.0582 (2)	0.5376 (2)	0.0556 (7)
H5A	0.7304	0.0028	0.5419	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0398 (2)	0.0381 (2)	0.0484 (3)	0.000	0.01243 (18)	0.000
Cl1	0.0636 (5)	0.0588 (4)	0.0761 (5)	0.0085 (3)	0.0311 (4)	0.0244 (4)
Cl2	0.0556 (4)	0.0519 (4)	0.0656 (5)	−0.0148 (3)	0.0046 (3)	−0.0023 (3)
N1	0.0571 (15)	0.0612 (16)	0.0533 (14)	0.0015 (13)	0.0096 (12)	−0.0039 (12)
N2	0.0394 (11)	0.0509 (13)	0.0591 (14)	−0.0010 (10)	0.0097 (10)	−0.0149 (11)
C1	0.0322 (11)	0.0480 (14)	0.0494 (15)	−0.0047 (10)	0.0016 (10)	−0.0103 (11)
C2	0.0431 (13)	0.0548 (16)	0.0554 (16)	0.0072 (12)	0.0050 (12)	−0.0104 (13)
C3	0.0556 (17)	0.0704 (19)	0.0509 (17)	0.0036 (14)	0.0127 (13)	−0.0078 (14)
C4	0.0625 (18)	0.0605 (18)	0.0595 (18)	−0.0003 (15)	0.0077 (14)	0.0036 (14)
C5	0.0500 (16)	0.0469 (14)	0.070 (2)	0.0017 (12)	0.0029 (14)	−0.0020 (13)

Geometric parameters (Å, º) top

Zn1—Cl1	2.2800 (8)	N2—H2A	0.87 (3)
Zn1—Cl1ⁱ	2.2800 (8)	C1—C2	1.419 (4)
Zn1—Cl2	2.2819 (8)	C2—C3	1.362 (4)
Zn1—Cl2ⁱ	2.2819 (8)	C2—H2B	0.9601
N1—C1	1.326 (4)	C3—C4	1.412 (5)
N1—H1B	0.90 (4)	C3—H3A	0.9599
N1—H1A	0.88 (4)	C4—C5	1.359 (4)
N2—C1	1.359 (4)	C4—H4A	0.9600
N2—C5	1.368 (4)	C5—H5A	0.9300

Cl1—Zn1—Cl1ⁱ	109.36 (5)	N2—C1—C2	116.9 (3)
Cl1—Zn1—Cl2	114.65 (4)	C3—C2—C1	119.7 (3)
Cl1ⁱ—Zn1—Cl2	104.40 (3)	C3—C2—H2B	120.2
Cl1—Zn1—Cl2ⁱ	104.40 (3)	C1—C2—H2B	120.1
Cl1ⁱ—Zn1—Cl2ⁱ	114.65 (4)	C2—C3—C4	121.8 (3)
Cl2—Zn1—Cl2ⁱ	109.70 (5)	C2—C3—H3A	119.2
C1—N1—H1B	120 (2)	C4—C3—H3A	119.0
C1—N1—H1A	121 (3)	C5—C4—C3	117.5 (3)
H1B—N1—H1A	120 (3)	C5—C4—H4A	121.3
C1—N2—C5	123.4 (2)	C3—C4—H4A	121.1
C1—N2—H2A	119 (2)	C4—C5—N2	120.6 (3)
C5—N2—H2A	117 (2)	C4—C5—H5A	119.7
N1—C1—N2	119.4 (3)	N2—C5—H5A	119.7
N1—C1—C2	123.6 (3)

C5—N2—C1—N1	177.9 (3)	C1—C2—C3—C4	0.0 (5)
C5—N2—C1—C2	−1.7 (4)	C2—C3—C4—C5	−1.0 (5)
N1—C1—C2—C3	−178.2 (3)	C3—C4—C5—N2	0.7 (5)
N2—C1—C2—C3	1.3 (4)	C1—N2—C5—C4	0.7 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl1	0.90 (4)	2.44 (4)	3.335 (3)	170 (3)
N1—H1A···Cl2ⁱⁱ	0.88 (4)	2.42 (4)	3.291 (3)	168 (4)
N2—H2A···Cl1ⁱⁱⁱ	0.87 (3)	2.61 (3)	3.325 (2)	140 (3)

Symmetry codes: (ii) −x+3/2, y−1/2, −z+1/2; (iii) x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	(C₅H₇N₂)₂[ZnCl₄]
M_r	397.42
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	8.3520 (17), 14.198 (3), 13.913 (3)
β (°)	93.70 (3)
V (Å³)	1646.5 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.13
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.653, 0.659
No. of measured, independent and observed [I > 2σ(I)] reflections	8175, 1870, 1612
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.103, 1.21
No. of reflections	1870
No. of parameters	99
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.94

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl1	0.90 (4)	2.44 (4)	3.335 (3)	170 (3)
N1—H1A···Cl2ⁱ	0.88 (4)	2.42 (4)	3.291 (3)	168 (4)
N2—H2A···Cl1ⁱⁱ	0.87 (3)	2.61 (3)	3.325 (2)	140 (3)

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x+1/2, y−1/2, z.

Acknowledgements

The authors are grateful to the starter fund of Southeast University for financial support to purchase the X-ray diffractometer.

References

Li, X. Z., Qu, Z. R. & Xiong, R. G. (2008). Chin. J. Chem. . 11, 1959–1962. Web of Science CSD CrossRef Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, H. Y., Fu, D. W., Zhang, Y., Zhang, W., Xiong, R. G. & Huang, S. D. (2009). J. Am. Chem. Soc. 131, 42–43. Web of Science CSD CrossRef PubMed CAS Google Scholar
Zhang, W., Ye, H. Y., Cai, H. L., Ge, J. Z., Xiong, R. G. & Huang, S. D. (2010). J. Am. Chem. Soc. 131, 7300–7302. Web of Science CSD CrossRef Google Scholar