Literature DB >> 21522283

Bis(2-amino-5-chloro-pyridinium) tetra-chloridozincate.

Riadh Kefi, Erwann Jeanneau, Frederic Lefebvre, Cherif Ben Nasr.

Abstract

The asymmetric unit of the title compound, (C(5)H(6)ClN(2))(2)[ZnCl(4)], contains two 2-amino-5-chloro-pyridinium cations and one [ZnCl(4)](2-) dianion which are held together by N-H⋯Cl and C-H⋯Cl hydrogen bonds. The [ZnCl(4)](2-) anions have a distorted tetra-hedral geometry. Weak inter-molecular π-π stacking inter-actions exist between neighbouring aromatic rings of the cations with a centroid-centroid distance of 3.712 (7) Å.

Entities: Chemical Disease Gene Species

Year: 2011 PMID： 21522283 PMCID： PMC3052069 DOI： 10.1107/S1600536811005691

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For common applications of organic–inorganic hybrid materials, see: Kobel & Hanack (1986 ▶); Pierpont & Jung (1994 ▶). For a related structure, see: Coomer et al. (2007 ▶). For π–π interactions between pyridinium cations, see: Albrecht et al. (2003 ▶). For aminium–iminium tautomerism, see: Jin et al. (2001 ▶). For a discussion of C—N—C pyridinium angles, see: Jin et al. (2005 ▶).

Experimental

Crystal data

(C5H6ClN2)2[ZnCl4] M = 466.33 Monoclinic, a = 13.317 (1) Å b = 14.817 (2) Å c = 8.571 (1) Å β = 92.923 (9)° V = 1689.0 (3) Å3 Z = 4 Mo Kα radiation μ = 2.40 mm−1 T = 110 K 0.23 × 0.15 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer Absorption correction: analytical CrysAlis PRO (Oxford Diffraction, 2009 ▶; Clark & Reid, 1995 ▶) T min = 0.711, T max = 0.835 22410 measured reflections 4360 independent reflections 3553 reflections with I > 2σ(I) R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.051 wR(F 2) = 0.108 S = 1.02 4356 reflections 190 parameters H-atom parameters constrained Δρmax = 1.27 e Å−3 Δρmin = −1.03 e Å−3 Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: CRYSTALS. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005691/cv5049sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005691/cv5049Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C₅H₆ClN₂)₂[ZnCl₄]	F(000) = 928
M_r = 466.33	D_x = 1.834 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 8999 reflections
a = 13.317 (1) Å	θ = 3.4–29.5°
b = 14.817 (2) Å	µ = 2.40 mm⁻¹
c = 8.571 (1) Å	T = 110 K
β = 92.923 (9)°	Block, colourless
V = 1689.0 (3) Å³	0.23 × 0.15 × 0.10 mm
Z = 4

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer	4360 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3553 reflections with I > 2σ(I)
graphite	R_int = 0.061
Detector resolution: 10.4685 pixels mm^-1	θ_max = 29.6°, θ_min = 3.4°
ω scans	h = −18→18
Absorption correction: analytical CrysAlis PRO (Oxford Diffraction, 2009; Clark & Reid, 1995)	k = −20→18
T_min = 0.711, T_max = 0.835	l = −11→11
22410 measured reflections

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.108	Method, part 1, Chebychev polynomial [Watkin, D. J. (1994). Acta Cryst. A50, 411–437; Prince, E. (1982). Mathematical Techniques in Crystallography and Materials Science Springer-Verlag, New York.] [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 425. 613. 311. 83.3
S = 1.02	(Δ/σ)_max = 0.001
4356 reflections	Δρ_max = 1.27 e Å⁻³
190 parameters	Δρ_min = −1.03 e Å⁻³
0 restraints

	x	y	z	U_iso*/U_eq
Zn1	0.25192 (4)	0.48608 (3)	1.01057 (6)	0.0183
Cl2	0.15870 (8)	0.47893 (8)	0.78203 (13)	0.0220
Cl3	0.13940 (9)	0.48449 (8)	1.19926 (13)	0.0255
Cl4	0.34397 (10)	0.35524 (8)	1.02302 (17)	0.0298
Cl5	0.35902 (9)	0.60259 (8)	1.04980 (15)	0.0249
Cl6	0.33629 (9)	0.37113 (8)	0.53253 (15)	0.0266
C7	0.3767 (3)	0.4786 (3)	0.5834 (6)	0.0213
C8	0.4484 (3)	0.4888 (3)	0.6981 (5)	0.0204
N9	0.4826 (3)	0.5725 (3)	0.7372 (5)	0.0201
C10	0.4457 (3)	0.6486 (3)	0.6703 (6)	0.0194
N11	0.4816 (3)	0.7281 (3)	0.7197 (5)	0.0263
C12	0.3706 (3)	0.6396 (3)	0.5495 (6)	0.0218
C13	0.3361 (4)	0.5555 (3)	0.5071 (6)	0.0242
H131	0.2865	0.5492	0.4259	0.0299*
H121	0.3449	0.6907	0.4991	0.0261*
H91	0.5254	0.5774	0.8160	0.0238*
H81	0.4748	0.4393	0.7511	0.0250*
Cl14	0.18546 (9)	0.74583 (10)	0.78663 (15)	0.0313
C15	0.0852 (3)	0.7508 (3)	0.9057 (5)	0.0221
C16	0.0460 (4)	0.8350 (3)	0.9491 (6)	0.0253
C17	−0.0331 (4)	0.8381 (3)	1.0446 (6)	0.0247
C18	−0.0742 (3)	0.7580 (3)	1.1000 (5)	0.0201
N19	−0.1504 (3)	0.7566 (3)	1.1978 (5)	0.0249
N20	−0.0342 (3)	0.6791 (3)	1.0543 (5)	0.0211
C21	0.0433 (4)	0.6741 (3)	0.9572 (5)	0.0211
H211	0.0658	0.6181	0.9267	0.0262*
H201	−0.0611	0.6300	1.0824	0.0252*
H171	−0.0594	0.8932	1.0719	0.0302*
H161	0.0734	0.8879	0.9135	0.0311*
H191	−0.1768	0.7063	1.2220	0.0299*
H192	−0.1759	0.8065	1.2265	0.0297*
H111	0.4608	0.7769	0.6733	0.0310*
H112	0.5310	0.7303	0.7899	0.0310*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0174 (2)	0.0137 (2)	0.0236 (3)	−0.00055 (19)	−0.00135 (19)	−0.0007 (2)
Cl2	0.0220 (5)	0.0207 (5)	0.0231 (5)	0.0011 (4)	−0.0009 (4)	−0.0009 (4)
Cl3	0.0301 (6)	0.0239 (5)	0.0229 (5)	−0.0059 (5)	0.0040 (4)	−0.0019 (4)
Cl4	0.0291 (6)	0.0153 (5)	0.0433 (7)	0.0046 (4)	−0.0137 (5)	−0.0039 (5)
Cl5	0.0241 (5)	0.0182 (5)	0.0322 (6)	−0.0055 (4)	−0.0004 (4)	−0.0025 (4)
Cl6	0.0257 (6)	0.0180 (5)	0.0363 (6)	−0.0038 (4)	0.0033 (5)	−0.0068 (5)
C7	0.021 (2)	0.0142 (19)	0.030 (2)	0.0002 (17)	0.0046 (18)	−0.0035 (18)
C8	0.026 (2)	0.0135 (19)	0.022 (2)	0.0044 (17)	−0.0003 (17)	0.0009 (16)
N9	0.0188 (18)	0.0164 (18)	0.025 (2)	0.0020 (14)	−0.0030 (15)	−0.0001 (15)
C10	0.019 (2)	0.0136 (19)	0.026 (2)	0.0032 (16)	0.0013 (17)	0.0001 (17)
N11	0.032 (2)	0.0140 (18)	0.032 (2)	0.0001 (16)	−0.0068 (18)	0.0007 (16)
C12	0.021 (2)	0.018 (2)	0.026 (2)	0.0048 (17)	−0.0008 (18)	0.0017 (18)
C13	0.023 (2)	0.023 (2)	0.025 (2)	0.0020 (18)	−0.0043 (18)	−0.0022 (19)
Cl14	0.0248 (6)	0.0439 (7)	0.0252 (6)	−0.0010 (5)	0.0001 (4)	−0.0005 (5)
C15	0.022 (2)	0.026 (2)	0.018 (2)	−0.0015 (18)	−0.0036 (17)	−0.0035 (18)
C16	0.033 (3)	0.019 (2)	0.024 (2)	−0.0047 (19)	−0.001 (2)	0.0014 (18)
C17	0.037 (3)	0.013 (2)	0.024 (2)	0.0019 (18)	−0.003 (2)	−0.0020 (17)
C18	0.019 (2)	0.019 (2)	0.022 (2)	0.0006 (17)	−0.0038 (17)	−0.0028 (17)
N19	0.025 (2)	0.023 (2)	0.027 (2)	0.0019 (16)	−0.0022 (16)	−0.0040 (17)
N20	0.024 (2)	0.0138 (17)	0.025 (2)	−0.0028 (15)	0.0017 (16)	−0.0010 (15)
C21	0.025 (2)	0.0147 (19)	0.023 (2)	0.0030 (17)	−0.0068 (18)	−0.0013 (17)

Zn1—Cl2	2.2674 (12)	C12—H121	0.928
Zn1—Cl3	2.2602 (13)	C13—H131	0.939
Zn1—Cl4	2.2934 (13)	Cl14—C15	1.723 (5)
Zn1—Cl5	2.2535 (12)	C15—C16	1.410 (7)
Cl6—C7	1.730 (5)	C15—C21	1.351 (7)
C7—C8	1.344 (6)	C16—C17	1.367 (7)
C7—C13	1.408 (7)	C16—H161	0.923
C8—N9	1.357 (6)	C17—C18	1.400 (7)
C8—H81	0.922	C17—H171	0.923
N9—C10	1.347 (6)	C18—N19	1.349 (6)
N9—H91	0.864	C18—N20	1.351 (6)
C10—N11	1.332 (6)	N19—H191	0.854
C10—C12	1.408 (6)	N19—H192	0.855
N11—H111	0.863	N20—C21	1.361 (6)
N11—H112	0.869	N20—H201	0.852
C12—C13	1.372 (7)	C21—H211	0.924

Cl2—Zn1—Cl3	105.30 (5)	C7—C13—C12	119.8 (4)
Cl2—Zn1—Cl4	105.57 (5)	C7—C13—H131	120.1
Cl3—Zn1—Cl4	109.28 (5)	C12—C13—H131	120.1
Cl2—Zn1—Cl5	118.63 (5)	Cl14—C15—C16	120.2 (4)
Cl3—Zn1—Cl5	109.81 (5)	Cl14—C15—C21	120.2 (4)
Cl4—Zn1—Cl5	107.93 (5)	C16—C15—C21	119.5 (4)
Cl6—C7—C8	119.2 (4)	C15—C16—C17	119.7 (4)
Cl6—C7—C13	121.4 (4)	C15—C16—H161	120.4
C8—C7—C13	119.4 (4)	C17—C16—H161	119.9
C7—C8—N9	120.0 (4)	C16—C17—C18	120.1 (4)
C7—C8—H81	120.7	C16—C17—H171	119.7
N9—C8—H81	119.3	C18—C17—H171	120.3
C8—N9—C10	123.4 (4)	C17—C18—N19	122.9 (4)
C8—N9—H91	118.0	C17—C18—N20	117.9 (4)
C10—N9—H91	118.3	N19—C18—N20	119.1 (4)
N9—C10—N11	119.2 (4)	C18—N19—H191	119.7
N9—C10—C12	117.6 (4)	C18—N19—H192	119.2
N11—C10—C12	123.1 (4)	H191—N19—H192	120.7
C10—N11—H111	119.5	C18—N20—C21	123.2 (4)
C10—N11—H112	120.0	C18—N20—H201	118.8
H111—N11—H112	120.1	C21—N20—H201	117.9
C10—C12—C13	119.8 (4)	N20—C21—C15	119.6 (4)
C10—C12—H121	119.8	N20—C21—H211	119.3
C13—C12—H121	120.4	C15—C21—H211	121.1

D—H···A	D—H	H···A	D···A	D—H···A
N19—H191···Cl2ⁱ	0.85	2.76	3.496 (5)	146
N20—H201···Cl2ⁱ	0.85	2.41	3.231 (6)	163
C21—H211···Cl2	0.92	2.73	3.635 (6)	165
N19—H192···Cl3ⁱⁱ	0.85	2.75	3.491 (5)	146
C13—H131···Cl3ⁱⁱⁱ	0.94	2.85	3.772 (5)	166
C16—H161···Cl3^iv	0.92	2.81	3.682 (7)	158
C17—H171···Cl3ⁱⁱ	0.92	2.65	3.442 (8)	144
N9—H91···Cl4^v	0.86	2.38	3.197 (4)	157
N11—H112···Cl4^v	0.87	2.58	3.356 (4)	148
N11—H111···Cl5^iv	0.86	2.45	3.291 (6)	165
C8—H81···Cl5^v	0.92	2.79	3.538 (4)	138

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N19—H191⋯Cl2ⁱ	0.85	2.76	3.496 (5)	146
N20—H201⋯Cl2ⁱ	0.85	2.41	3.231 (6)	163
N19—H192⋯Cl3ⁱⁱ	0.85	2.75	3.491 (5)	146
C17—H171⋯Cl3ⁱⁱ	0.92	2.65	3.442 (8)	144
N9—H91⋯Cl4ⁱⁱⁱ	0.86	2.38	3.197 (4)	157
N11—H112⋯Cl4ⁱⁱⁱ	0.87	2.58	3.356 (4)	148
N11—H111⋯Cl5^iv	0.86	2.45	3.291 (6)	165

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

1 in total

1. Bis(2-amino-6-methylpyridinium) tetrachlorozincate(II).

Authors: Zhi-Min Jin; Nan Shun; Ya-Ping Lü; Mao-Lin Hu; Liang Shen
Journal: Acta Crystallogr C Date: 2004-12-18 Impact factor: 1.172

1 in total

1. Crystal structure of bis-(2-amino-5-chloro-pyridinium) tetra-chlorido-cobaltate(II).

Authors: Marwa Mghandef; Habib Boughzala
Journal: Acta Crystallogr E Crystallogr Commun Date: 2015-04-25

1 in total