2-{2-[4-(Dimethyl-amino)-phen-yl]diazen-1-ium-1-yl}pyridinium tetra-chlorido-zincate.

The title compound, (C(13)H(16)N(4))[ZnCl(4)], consists of a tetra-hedral [ZnCl(4)](2-) anion and a 2-{2-[4-(dimethyl-amino)-phen-yl]diazen-1-ium-1-yl}pyridinium dication. The pyridinium-N atom is syn to the azo bond which allows for the formation of an intramolecular N-H⋯N hydrogen bond. In the crystal, the cation and anion are held together by N-H⋯Cl hydrogen-bond inter-actions involving the pyridinium and diazen-1-ium N atoms. π-π stacking inter-actions occur between the pyridine and benzene rings of adjacent cations [centroid-centroid distances = 3.6270 (18) and 3.8685 (18) Å]; the stacks are parallel to the a axis.

Related literature

For background to azo complexes, see: Chand et al. (2003 ▶); Das et al. (2006 ▶); Arslan (2007 ▶). For structures of related azoimine compounds and complexes, see: Panneerselvam et al. (2000 ▶); Leesakul et al. (2010 ▶, 2011 ▶). For structure of tetra­chloro­zincate (II), see: Harrison (2005 ▶); Valdés-Martínez et al. (2005 ▶); Bringley & Rajeswaran (2006 ▶); Xu et al. (2005 ▶).

Experimental

Crystal data

(C13H16N4)[ZnCl4]

M = 435.47

Monoclinic,

a = 7.4556 (4) Å

b = 21.4126 (10) Å

c = 11.1924 (5) Å

β = 99.883 (1)°

V = 1760.28 (15) Å3

Z = 4

Mo Kα radiation

μ = 2.00 mm−1

T = 293 K

0.18 × 0.17 × 0.04 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003) ▶ T min = 0.699, T max = 0.929

16401 measured reflections

3094 independent reflections

2687 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.082

S = 1.10

3094 reflections

209 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrea et al., 2008 ▶); software used to prepare material for publication: SHELXL97, WinGX (Farrugia, 1999 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023689/qm2069sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023689/qm2069Isup2.hkl

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

(C13H16N4)[ZnCl4]	F(000) = 880
Mr = 435.47	Dx = 1.643 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3620 reflections
a = 7.4556 (4) Å	θ = 2.7–23.6°
b = 21.4126 (10) Å	µ = 2.00 mm−1
c = 11.1924 (5) Å	T = 293 K
β = 99.883 (1)°	Block, redbrown
V = 1760.28 (15) Å3	0.18 × 0.17 × 0.04 mm
Z = 4

Bruker APEX CCD area-detector diffractometer	3094 independent reflections
Radiation source: fine-focus sealed tube	2687 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
Frames, each covering 0.3 ° in ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −8→8
Tmin = 0.699, Tmax = 0.929	k = −25→25
16401 measured reflections	l = −13→13

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ2(Fo2) + (0.038P)2 + 0.8053P] where P = (Fo2 + 2Fc2)/3
3094 reflections	(Δ/σ)max = 0.008
209 parameters	Δρmax = 0.36 e Å−3
2 restraints	Δρmin = −0.22 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 > 2σ (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
H2A	0.850 (5)	1.0694 (15)	0.076 (3)	0.078 (12)*
H1A	0.605 (4)	0.9976 (9)	−0.157 (3)	0.048 (9)*
Zn1	0.31545 (5)	0.131012 (15)	0.31166 (3)	0.03901 (12)
Cl1	0.53360 (12)	0.10101 (4)	0.20333 (8)	0.0551 (2)
Cl2	0.27049 (11)	0.05405 (4)	0.44071 (7)	0.0493 (2)
Cl3	0.05128 (12)	0.14947 (4)	0.18109 (7)	0.0590 (2)
Cl4	0.41086 (13)	0.21647 (3)	0.42151 (7)	0.0553 (2)
N1	0.6143 (3)	1.03805 (11)	−0.1729 (2)	0.0392 (6)
C1	0.5358 (4)	1.06175 (15)	−0.2791 (3)	0.0428 (7)
H1	0.4752	1.0356	−0.3392	0.051*
C2	0.5442 (4)	1.12383 (15)	−0.2993 (3)	0.0467 (8)
H2	0.4896	1.1406	−0.3733	0.056*
C3	0.6348 (4)	1.16232 (15)	−0.2090 (3)	0.0465 (8)
H3	0.6396	1.2052	−0.2219	0.056*
C4	0.7171 (4)	1.13728 (14)	−0.1010 (3)	0.0448 (7)
H4	0.7791	1.1626	−0.0400	0.054*
C5	0.7062 (4)	1.07333 (14)	−0.0843 (2)	0.0383 (7)
N2	0.7867 (4)	1.04376 (12)	0.0205 (2)	0.0426 (6)
N3	0.7675 (3)	0.98290 (11)	0.0249 (2)	0.0416 (6)
C6	0.8345 (4)	0.95095 (13)	0.1231 (2)	0.0361 (6)
C7	0.9312 (4)	0.97440 (14)	0.2352 (2)	0.0423 (7)
H7	0.9528	1.0171	0.2442	0.051*
C8	0.9916 (4)	0.93585 (15)	0.3278 (3)	0.0452 (7)
H8	1.0536	0.9524	0.4000	0.054*
C9	0.9629 (4)	0.86986 (15)	0.3183 (3)	0.0430 (7)
C10	0.8646 (5)	0.84604 (15)	0.2046 (3)	0.0500 (8)
H10	0.8424	0.8034	0.1953	0.060*
C11	0.8059 (4)	0.88491 (14)	0.1132 (3)	0.0451 (7)
H11	0.7444	0.8686	0.0406	0.054*
N4	1.0275 (4)	0.83274 (14)	0.4091 (2)	0.0580 (8)
C12	1.1324 (6)	0.8561 (2)	0.5244 (3)	0.0789 (13)
H12A	1.2590	0.8583	0.5181	0.118*
H12B	1.1169	0.8281	0.5890	0.118*
H12C	1.0894	0.8969	0.5411	0.118*
C13	1.0056 (8)	0.7651 (2)	0.4030 (4)	0.1017 (17)
H13A	1.0638	0.7489	0.3394	0.152*
H13B	0.8784	0.7549	0.3867	0.152*
H13C	1.0604	0.7470	0.4790	0.152*

	U11	U22	U33	U12	U13	U23
Zn1	0.0420 (2)	0.0397 (2)	0.0336 (2)	0.00047 (15)	0.00148 (14)	−0.00352 (14)
Cl1	0.0547 (5)	0.0528 (5)	0.0623 (5)	−0.0067 (4)	0.0225 (4)	−0.0154 (4)
Cl2	0.0582 (5)	0.0471 (4)	0.0393 (4)	−0.0050 (4)	−0.0010 (3)	0.0049 (3)
Cl3	0.0521 (5)	0.0764 (6)	0.0420 (4)	−0.0008 (4)	−0.0100 (4)	0.0068 (4)
Cl4	0.0763 (6)	0.0344 (4)	0.0496 (4)	0.0049 (4)	−0.0055 (4)	−0.0063 (3)
N1	0.0417 (14)	0.0384 (14)	0.0374 (13)	0.0002 (11)	0.0067 (11)	−0.0037 (11)
C1	0.0406 (17)	0.0515 (18)	0.0347 (15)	0.0010 (14)	0.0015 (13)	−0.0043 (14)
C2	0.0456 (18)	0.058 (2)	0.0344 (16)	0.0057 (15)	0.0001 (14)	0.0040 (14)
C3	0.0498 (19)	0.0415 (17)	0.0477 (18)	−0.0028 (14)	0.0068 (15)	0.0051 (14)
C4	0.0456 (18)	0.0466 (18)	0.0398 (17)	−0.0047 (14)	0.0008 (14)	−0.0094 (14)
C5	0.0327 (15)	0.0524 (18)	0.0297 (14)	0.0057 (13)	0.0054 (12)	0.0029 (13)
N2	0.0463 (15)	0.0449 (15)	0.0353 (14)	0.0000 (12)	0.0033 (11)	−0.0046 (11)
N3	0.0438 (15)	0.0418 (14)	0.0394 (13)	0.0019 (11)	0.0084 (11)	−0.0007 (11)
C6	0.0349 (15)	0.0420 (16)	0.0326 (14)	0.0010 (12)	0.0092 (12)	−0.0003 (12)
C7	0.0467 (18)	0.0425 (16)	0.0374 (16)	−0.0050 (14)	0.0064 (13)	−0.0020 (13)
C8	0.0451 (18)	0.0538 (19)	0.0355 (16)	−0.0011 (15)	0.0034 (14)	−0.0026 (14)
C9	0.0403 (17)	0.0527 (18)	0.0387 (16)	0.0078 (14)	0.0141 (14)	0.0064 (14)
C10	0.061 (2)	0.0394 (17)	0.0510 (19)	−0.0001 (15)	0.0144 (17)	−0.0018 (15)
C11	0.0525 (19)	0.0450 (17)	0.0367 (16)	−0.0015 (14)	0.0048 (14)	−0.0056 (14)
N4	0.0671 (19)	0.0623 (18)	0.0488 (16)	0.0211 (15)	0.0216 (15)	0.0134 (14)
C12	0.086 (3)	0.107 (3)	0.042 (2)	0.045 (3)	0.004 (2)	0.017 (2)
C13	0.166 (5)	0.062 (3)	0.081 (3)	0.032 (3)	0.033 (3)	0.031 (2)

Zn1—Cl4	2.2508 (8)	C6—C7	1.427 (4)
Zn1—Cl2	2.2539 (8)	C6—C11	1.431 (4)
Zn1—Cl3	2.2766 (8)	C7—C8	1.341 (4)
Zn1—Cl1	2.2815 (9)	C7—H7	0.9300
N1—C1	1.332 (4)	C8—C9	1.430 (4)
N1—C5	1.338 (4)	C8—H8	0.9300
N1—H1A	0.889 (17)	C9—N4	1.314 (4)
C1—C2	1.352 (4)	C9—C10	1.448 (4)
C1—H1	0.9300	C10—C11	1.333 (4)
C2—C3	1.387 (4)	C10—H10	0.9300
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.368 (4)	N4—C13	1.458 (5)
C3—H3	0.9300	N4—C12	1.476 (5)
C4—C5	1.386 (4)	C12—H12A	0.9600
C4—H4	0.9300	C12—H12B	0.9600
C5—N2	1.376 (4)	C12—H12C	0.9600
N2—N3	1.313 (3)	C13—H13A	0.9600
N2—H2A	0.901 (18)	C13—H13B	0.9600
N3—C6	1.318 (4)	C13—H13C	0.9600
Cl4—Zn1—Cl2	108.19 (3)	C8—C7—C6	121.0 (3)
Cl4—Zn1—Cl3	111.53 (3)	C8—C7—H7	119.5
Cl2—Zn1—Cl3	109.32 (3)	C6—C7—H7	119.5
Cl4—Zn1—Cl1	109.38 (4)	C7—C8—C9	121.7 (3)
Cl2—Zn1—Cl1	109.43 (3)	C7—C8—H8	119.2
Cl3—Zn1—Cl1	108.95 (4)	C9—C8—H8	119.2
C1—N1—C5	122.5 (3)	N4—C9—C8	120.7 (3)
C1—N1—H1A	121 (2)	N4—C9—C10	122.0 (3)
C5—N1—H1A	117 (2)	C8—C9—C10	117.4 (3)
N1—C1—C2	119.9 (3)	C11—C10—C9	120.3 (3)
N1—C1—H1	120.1	C11—C10—H10	119.8
C2—C1—H1	120.1	C9—C10—H10	119.8
C1—C2—C3	119.5 (3)	C10—C11—C6	122.2 (3)
C1—C2—H2	120.2	C10—C11—H11	118.9
C3—C2—H2	120.2	C6—C11—H11	118.9
C4—C3—C2	120.0 (3)	C9—N4—C13	122.8 (3)
C4—C3—H3	120.0	C9—N4—C12	122.7 (3)
C2—C3—H3	120.0	C13—N4—C12	114.5 (3)
C3—C4—C5	118.6 (3)	N4—C12—H12A	109.5
C3—C4—H4	120.7	N4—C12—H12B	109.5
C5—C4—H4	120.7	H12A—C12—H12B	109.5
N1—C5—N2	117.7 (3)	N4—C12—H12C	109.5
N1—C5—C4	119.5 (3)	H12A—C12—H12C	109.5
N2—C5—C4	122.8 (3)	H12B—C12—H12C	109.5
N3—N2—C5	117.0 (2)	N4—C13—H13A	109.5
N3—N2—H2A	129 (2)	N4—C13—H13B	109.5
C5—N2—H2A	114 (2)	H13A—C13—H13B	109.5
N2—N3—C6	121.2 (2)	N4—C13—H13C	109.5
N3—C6—C7	127.8 (3)	H13A—C13—H13C	109.5
N3—C6—C11	114.7 (3)	H13B—C13—H13C	109.5
C7—C6—C11	117.5 (3)
C5—N1—C1—C2	−1.4 (5)	C11—C6—C7—C8	−0.5 (4)
N1—C1—C2—C3	0.0 (5)	C6—C7—C8—C9	0.4 (5)
C1—C2—C3—C4	1.0 (5)	C7—C8—C9—N4	178.2 (3)
C2—C3—C4—C5	−0.5 (5)	C7—C8—C9—C10	−0.4 (5)
C1—N1—C5—N2	−178.1 (3)	N4—C9—C10—C11	−177.9 (3)
C1—N1—C5—C4	1.8 (4)	C8—C9—C10—C11	0.6 (5)
C3—C4—C5—N1	−0.8 (5)	C9—C10—C11—C6	−0.8 (5)
C3—C4—C5—N2	179.1 (3)	N3—C6—C11—C10	−179.7 (3)
N1—C5—N2—N3	0.4 (4)	C7—C6—C11—C10	0.7 (5)
C4—C5—N2—N3	−179.5 (3)	C8—C9—N4—C13	−178.5 (4)
C5—N2—N3—C6	−177.6 (3)	C10—C9—N4—C13	−0.1 (5)
N2—N3—C6—C7	0.7 (5)	C8—C9—N4—C12	−0.2 (5)
N2—N3—C6—C11	−178.8 (3)	C10—C9—N4—C12	178.2 (3)
N3—C6—C7—C8	−180.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N3	0.89 (2)	2.21 (3)	2.595 (3)	106 (2)
N2—H2A···Cl3i	0.90 (2)	2.45 (2)	3.322 (3)	165 (3)
N1—H1A···Cl1ii	0.89 (2)	2.37 (2)	3.173 (3)	150 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N3	0.89 (2)	2.21 (3)	2.595 (3)	106 (2)
N2—H2A⋯Cl3i	0.90 (2)	2.45 (2)	3.322 (3)	165 (3)
N1—H1A⋯Cl1ii	0.89 (2)	2.37 (2)	3.173 (3)	150 (3)

Symmetry codes: (i) ; (ii) .