Dichlorido[2-(3,5-dimethyl-1H-pyrazol-1-yl-κN)ethanamine-κN]zinc(II).

The amine title complex, [ZnCl(2)(C(7)H(13)N(3))], resulted from imine hydrolysis in a Schiff base compound. The Zn metal atom has a distorted tetra-hedral geometry with the most significant deviation identified in the magnitude of the N-Zn-N angle. This deviation stems from the participation of the Zn and N atoms in a six-membered metallocyclic ring. The latter is in an approximate screw-boat conformation. Two strong N-H⋯Cl hydrogen bonds link the mol-ecules into ribbons propagating along the b-axis direction. The ribbons contain two second-order hydrogen-bonded motifs: a chain and a ring. The chain described by the graph set notation C(2) (2)(6) is formed by one hydrogen bond going in the forward direction (donor to acceptor) and the other in the backward direction (acceptor to donor). In the ring motif R(2) (2)(8), both hydrogen bonds propagate in the forward direction.

Related literature

For imine hydrolysis in Schiff base compounds, see: Guzei et al. (2010 ▶); Czaun et al. (2010 ▶); Bu et al. (1997 ▶); Koner & Ray (2008 ▶); Sinha et al. (2003 ▶). For graph-set analysis, see: Bernstein et al. (1995 ▶). Related structures were found from the Cambridge Structural Database (Allen, 2002 ▶). Bond distances and angles were confirmed to be typical by a Mogul structural check (Bruno et al., 2002 ▶). For ring analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

[ZnCl2(C7n class="Species">H13N3)]

M = 275.47

Monoclinic,

a = 9.060 (3) Å

b = 8.894 (2) Å

c = 14.260 (4) Å

β = 97.95 (3)°

V = 1138.1 (6) Å3

Z = 4

Cu Kα radiation

μ = 7.00 mm−1

T = 100 K

0.48 × 0.28 × 0.21 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.134, T max = 0.321

16711 measured reflections

2123 independent reflections

2053 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.051

S = 1.03

2123 reflections

120 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −0.19 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL, FCF_filter (Guzei, 2007 ▶) and INSerter (Guzei, 2007 ▶); molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL, publCIF (Westrip, 2010 ▶) and modiCIFer (Guzei, 2007 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811044217/zq2129sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044217/zq2129Isup2.hkl

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

[ZnCl2(C7H13N3)]	F(000) = 560
Mr = 275.47	Dx = 1.608 Mg m−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2yn	Cell parameters from 9893 reflections
a = 9.060 (3) Å	θ = 4.9–69.5°
b = 8.894 (2) Å	µ = 7.00 mm−1
c = 14.260 (4) Å	T = 100 K
β = 97.95 (3)°	Block, colourless
V = 1138.1 (6) Å3	0.48 × 0.28 × 0.21 mm
Z = 4

Bruker SMART APEXII area-detector diffractometer	2123 independent reflections
Radiation source: fine-focus sealed tube	2053 reflections with I > 2σ(I)
graphite	Rint = 0.019
0.50° ω and 0.5 ° φ scans	θmax = 70.0°, θmin = 5.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
Tmin = 0.134, Tmax = 0.321	k = −10→10
16711 measured reflections	l = −17→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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.051	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.030P)2 + 0.6489P] where P = (Fo2 + 2Fc2)/3
2123 reflections	(Δ/σ)max = 0.001
120 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.19 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
Zn1	0.57494 (2)	0.15806 (2)	0.280022 (13)	0.01647 (8)
Cl1	0.48746 (4)	−0.06529 (4)	0.22820 (3)	0.02530 (10)
Cl2	0.53128 (4)	0.33130 (4)	0.16443 (3)	0.02379 (10)
N1	0.50886 (14)	0.22053 (14)	0.40401 (8)	0.0181 (3)
N2	0.60299 (14)	0.29662 (15)	0.47094 (9)	0.0190 (3)
N3	0.79922 (14)	0.16142 (14)	0.32554 (9)	0.0197 (3)
H3A	0.8369	0.0670	0.3173	0.030*
H3B	0.8433	0.2264	0.2876	0.030*
C1	0.25483 (18)	0.1137 (2)	0.38927 (12)	0.0251 (3)
H1A	0.2064	0.1791	0.3389	0.030*
H1C	0.1835	0.0876	0.4324	0.030*
H1B	0.2894	0.0217	0.3613	0.030*
C2	0.38499 (17)	0.19396 (18)	0.44299 (11)	0.0198 (3)
C3	0.40007 (18)	0.25371 (18)	0.53388 (11)	0.0226 (3)
H3	0.3282	0.2508	0.5765	0.027*
C4	0.54005 (18)	0.31816 (18)	0.55017 (11)	0.0213 (3)
C5	0.61843 (19)	0.3966 (2)	0.63528 (11)	0.0263 (3)
H5B	0.5498	0.4094	0.6821	0.032*
H5A	0.6527	0.4953	0.6168	0.032*
H5C	0.7042	0.3364	0.6628	0.032*
C6	0.75227 (18)	0.33978 (18)	0.45274 (12)	0.0229 (3)
H6B	0.8057	0.3882	0.5101	0.027*
H6A	0.7433	0.4145	0.4008	0.027*
C7	0.84300 (17)	0.2068 (2)	0.42600 (11)	0.0233 (3)
H7B	0.9501	0.2336	0.4360	0.028*
H7A	0.8286	0.1207	0.4678	0.028*

	U11	U22	U33	U12	U13	U23
Zn1	0.01851 (12)	0.01557 (12)	0.01536 (12)	0.00055 (7)	0.00246 (8)	−0.00065 (7)
Cl1	0.02428 (19)	0.01691 (18)	0.0344 (2)	−0.00008 (14)	0.00302 (15)	−0.00614 (15)
Cl2	0.0279 (2)	0.02177 (19)	0.02037 (19)	−0.00225 (14)	−0.00132 (15)	0.00530 (13)
N1	0.0190 (6)	0.0199 (7)	0.0151 (6)	−0.0028 (5)	0.0018 (5)	−0.0018 (5)
N2	0.0185 (6)	0.0220 (6)	0.0164 (6)	−0.0032 (5)	0.0024 (5)	−0.0029 (5)
N3	0.0200 (6)	0.0183 (7)	0.0213 (7)	0.0008 (5)	0.0043 (5)	0.0008 (5)
C1	0.0209 (8)	0.0301 (9)	0.0247 (8)	−0.0056 (7)	0.0044 (6)	−0.0018 (7)
C2	0.0202 (7)	0.0201 (7)	0.0190 (7)	0.0001 (6)	0.0030 (6)	0.0031 (6)
C3	0.0240 (8)	0.0268 (8)	0.0181 (7)	−0.0012 (6)	0.0066 (6)	0.0011 (6)
C4	0.0247 (8)	0.0220 (7)	0.0173 (7)	0.0012 (6)	0.0036 (6)	0.0004 (6)
C5	0.0296 (8)	0.0311 (9)	0.0182 (7)	−0.0024 (7)	0.0036 (6)	−0.0043 (7)
C6	0.0198 (8)	0.0282 (9)	0.0211 (8)	−0.0062 (6)	0.0041 (6)	−0.0037 (6)
C7	0.0186 (7)	0.0313 (9)	0.0197 (7)	0.0020 (6)	0.0011 (6)	0.0022 (7)

Zn1—N1	2.0214 (13)	C1—H1B	0.9800
Zn1—N3	2.0461 (14)	C2—C3	1.390 (2)
Zn1—Cl1	2.2266 (6)	C3—C4	1.382 (2)
Zn1—Cl2	2.2512 (6)	C3—H3	0.9500
N1—C2	1.340 (2)	C4—C5	1.492 (2)
N1—N2	1.3679 (18)	C5—H5B	0.9800
N2—C4	1.348 (2)	C5—H5A	0.9800
N2—C6	1.463 (2)	C5—H5C	0.9800
N3—C7	1.489 (2)	C6—C7	1.519 (2)
N3—H3A	0.9200	C6—H6B	0.9900
N3—H3B	0.9200	C6—H6A	0.9900
C1—C2	1.496 (2)	C7—H7B	0.9900
C1—H1A	0.9800	C7—H7A	0.9900
C1—H1C	0.9800
N1—Zn1—N3	96.88 (6)	C3—C2—C1	128.97 (14)
N1—Zn1—Cl1	113.62 (4)	C4—C3—C2	106.55 (14)
N3—Zn1—Cl1	114.24 (4)	C4—C3—H3	126.7
N1—Zn1—Cl2	114.15 (4)	C2—C3—H3	126.7
N3—Zn1—Cl2	106.77 (4)	N2—C4—C3	106.56 (14)
Cl1—Zn1—Cl2	110.44 (3)	N2—C4—C5	122.65 (14)
C2—N1—N2	105.95 (12)	C3—C4—C5	130.79 (15)
C2—N1—Zn1	132.88 (11)	C4—C5—H5B	109.5
N2—N1—Zn1	120.99 (10)	C4—C5—H5A	109.5
C4—N2—N1	111.10 (13)	H5B—C5—H5A	109.5
C4—N2—C6	128.32 (13)	C4—C5—H5C	109.5
N1—N2—C6	120.56 (12)	H5B—C5—H5C	109.5
C7—N3—Zn1	115.47 (10)	H5A—C5—H5C	109.5
C7—N3—H3A	108.4	N2—C6—C7	112.70 (13)
Zn1—N3—H3A	108.4	N2—C6—H6B	109.1
C7—N3—H3B	108.4	C7—C6—H6B	109.1
Zn1—N3—H3B	108.4	N2—C6—H6A	109.1
H3A—N3—H3B	107.5	C7—C6—H6A	109.1
C2—C1—H1A	109.5	H6B—C6—H6A	107.8
C2—C1—H1C	109.5	N3—C7—C6	111.80 (13)
H1A—C1—H1C	109.5	N3—C7—H7B	109.3
C2—C1—H1B	109.5	C6—C7—H7B	109.3
H1A—C1—H1B	109.5	N3—C7—H7A	109.3
H1C—C1—H1B	109.5	C6—C7—H7A	109.3
N1—C2—C3	109.84 (14)	H7B—C7—H7A	107.9
N1—C2—C1	121.18 (14)
N3—Zn1—N1—C2	−151.81 (14)	N2—N1—C2—C1	179.17 (14)
Cl1—Zn1—N1—C2	−31.54 (15)	Zn1—N1—C2—C1	−5.9 (2)
Cl2—Zn1—N1—C2	96.31 (14)	N1—C2—C3—C4	−0.41 (18)
N3—Zn1—N1—N2	22.52 (12)	C1—C2—C3—C4	−179.06 (16)
Cl1—Zn1—N1—N2	142.79 (10)	N1—N2—C4—C3	−0.02 (18)
Cl2—Zn1—N1—N2	−89.35 (11)	C6—N2—C4—C3	−178.15 (15)
C2—N1—N2—C4	−0.23 (17)	N1—N2—C4—C5	179.25 (14)
Zn1—N1—N2—C4	−175.91 (10)	C6—N2—C4—C5	1.1 (3)
C2—N1—N2—C6	178.07 (13)	C2—C3—C4—N2	0.25 (18)
Zn1—N1—N2—C6	2.38 (18)	C2—C3—C4—C5	−178.94 (17)
N1—Zn1—N3—C7	−0.89 (11)	C4—N2—C6—C7	122.45 (17)
Cl1—Zn1—N3—C7	−120.69 (10)	N1—N2—C6—C7	−55.52 (19)
Cl2—Zn1—N3—C7	116.93 (10)	Zn1—N3—C7—C6	−42.60 (16)
N2—N1—C2—C3	0.39 (17)	N2—C6—C7—N3	78.30 (17)
Zn1—N1—C2—C3	175.34 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl2i	0.92	2.41	3.3073 (15)	165.
N3—H3B···Cl1ii	0.92	2.43	3.2620 (15)	150.

Zn1—N1	2.0214 (13)
Zn1—N3	2.0461 (14)
Zn1—Cl1	2.2266 (6)
Zn1—Cl2	2.2512 (6)

N1—Zn1—N3	96.88 (6)
N1—Zn1—Cl1	113.62 (4)
N3—Zn1—Cl1	114.24 (4)
N1—Zn1—Cl2	114.15 (4)
N3—Zn1—Cl2	106.77 (4)
Cl1—Zn1—Cl2	110.44 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl2i	0.92	2.41	3.3073 (15)	165
N3—H3B⋯Cl1ii	0.92	2.43	3.2620 (15)	150

Symmetry codes: (i) ; (ii) .