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

The Zn(II) atom in the title compound, [ZnCl(2)(C(14)H(13)N(3))], is coordinated by a Cl(2)N(2) donor set defined by quinoline and pyrazole N atoms of the chelating ligand and two Cl atoms. Distortions from the ideal tetra-hedral geometry relate to the restricted bite angle of the chelating ligand [N-Zn-N = 78.54 (12)°]. In the crystal, mol-ecules are connected into a three-dimensional structure by C-H⋯Cl inter-actions, involving both Cl atoms, and π-π inter-actions that occur between the pyrazole ring and each of the pyridine and benzene rings of the quinoline residue [inter-centroid distances = 3.655 (2) and 3.676 (2) Å].

Related literature

For background to luminescent coordination complexes, see: Bai et al. (2012 ▶); Chou et al., (2011 ▶); Hu et al. (2011 ▶); Wang (2001 ▶). For the synthesis, see: Savel’eva et al. (2009 ▶); Scott et al. (1952 ▶).

Experimental

Crystal data

[ZnCl2(C14H13N3)]

M = 359.54

Monoclinic,

a = 14.3353 (10) Å

b = 8.7683 (5) Å

c = 11.9839 (8) Å

β = 102.181 (7)°

V = 1472.42 (17) Å3

Z = 4

Mo Kα radiation

μ = 2.02 mm−1

T = 100 K

0.25 × 0.20 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.597, T max = 1.000

6070 measured reflections

3370 independent reflections

2438 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.124

S = 1.02

3370 reflections

183 parameters

H-atom parameters constrained

Δρmax = 1.04 e Å−3

Δρmin = −0.66 e Å−3

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812014390/hg5206sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014390/hg5206Isup2.hkl

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

[ZnCl2(C14H13N3)]	F(000) = 728
Mr = 359.54	Dx = 1.622 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1666 reflections
a = 14.3353 (10) Å	θ = 2.5–27.5°
b = 8.7683 (5) Å	µ = 2.02 mm−1
c = 11.9839 (8) Å	T = 100 K
β = 102.181 (7)°	Plate, colourless
V = 1472.42 (17) Å3	0.25 × 0.20 × 0.02 mm
Z = 4

Agilent SuperNova Dual diffractometer with an Atlas detector	3370 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2438 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.047
Detector resolution: 10.4041 pixels mm-1	θmax = 27.6°, θmin = 2.7°
ω scan	h = −17→18
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→8
Tmin = 0.597, Tmax = 1.000	l = −9→15
6070 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0519P)2 + 0.2907P] where P = (Fo2 + 2Fc2)/3
3370 reflections	(Δ/σ)max = 0.001
183 parameters	Δρmax = 1.04 e Å−3
0 restraints	Δρmin = −0.66 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
Zn	0.26453 (3)	0.53715 (5)	0.58123 (4)	0.02140 (16)
Cl1	0.37804 (7)	0.65835 (11)	0.70222 (9)	0.0296 (3)
Cl2	0.14937 (7)	0.67975 (11)	0.48204 (9)	0.0300 (3)
N1	0.3193 (2)	0.3781 (3)	0.4912 (3)	0.0185 (7)
N3	0.2198 (2)	0.3372 (3)	0.6458 (3)	0.0179 (7)
C1	0.4079 (3)	0.5145 (4)	0.3689 (4)	0.0255 (9)
H1A	0.4758	0.5071	0.3671	0.038*
H1B	0.3979	0.6015	0.4163	0.038*
H1C	0.3706	0.5289	0.2911	0.038*
C2	0.3767 (3)	0.3710 (4)	0.4180 (3)	0.0194 (8)
C3	0.4000 (3)	0.2193 (4)	0.4009 (3)	0.0200 (8)
H3	0.4400	0.1841	0.3524	0.024*
C4	0.3546 (2)	0.1306 (4)	0.4674 (3)	0.0186 (8)
C5	0.3603 (3)	−0.0381 (4)	0.4822 (4)	0.0249 (9)
H5A	0.3798	−0.0626	0.5636	0.037*
H5B	0.4073	−0.0793	0.4415	0.037*
H5C	0.2977	−0.0833	0.4513	0.037*
C6	0.2458 (2)	0.2097 (4)	0.6031 (3)	0.0174 (8)
C7	0.2184 (3)	0.0628 (4)	0.6327 (3)	0.0189 (8)
H7A	0.2373	−0.0265	0.5984	0.023*
C8	0.1632 (3)	0.0549 (4)	0.7129 (3)	0.0207 (8)
H8A	0.1442	−0.0421	0.7358	0.025*
C9	0.1340 (2)	0.1877 (4)	0.7623 (3)	0.0186 (8)
C10	0.0765 (2)	0.1852 (4)	0.8457 (3)	0.0216 (8)
H10A	0.0563	0.0905	0.8710	0.026*
C11	0.0505 (3)	0.3181 (5)	0.8891 (3)	0.0243 (9)
H11A	0.0119	0.3161	0.9446	0.029*
C12	0.0805 (3)	0.4586 (4)	0.8521 (3)	0.0229 (9)
H12A	0.0617	0.5506	0.8830	0.027*
C13	0.1360 (3)	0.4656 (4)	0.7729 (3)	0.0222 (8)
H13A	0.1565	0.5614	0.7499	0.027*
C14	0.1628 (2)	0.3301 (4)	0.7257 (3)	0.0187 (8)
N2	0.3048 (2)	0.2299 (3)	0.5218 (3)	0.0173 (7)

	U11	U22	U33	U12	U13	U23
Zn	0.0306 (3)	0.0144 (2)	0.0210 (3)	−0.00055 (19)	0.00946 (19)	0.00027 (19)
Cl1	0.0423 (6)	0.0242 (5)	0.0237 (6)	−0.0104 (4)	0.0104 (4)	−0.0047 (4)
Cl2	0.0364 (6)	0.0193 (5)	0.0355 (6)	0.0071 (4)	0.0102 (5)	0.0038 (4)
N1	0.0250 (16)	0.0152 (16)	0.0151 (16)	−0.0005 (13)	0.0042 (13)	−0.0004 (13)
N3	0.0248 (16)	0.0180 (16)	0.0116 (16)	−0.0026 (13)	0.0054 (13)	−0.0017 (13)
C1	0.031 (2)	0.024 (2)	0.021 (2)	−0.0040 (18)	0.0050 (17)	0.0009 (17)
C2	0.0212 (18)	0.023 (2)	0.0139 (19)	−0.0034 (16)	0.0029 (15)	0.0013 (16)
C3	0.0205 (18)	0.024 (2)	0.0145 (19)	0.0024 (16)	0.0024 (14)	0.0005 (16)
C4	0.0213 (18)	0.0184 (19)	0.0154 (19)	0.0020 (16)	0.0025 (15)	−0.0039 (16)
C5	0.033 (2)	0.017 (2)	0.028 (2)	0.0027 (17)	0.0137 (18)	0.0029 (17)
C6	0.0211 (19)	0.0185 (19)	0.0113 (19)	−0.0014 (16)	0.0004 (14)	−0.0012 (15)
C7	0.0243 (19)	0.0157 (18)	0.0168 (19)	−0.0003 (16)	0.0047 (15)	−0.0017 (15)
C8	0.027 (2)	0.0168 (19)	0.019 (2)	−0.0016 (16)	0.0064 (16)	0.0047 (16)
C9	0.0199 (18)	0.0198 (19)	0.0149 (19)	−0.0009 (16)	0.0011 (14)	0.0004 (16)
C10	0.024 (2)	0.023 (2)	0.018 (2)	−0.0061 (16)	0.0044 (16)	0.0004 (17)
C11	0.024 (2)	0.033 (2)	0.018 (2)	−0.0044 (18)	0.0078 (16)	−0.0030 (18)
C12	0.0244 (19)	0.025 (2)	0.019 (2)	0.0049 (17)	0.0024 (16)	−0.0033 (17)
C13	0.0230 (19)	0.023 (2)	0.020 (2)	−0.0048 (17)	0.0036 (16)	0.0005 (17)
C14	0.0191 (18)	0.0210 (19)	0.0153 (19)	0.0005 (16)	0.0020 (15)	0.0021 (16)
N2	0.0230 (16)	0.0139 (15)	0.0152 (16)	−0.0003 (13)	0.0039 (13)	0.0007 (13)

Zn—N1	2.021 (3)	C5—H5B	0.9800
Zn—N3	2.072 (3)	C5—H5C	0.9800
Zn—Cl1	2.2099 (11)	C6—C7	1.414 (5)
Zn—Cl2	2.2076 (11)	C6—N2	1.429 (5)
N1—C2	1.325 (5)	C7—C8	1.370 (5)
N1—N2	1.378 (4)	C7—H7A	0.9500
N3—C6	1.316 (5)	C8—C9	1.409 (5)
N3—C14	1.385 (5)	C8—H8A	0.9500
C1—C2	1.497 (5)	C9—C14	1.414 (5)
C1—H1A	0.9800	C9—C10	1.423 (5)
C1—H1B	0.9800	C10—C11	1.361 (5)
C1—H1C	0.9800	C10—H10A	0.9500
C2—C3	1.397 (5)	C11—C12	1.407 (5)
C3—C4	1.373 (5)	C11—H11A	0.9500
C3—H3	0.9500	C12—C13	1.362 (5)
C4—N2	1.375 (4)	C12—H12A	0.9500
C4—C5	1.490 (5)	C13—C14	1.403 (5)
C5—H5A	0.9800	C13—H13A	0.9500
N1—Zn—N3	78.54 (12)	H5B—C5—H5C	109.5
N1—Zn—Cl2	115.73 (9)	N3—C6—C7	124.0 (3)
N3—Zn—Cl2	115.15 (9)	N3—C6—N2	114.6 (3)
N1—Zn—Cl1	111.52 (9)	C7—C6—N2	121.3 (3)
N3—Zn—Cl1	113.89 (9)	C8—C7—C6	117.0 (3)
Cl2—Zn—Cl1	116.38 (4)	C8—C7—H7A	121.5
C2—N1—N2	106.4 (3)	C6—C7—H7A	121.5
C2—N1—Zn	138.7 (3)	C7—C8—C9	121.3 (3)
N2—N1—Zn	114.3 (2)	C7—C8—H8A	119.3
C6—N3—C14	119.2 (3)	C9—C8—H8A	119.3
C6—N3—Zn	116.0 (2)	C8—C9—C14	117.9 (3)
C14—N3—Zn	124.8 (2)	C8—C9—C10	123.3 (3)
C2—C1—H1A	109.5	C14—C9—C10	118.8 (3)
C2—C1—H1B	109.5	C11—C10—C9	120.1 (4)
H1A—C1—H1B	109.5	C11—C10—H10A	119.9
C2—C1—H1C	109.5	C9—C10—H10A	119.9
H1A—C1—H1C	109.5	C10—C11—C12	120.2 (4)
H1B—C1—H1C	109.5	C10—C11—H11A	119.9
N1—C2—C3	110.0 (3)	C12—C11—H11A	119.9
N1—C2—C1	120.0 (3)	C13—C12—C11	121.4 (4)
C3—C2—C1	129.9 (3)	C13—C12—H12A	119.3
C4—C3—C2	107.3 (3)	C11—C12—H12A	119.3
C4—C3—H3	126.3	C12—C13—C14	119.5 (4)
C2—C3—H3	126.3	C12—C13—H13A	120.3
C3—C4—N2	105.9 (3)	C14—C13—H13A	120.3
C3—C4—C5	127.7 (3)	N3—C14—C13	119.5 (3)
N2—C4—C5	126.4 (3)	N3—C14—C9	120.5 (3)
C4—C5—H5A	109.5	C13—C14—C9	120.0 (3)
C4—C5—H5B	109.5	C4—N2—N1	110.4 (3)
H5A—C5—H5B	109.5	C4—N2—C6	133.3 (3)
C4—C5—H5C	109.5	N1—N2—C6	116.3 (3)
H5A—C5—H5C	109.5
N3—Zn—N1—C2	−172.9 (4)	C7—C8—C9—C10	179.8 (4)
Cl2—Zn—N1—C2	74.6 (4)	C8—C9—C10—C11	−179.6 (3)
Cl1—Zn—N1—C2	−61.5 (4)	C14—C9—C10—C11	−0.2 (5)
N3—Zn—N1—N2	−3.5 (2)	C9—C10—C11—C12	−0.2 (5)
Cl2—Zn—N1—N2	−116.1 (2)	C10—C11—C12—C13	−0.2 (6)
Cl1—Zn—N1—N2	107.8 (2)	C11—C12—C13—C14	1.0 (6)
N1—Zn—N3—C6	0.5 (2)	C6—N3—C14—C13	179.0 (3)
Cl2—Zn—N3—C6	113.7 (2)	Zn—N3—C14—C13	−3.6 (5)
Cl1—Zn—N3—C6	−108.2 (2)	C6—N3—C14—C9	0.9 (5)
N1—Zn—N3—C14	−177.0 (3)	Zn—N3—C14—C9	178.3 (2)
Cl2—Zn—N3—C14	−63.8 (3)	C12—C13—C14—N3	−179.5 (3)
Cl1—Zn—N3—C14	74.3 (3)	C12—C13—C14—C9	−1.5 (5)
N2—N1—C2—C3	−0.2 (4)	C8—C9—C14—N3	−1.5 (5)
Zn—N1—C2—C3	169.6 (3)	C10—C9—C14—N3	179.1 (3)
N2—N1—C2—C1	−179.2 (3)	C8—C9—C14—C13	−179.6 (3)
Zn—N1—C2—C1	−9.3 (6)	C10—C9—C14—C13	1.1 (5)
N1—C2—C3—C4	−0.1 (4)	C3—C4—N2—N1	−0.6 (4)
C1—C2—C3—C4	178.7 (4)	C5—C4—N2—N1	177.2 (3)
C2—C3—C4—N2	0.5 (4)	C3—C4—N2—C6	−178.4 (4)
C2—C3—C4—C5	−177.3 (4)	C5—C4—N2—C6	−0.6 (6)
C14—N3—C6—C7	0.7 (5)	C2—N1—N2—C4	0.5 (4)
Zn—N3—C6—C7	−176.9 (3)	Zn—N1—N2—C4	−172.2 (2)
C14—N3—C6—N2	−179.8 (3)	C2—N1—N2—C6	178.7 (3)
Zn—N3—C6—N2	2.6 (4)	Zn—N1—N2—C6	6.0 (4)
N3—C6—C7—C8	−1.7 (5)	N3—C6—N2—C4	172.0 (3)
N2—C6—C7—C8	178.9 (3)	C7—C6—N2—C4	−8.5 (6)
C6—C7—C8—C9	1.0 (6)	N3—C6—N2—N1	−5.7 (4)
C7—C8—C9—C14	0.5 (5)	C7—C6—N2—N1	173.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···Cl1i	0.98	2.81	3.680 (4)	148
C12—H12A···Cl2ii	0.95	2.82	3.579 (4)	138

Table 1

Selected bond lengths (Å)

Zn—N1	2.021 (3)
Zn—N3	2.072 (3)
Zn—Cl1	2.2099 (11)
Zn—Cl2	2.2076 (11)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯Cl1i	0.98	2.81	3.680 (4)	148
C12—H12A⋯Cl2ii	0.95	2.82	3.579 (4)	138

Symmetry codes: (i) ; (ii) .