{1,2-Bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN)meth-yl]benzene}-dichloridozinc(II).

The title zinc complex, [ZnCl(2)(C(18)H(22)N(4))], contains a bidentate 1,2-bis(3,5-dimethyl-1H-pyrazol-1-ylmeth-yl)benz-ene ligand that binds to the zinc atom, forming a nine-membered metallocyclic ring. The geometry about the Zn atom is distorted tetra-hedral, with the largest deviation observed in the magnitude of the Cl-Zn-Cl angle. Similar distortions are observed in the cobalt analogue and related zinc compounds containing metallocyclic rings with more than six members. The copper analogue exhibits a more severe distortion of the metal coordination sphere than is observed in the title compound.

Related literature

For the coordination modes of poly(pyrazol-1-ylmeth­yl)benzene see: Hartshorn & Steel (1995 ▶, 1997 ▶, 1998 ▶); Guerrero et al. (2002 ▶). For 1,2-bis(3,5-dimethyl-1H-pyrazol-1-ylmeth­yl)benzene complexes with palladium in square-planar coord­ination, see: Motsoane et al. (2007 ▶). For the cobalt and copper analogues, see: Chang et al. (1994 ▶). Discussion of the effect of the size of metallocyclic rings on the distortion of tetra­hedral dipyrazole dizinc complexes can be found in Guzei et al. (2011 ▶). Related structures were found in the Cambridge Structural Database (Allen, 2002 ▶). Bond lengths and angles were confirmed to be typical by a Mogul structural check (Bruno et al., 2002 ▶).

Experimental

Crystal data

[ZnCl2(C18H22N4)]

M = 430.67

Triclinic,

a = 9.0830 (8) Å

b = 10.6375 (9) Å

c = 11.9558 (10) Å

α = 111.853 (1)°

β = 95.476 (1)°

γ = 112.636 (1)°

V = 950.38 (14) Å3

Z = 2

Mo Kα radiation

μ = 1.58 mm−1

T = 100 K

0.43 × 0.32 × 0.28 mm

Data collection

Bruker CCD-1000 area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.550, T max = 0.666

13237 measured reflections

4672 independent reflections

4403 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.065

S = 1.04

4672 reflections

230 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL and FCF_filter (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/S1600536811046368/lr2035sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046368/lr2035Isup2.hkl

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

[ZnCl2(C18H22N4)]	Z = 2
Mr = 430.67	F(000) = 444
Triclinic, P1	Dx = 1.505 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0830 (8) Å	Cell parameters from 9448 reflections
b = 10.6375 (9) Å	θ = 2.3–28.3°
c = 11.9558 (10) Å	µ = 1.58 mm−1
α = 111.853 (1)°	T = 100 K
β = 95.476 (1)°	Block, colourless
γ = 112.636 (1)°	0.43 × 0.32 × 0.28 mm
V = 950.38 (14) Å3

Bruker CCD-1000 area-detector diffractometer	4672 independent reflections
Radiation source: fine-focus sealed tube	4403 reflections with I > 2σ(I)
graphite	Rint = 0.020
0.30° ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −12→12
Tmin = 0.550, Tmax = 0.666	k = −14→14
13237 measured reflections	l = −15→15

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.065	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0389P)2 + 0.3716P] where P = (Fo2 + 2Fc2)/3
4672 reflections	(Δ/σ)max = 0.001
230 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.23 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	0.447154 (17)	0.646823 (15)	0.225301 (13)	0.01268 (6)
Cl1	0.33460 (4)	0.70562 (4)	0.38540 (3)	0.01945 (8)
Cl2	0.36462 (4)	0.40099 (3)	0.11091 (3)	0.02033 (8)
N1	0.39991 (13)	0.75623 (12)	0.12959 (10)	0.0141 (2)
N2	0.45625 (13)	0.91072 (12)	0.18533 (10)	0.0134 (2)
N3	0.83014 (13)	0.82791 (12)	0.28085 (10)	0.0142 (2)
N4	0.69672 (13)	0.73599 (12)	0.30515 (10)	0.0150 (2)
C1	0.19365 (18)	0.53631 (16)	−0.06690 (14)	0.0231 (3)
H1A	0.1488	0.4774	−0.0211	0.035*
H1B	0.2708	0.5047	−0.1071	0.035*
H1C	0.1024	0.5183	−0.1311	0.035*
C2	0.28349 (16)	0.70176 (15)	0.02240 (12)	0.0168 (2)
C3	0.26618 (17)	0.82135 (16)	0.01074 (13)	0.0192 (3)
H3	0.1924	0.8139	−0.0560	0.023*
C4	0.37729 (16)	0.95269 (15)	0.11533 (13)	0.0164 (2)
C5	0.40993 (18)	1.11322 (16)	0.15328 (15)	0.0232 (3)
H5A	0.5219	1.1720	0.1503	0.035*
H5B	0.4011	1.1574	0.2388	0.035*
H5C	0.3282	1.1160	0.0957	0.035*
C6	0.58545 (15)	1.01004 (14)	0.30583 (12)	0.0141 (2)
H6A	0.6018	0.9463	0.3438	0.017*
H6B	0.5468	1.0772	0.3633	0.017*
C7	0.75061 (15)	1.10757 (14)	0.29404 (12)	0.0141 (2)
C8	0.80300 (17)	1.26401 (15)	0.34196 (12)	0.0170 (2)
H8	0.7353	1.3055	0.3812	0.020*
C9	0.95267 (17)	1.36036 (15)	0.33336 (13)	0.0194 (3)
H9	0.9869	1.4666	0.3671	0.023*
C10	1.05119 (16)	1.30043 (16)	0.27536 (13)	0.0198 (3)
H10	1.1526	1.3650	0.2679	0.024*
C11	1.00063 (16)	1.14496 (15)	0.22812 (13)	0.0177 (2)
H11	1.0685	1.1044	0.1881	0.021*
C12	0.85275 (15)	1.04717 (14)	0.23806 (12)	0.0145 (2)
C13	0.80739 (16)	0.87931 (14)	0.18550 (12)	0.0146 (2)
H13A	0.6897	0.8196	0.1348	0.017*
H13B	0.8760	0.8575	0.1286	0.017*
C14	1.13949 (17)	0.93722 (17)	0.33455 (15)	0.0228 (3)
H14A	1.1667	1.0453	0.3732	0.034*
H14B	1.1362	0.9036	0.2457	0.034*
H14C	1.2243	0.9222	0.3773	0.034*
C15	0.97434 (16)	0.84694 (15)	0.34583 (13)	0.0167 (2)
C16	0.93254 (17)	0.76621 (15)	0.41487 (13)	0.0183 (3)
H16	1.0067	0.7584	0.4705	0.022*
C17	0.75974 (17)	0.69826 (15)	0.38680 (13)	0.0172 (2)
C18	0.65037 (18)	0.59516 (17)	0.43404 (15)	0.0236 (3)
H18A	0.5678	0.5006	0.3627	0.035*
H18B	0.5936	0.6454	0.4858	0.035*
H18C	0.7181	0.5720	0.4846	0.035*

	U11	U22	U33	U12	U13	U23
Zn1	0.01343 (8)	0.01059 (8)	0.01304 (9)	0.00483 (6)	0.00326 (6)	0.00506 (6)
Cl1	0.02365 (16)	0.01755 (15)	0.01855 (16)	0.00964 (13)	0.01082 (12)	0.00796 (12)
Cl2	0.02673 (17)	0.01197 (14)	0.01843 (16)	0.00796 (12)	0.00488 (12)	0.00416 (12)
N1	0.0146 (5)	0.0122 (5)	0.0141 (5)	0.0056 (4)	0.0033 (4)	0.0052 (4)
N2	0.0134 (5)	0.0122 (5)	0.0146 (5)	0.0055 (4)	0.0036 (4)	0.0063 (4)
N3	0.0129 (5)	0.0140 (5)	0.0155 (5)	0.0060 (4)	0.0040 (4)	0.0065 (4)
N4	0.0142 (5)	0.0141 (5)	0.0162 (5)	0.0054 (4)	0.0039 (4)	0.0073 (4)
C1	0.0227 (7)	0.0197 (6)	0.0180 (7)	0.0080 (5)	−0.0017 (5)	0.0033 (5)
C2	0.0153 (6)	0.0196 (6)	0.0149 (6)	0.0076 (5)	0.0043 (5)	0.0073 (5)
C3	0.0184 (6)	0.0244 (7)	0.0179 (6)	0.0108 (5)	0.0040 (5)	0.0116 (5)
C4	0.0165 (6)	0.0199 (6)	0.0198 (6)	0.0107 (5)	0.0078 (5)	0.0127 (5)
C5	0.0228 (7)	0.0203 (6)	0.0342 (8)	0.0127 (6)	0.0092 (6)	0.0165 (6)
C6	0.0156 (6)	0.0126 (5)	0.0122 (5)	0.0053 (5)	0.0039 (4)	0.0051 (5)
C7	0.0144 (5)	0.0141 (5)	0.0122 (5)	0.0048 (5)	0.0022 (4)	0.0065 (5)
C8	0.0199 (6)	0.0152 (6)	0.0146 (6)	0.0068 (5)	0.0030 (5)	0.0069 (5)
C9	0.0218 (6)	0.0143 (6)	0.0171 (6)	0.0033 (5)	0.0011 (5)	0.0080 (5)
C10	0.0150 (6)	0.0197 (6)	0.0202 (6)	0.0015 (5)	0.0016 (5)	0.0120 (5)
C11	0.0150 (6)	0.0212 (6)	0.0174 (6)	0.0068 (5)	0.0037 (5)	0.0108 (5)
C12	0.0146 (6)	0.0150 (6)	0.0132 (6)	0.0054 (5)	0.0023 (4)	0.0074 (5)
C13	0.0150 (6)	0.0153 (6)	0.0137 (6)	0.0067 (5)	0.0044 (4)	0.0068 (5)
C14	0.0147 (6)	0.0255 (7)	0.0303 (8)	0.0095 (5)	0.0061 (5)	0.0141 (6)
C15	0.0146 (6)	0.0164 (6)	0.0180 (6)	0.0086 (5)	0.0027 (5)	0.0055 (5)
C16	0.0182 (6)	0.0174 (6)	0.0184 (6)	0.0093 (5)	0.0009 (5)	0.0068 (5)
C17	0.0196 (6)	0.0154 (6)	0.0160 (6)	0.0081 (5)	0.0031 (5)	0.0066 (5)
C18	0.0230 (7)	0.0250 (7)	0.0265 (7)	0.0085 (6)	0.0040 (5)	0.0183 (6)

Zn1—N1	2.0323 (11)	C6—H6B	0.9900
Zn1—N4	2.0512 (11)	C7—C8	1.3974 (17)
Zn1—Cl2	2.2145 (4)	C7—C12	1.4066 (18)
Zn1—Cl1	2.2526 (4)	C8—C9	1.3934 (19)
N1—C2	1.3466 (17)	C8—H8	0.9500
N1—N2	1.3707 (14)	C9—C10	1.384 (2)
N2—C4	1.3506 (16)	C9—H9	0.9500
N2—C6	1.4693 (16)	C10—C11	1.3912 (19)
N3—C15	1.3581 (16)	C10—H10	0.9500
N3—N4	1.3695 (15)	C11—C12	1.3954 (18)
N3—C13	1.4654 (16)	C11—H11	0.9500
N4—C17	1.3429 (17)	C12—C13	1.5173 (17)
C1—C2	1.4942 (19)	C13—H13A	0.9900
C1—H1A	0.9800	C13—H13B	0.9900
C1—H1B	0.9800	C14—C15	1.4889 (19)
C1—H1C	0.9800	C14—H14A	0.9800
C2—C3	1.3944 (19)	C14—H14B	0.9800
C3—C4	1.3810 (19)	C14—H14C	0.9800
C3—H3	0.9500	C15—C16	1.378 (2)
C4—C5	1.4892 (18)	C16—C17	1.3943 (19)
C5—H5A	0.9800	C16—H16	0.9500
C5—H5B	0.9800	C17—C18	1.4961 (19)
C5—H5C	0.9800	C18—H18A	0.9800
C6—C7	1.5159 (17)	C18—H18B	0.9800
C6—H6A	0.9900	C18—H18C	0.9800
N1—Zn1—N4	111.72 (4)	C8—C7—C12	119.12 (12)
N1—Zn1—Cl2	115.14 (3)	C8—C7—C6	118.15 (11)
N4—Zn1—Cl2	104.72 (3)	C12—C7—C6	122.74 (11)
N1—Zn1—Cl1	103.37 (3)	C9—C8—C7	121.27 (13)
N4—Zn1—Cl1	106.19 (3)	C9—C8—H8	119.4
Cl2—Zn1—Cl1	115.538 (13)	C7—C8—H8	119.4
C2—N1—N2	105.94 (10)	C10—C9—C8	119.63 (12)
C2—N1—Zn1	130.14 (9)	C10—C9—H9	120.2
N2—N1—Zn1	121.78 (8)	C8—C9—H9	120.2
C4—N2—N1	110.96 (10)	C9—C10—C11	119.51 (12)
C4—N2—C6	127.34 (11)	C9—C10—H10	120.2
N1—N2—C6	121.69 (10)	C11—C10—H10	120.2
C15—N3—N4	110.72 (11)	C10—C11—C12	121.65 (13)
C15—N3—C13	127.79 (11)	C10—C11—H11	119.2
N4—N3—C13	121.15 (10)	C12—C11—H11	119.2
C17—N4—N3	105.97 (10)	C11—C12—C7	118.78 (12)
C17—N4—Zn1	123.61 (9)	C11—C12—C13	118.43 (11)
N3—N4—Zn1	130.10 (8)	C7—C12—C13	122.78 (11)
C2—C1—H1A	109.5	N3—C13—C12	114.37 (10)
C2—C1—H1B	109.5	N3—C13—H13A	108.7
H1A—C1—H1B	109.5	C12—C13—H13A	108.7
C2—C1—H1C	109.5	N3—C13—H13B	108.7
H1A—C1—H1C	109.5	C12—C13—H13B	108.7
H1B—C1—H1C	109.5	H13A—C13—H13B	107.6
N1—C2—C3	109.73 (12)	C15—C14—H14A	109.5
N1—C2—C1	122.31 (12)	C15—C14—H14B	109.5
C3—C2—C1	127.95 (12)	H14A—C14—H14B	109.5
C4—C3—C2	106.51 (12)	C15—C14—H14C	109.5
C4—C3—H3	126.7	H14A—C14—H14C	109.5
C2—C3—H3	126.7	H14B—C14—H14C	109.5
N2—C4—C3	106.85 (11)	N3—C15—C16	106.88 (12)
N2—C4—C5	123.21 (12)	N3—C15—C14	122.67 (12)
C3—C4—C5	129.92 (13)	C16—C15—C14	130.42 (12)
C4—C5—H5A	109.5	C15—C16—C17	106.36 (12)
C4—C5—H5B	109.5	C15—C16—H16	126.8
H5A—C5—H5B	109.5	C17—C16—H16	126.8
C4—C5—H5C	109.5	N4—C17—C16	110.06 (12)
H5A—C5—H5C	109.5	N4—C17—C18	121.69 (12)
H5B—C5—H5C	109.5	C16—C17—C18	128.24 (12)
N2—C6—C7	113.37 (10)	C17—C18—H18A	109.5
N2—C6—H6A	108.9	C17—C18—H18B	109.5
C7—C6—H6A	108.9	H18A—C18—H18B	109.5
N2—C6—H6B	108.9	C17—C18—H18C	109.5
C7—C6—H6B	108.9	H18A—C18—H18C	109.5
H6A—C6—H6B	107.7	H18B—C18—H18C	109.5
N4—Zn1—N1—C2	144.03 (11)	C4—N2—C6—C7	−71.13 (16)
Cl2—Zn1—N1—C2	24.75 (12)	N1—N2—C6—C7	109.17 (12)
Cl1—Zn1—N1—C2	−102.19 (11)	N2—C6—C7—C8	109.89 (13)
N4—Zn1—N1—N2	−55.03 (10)	N2—C6—C7—C12	−70.62 (15)
Cl2—Zn1—N1—N2	−174.31 (8)	C12—C7—C8—C9	1.10 (19)
Cl1—Zn1—N1—N2	58.75 (9)	C6—C7—C8—C9	−179.40 (12)
C2—N1—N2—C4	0.12 (14)	C7—C8—C9—C10	0.6 (2)
Zn1—N1—N2—C4	−164.83 (9)	C8—C9—C10—C11	−1.0 (2)
C2—N1—N2—C6	179.86 (11)	C9—C10—C11—C12	−0.3 (2)
Zn1—N1—N2—C6	14.91 (15)	C10—C11—C12—C7	1.91 (19)
C15—N3—N4—C17	0.24 (14)	C10—C11—C12—C13	−179.28 (12)
C13—N3—N4—C17	174.00 (11)	C8—C7—C12—C11	−2.29 (18)
C15—N3—N4—Zn1	−173.30 (9)	C6—C7—C12—C11	178.22 (11)
C13—N3—N4—Zn1	0.46 (16)	C8—C7—C12—C13	178.96 (12)
N1—Zn1—N4—C17	170.83 (10)	C6—C7—C12—C13	−0.53 (19)
Cl2—Zn1—N4—C17	−63.89 (11)	C15—N3—C13—C12	−78.13 (16)
Cl1—Zn1—N4—C17	58.82 (11)	N4—N3—C13—C12	109.26 (13)
N1—Zn1—N4—N3	−16.63 (12)	C11—C12—C13—N3	105.38 (13)
Cl2—Zn1—N4—N3	108.65 (10)	C7—C12—C13—N3	−75.87 (15)
Cl1—Zn1—N4—N3	−128.64 (10)	N4—N3—C15—C16	−0.62 (14)
N2—N1—C2—C3	−0.15 (14)	C13—N3—C15—C16	−173.86 (12)
Zn1—N1—C2—C3	163.06 (9)	N4—N3—C15—C14	177.89 (12)
N2—N1—C2—C1	178.95 (12)	C13—N3—C15—C14	4.6 (2)
Zn1—N1—C2—C1	−17.83 (19)	N3—C15—C16—C17	0.73 (15)
N1—C2—C3—C4	0.13 (16)	C14—C15—C16—C17	−177.61 (14)
C1—C2—C3—C4	−178.91 (13)	N3—N4—C17—C16	0.24 (14)
N1—N2—C4—C3	−0.04 (15)	Zn1—N4—C17—C16	174.30 (9)
C6—N2—C4—C3	−179.76 (12)	N3—N4—C17—C18	−178.81 (12)
N1—N2—C4—C5	178.73 (12)	Zn1—N4—C17—C18	−4.75 (18)
C6—N2—C4—C5	−1.0 (2)	C15—C16—C17—N4	−0.61 (15)
C2—C3—C4—N2	−0.05 (15)	C15—C16—C17—C18	178.36 (14)
C2—C3—C4—C5	−178.72 (13)

Zn1—N1	2.0323 (11)
Zn1—N4	2.0512 (11)
Zn1—Cl2	2.2145 (4)
Zn1—Cl1	2.2526 (4)

N1—Zn1—N4	111.72 (4)
N1—Zn1—Cl2	115.14 (3)
N4—Zn1—Cl2	104.72 (3)
N1—Zn1—Cl1	103.37 (3)
N4—Zn1—Cl1	106.19 (3)
Cl2—Zn1—Cl1	115.538 (13)