{1,2-Bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN2)meth­yl]benzene}­dichloridozinc(II)

Guzei, I.A.; Spencer, L.C.; Budhai, A.; Darkwa, J.

doi:10.1107/S1600536811046368

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1715-m1716

https://doi.org/10.1107/S1600536811046368

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{1,2-Bis[(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]benzene}dichloridozinc(II)

Ilia A. Guzei,^a ^* Lara C. Spencer,^a Asheena Budhai ^b and James Darkwa ^b

^aDepartment of Chemistry, University of Wisconsin-Madison, 1101 University Ave, Madison, WI 53706, USA, and ^bDepartment of Chemistry, University of Johannesburg, Auckland Park Kingsway Campus, Johannesburg 2006, South Africa
^*Correspondence e-mail: iguzei@chem.wisc.edu

(Received 18 October 2011; accepted 3 November 2011; online 9 November 2011)

The title zinc complex, [ZnCl₂(C₁₈H₂₂N₄)], contains a bidentate 1,2-bis(3,5-dimethyl-1H-pyrazol-1-ylmethyl)benzene ligand that binds to the zinc atom, forming a nine-membered metallocyclic ring. The geometry about the Zn atom is distorted tetrahedral, 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_r = 430.67
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.024
wR(F²) = 0.065
S = 1.04
4672 reflections
230 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

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)

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).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811046368/lr2035sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811046368/lr2035Isup2.hkl

checkCIF report

Comment top

Poly(pyrazol-1-ylmethyl)benzene exhibits several coordination modes depending on the positions of the pyrazolyl unit on the benzene ring (Hartshorn & Steel, 1995, 1997, 1998; Guerrero et al. 2002). There are two types of coordination for the 1,2-bis(pyrazol-1-ylmethyl)benzene analogue. For square planar complexes 1,2-bis(pyrazol-1-ylmethyl)benzene behaves as a monodentate ligand as observed for palladium (Motsoane et al., 2007), whereas for tetrahedral complexes the ligand is bidentate binding to the metal center through nitrogen atoms on each of the pyrazole groups.

In the title complex (I) the bis-pyrazolyl ligand binds to the zinc center to form a nine-membered metallocycle. The dependence of the magnitude of the N—Zn—N angle on the size of the metallocycle was discussed by Guzei et al. (2011) for 2-(3,5-dimethyl-pyrazol-1-yl)-ethylamine zinc(II) chloride (II). In (I) the N—Zn—N angle (111.72 (4)°) is much closer to the ideal tetrahedral value because the size of the ring (nine atoms) exceeds 6, whereas in (II) the metallocycle is six-membered and more sterically constrained, which leads to a smaller angle of 96.88 (6)°. The Zn center in (I) possesses a distorted tetrahedral geometry; the dihedral angle between the planes defined by atoms Zn1, N1, N4 and Zn1, Cl1, Cl2 spans 85.91 (3)°, which is in good agreement with the corresponding angle of 86.77 (4)° in (II). The geometrical distortion of the Zn coordination sphere can be compared to those in the Co and Cu analogues ((III) and (IV), Chang et al., 1994). The Cu analogue is substantially more distorted as revealed by the following values of the Cl—M—Cl angle, N—M—N angle, and a range of the N—M—Cl angles. These values for (I), (III) and (IV), correspondingly are 115.538 (13), 111.72 (4), 103.37 (3)–115.14 (3)°; 115.50 (3), 110.62 (8), 102.56 (6)–112.71 (6)°; 133.4 (7),141 (7), 95.01 (13)–100.68 (12)°. It is noteworthy that the overall molecular geometry of (I) approximately conforms to C₂-symmetry, whereas geometries of (III) and (IV) are essentially C_S-symmetrical.

The distortion in (I) is noticeably smaller than in relevant compounds in the Cambridge Structural Database (Allen, 2002; Guzei et al. 2011). A structural check of (I) in Mogul confirmed its other geometrical parameters to be typical (Bruno et al. 2002).

Related literature top

For the coordination modes of poly(pyrazol-1-ylmethyl)benzene see: Hartshorn & Steel (1995, 1997, 1998); Guerrero et al. (2002). For square-planar palladium 1,2-bis(pyrazol-1-ylmethyl)benzene complexes 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, dichloride zinc complexes can be found in Guzei et al. (2011). Related structures were found in the Cambridge Structural Database (Allen, 2002). Bond distances and angles were confirmed to be typical by a Mogul structural check (Bruno et al., 2002).

Experimental top

A mixture of solid 1,2-bis(pyrazol-1-ylmethyl)benzene (0.27 g, 0.92 mmol) and anhydrous ZnCl₂ (0.120 g, 0.92 mmol) was dissolved in methanol (20 ml), and the resulting solution stirred at room temperature for 12 h. The solvent was removed in vacuo and the residue recrystallized from dichloromethane and hexane. Yield: 0.25 g (64%).

Structure description top

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008) and FCF_filter (Guzei, 2007); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and modiCIFer (Guzei, 2007).

Figures top

Fig. 1. Molecular structure of (I) (Brandenburg, 1999). The thermal ellipsoids are shown at 50% probability level. All hydrogen atoms were omitted for clarity.

{1,2-Bis[(3,5-dimethyl-1H-pyrazol-1-yl- κN²)methyl]benzene}dichloridozinc(II) top

Crystal data top

[ZnCl₂(C₁₈H₂₂N₄)]	Z = 2
M_r = 430.67	F(000) = 444
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0389P)² + 0.3716P] where P = (F_o² + 2F_c²)/3
4672 reflections	(Δ/σ)_max = 0.001
230 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[ZnCl₂(C₁₈H₂₂N₄)]	γ = 112.636 (1)°
M_r = 430.67	V = 950.38 (14) Å³
Triclinic, P1	Z = 2
a = 9.0830 (8) Å	Mo Kα radiation
b = 10.6375 (9) Å	µ = 1.58 mm⁻¹
c = 11.9558 (10) Å	T = 100 K
α = 111.853 (1)°	0.43 × 0.32 × 0.28 mm
β = 95.476 (1)°

Data collection top

Bruker CCD-1000 area-detector diffractometer	4672 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	4403 reflections with I > 2σ(I)
T_min = 0.550, T_max = 0.666	R_int = 0.020
13237 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.065	H-atom parameters constrained
S = 1.04	Δρ_max = 0.47 e Å⁻³
4672 reflections	Δρ_min = −0.23 e Å⁻³
230 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₈H₂₂N₄)]
M_r	430.67
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.0830 (8), 10.6375 (9), 11.9558 (10)
α, β, γ (°)	111.853 (1), 95.476 (1), 112.636 (1)
V (Å³)	950.38 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.58
Crystal size (mm)	0.43 × 0.32 × 0.28

Data collection
Diffractometer	Bruker CCD-1000 area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.550, 0.666
No. of measured, independent and observed [I > 2σ(I)] reflections	13237, 4672, 4403
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.065, 1.04
No. of reflections	4672
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.23

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008) and FCF_filter (Guzei, 2007), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010) and modiCIFer (Guzei, 2007).

Selected geometric parameters (Å, º) top

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

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

Acknowledgements

We are grateful for financial support for this work through a postdoctoral fellowship to AB by the National Research Foundation (NRF) and the NRF–DST Centre of Excellence in Catalysis (c*change).

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