Dichlorido[1-(1-naphthyl­meth­yl)-3-(2-pyrid­yl)-1H-pyrazole-κ²N²,N³]zinc(II)

In the title compound, [ZnCl₂(C₁₉H₁₅N₃)], the Zn^II atom is four-coordinated by two N atoms from the 1-(1-naphthyl­meth­yl)-3-(2-pyrid­yl)-1H-pyrazole (L) ligand and two terminal Cl atoms in a distorted tetra­hedral coordination environment. In the crystal structure, inversion-related Zn^II mononuclear units are linked to form dimers through π–π stacking inter­actions between the pyridine and pyrazole rings, the centroid–centroid distance being 3.5166 (19) Å. The dimers are inter­linked to form a chain along the a axis by C—H...π inter­actions involving both benzene rings of the L ligand.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.093
• Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.95

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.98

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

In recent years, much attention has been focused on the synthetic approach and the structural control of metal-organic coordination architectures with ligands based on pyrazolyl-pyridine chelating units (Steel et al., 2005; Ward et al., 2001). Many novel functional complexes with 3-(2-pyridyl)pyrazole and/or 3-(2-pyridyl)pyrazole ligands have been reported (Bell et al., 2003; Paul et al., 2004; Ward et al., 2001). Recently, we have reported the preparation of a non-planar flexible ligand, 1-[3-(2-pyridyl)pyrazol-1-ylmethyl]naphthalene (L) (Zhang et al., 2005). Now we report here the crystal structure of a zinc(II) complex of this ligand, [Zn(L)Cl₂], the title compound.

In the title compound, the Zn^II center is four-coordinated by two N donors from one L ligand and two Cl^- anions (Table 1). The coordination geometry around the Zn^II center can be described as a distorted tetrahedron (Fig. 1).

In the crystal structure, the Zn^II mononuclear units at (x, y, z) and (-x, -y, -z) are interconnected to form a dimer through π-π stacking interactions between the adjacent pyridine and pyrazole rings of the L ligand, with their centroids separated by 3.5166 (19) Å. The dimers are linked to form a chain along the a axis by C—H···π interactions (Table 2) involving the C2—C6/C11 (centroid Cg1) and C6—C11 (centroid Cg2) benzene rings of the L ligand (Fig. 2).

Related literature

For synthesis, see: Zhang et al. (2005). For related literature, see: Bell et al. (2003); Paul et al. (2004); Steel (2005); Ward et al. (2001).

S2. Experimental

The ligand 1-[3-(2-pyridyl)pyrazol-1-ylmethyl]naphthalene (L) was synthesized according to the method reported in the literature (Zhang et al., 2005). A solution of ZnCl₂ (0.1 mmol) in methanol (15 ml) was added to L (0.1 mmol). A yellow solid formed was filtered off and the resulting solution was kept at room temperature. Yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent after several days (yield: 30%). Analysis calculated for (C₁₉H₁₅ZnCl₂N₃): C 54.12, H 3.59, N 9.97%; found: C 54.26, H 3.44, N 10.11%.

S3. Refinement

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (methylene) and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.

Dichlorido[1-(1-naphthylmethyl)-3-(2-pyridyl)-1H-pyrazole- κ²N²,N³]zinc(II)

Crystal data

[ZnCl2(C19H15N3)]	F(000) = 856
Mr = 421.61	Dx = 1.559 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3039 reflections
a = 12.069 (2) Å	θ = 2.3–25.2°
b = 10.9474 (18) Å	µ = 1.67 mm^−1
c = 13.609 (2) Å	T = 293 K
β = 92.662 (3)°	Block, yellow
V = 1796.1 (5) Å^3	0.24 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3673 independent reflections
Radiation source: fine-focus sealed tube	2533 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
φ and ω scans	θmax = 26.4°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −15→14
Tmin = 0.731, Tmax = 0.776	k = −9→13
10232 measured reflections	l = −17→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0371P)^2 + 0.4714P] where P = (Fo^2 + 2Fc^2)/3
3673 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.46 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.11994 (3)	0.26266 (3)	0.11428 (2)	0.03872 (13)
Cl1	0.05436 (8)	0.22829 (10)	0.25927 (7)	0.0695 (3)
Cl2	0.20707 (8)	0.43809 (7)	0.10055 (6)	0.0578 (2)
N1	0.29477 (18)	0.0502 (2)	0.06734 (18)	0.0383 (6)
N2	0.20198 (18)	0.1170 (2)	0.05350 (17)	0.0337 (5)
N3	0.01157 (18)	0.2225 (2)	−0.00402 (17)	0.0374 (6)
C1	0.3734 (2)	0.0719 (3)	0.1492 (2)	0.0430 (7)
H1A	0.4103	−0.0042	0.1669	0.052*
H1B	0.3335	0.0990	0.2055	0.052*
C2	0.4602 (2)	0.1669 (3)	0.1263 (2)	0.0353 (6)
C3	0.4487 (3)	0.2406 (3)	0.0461 (2)	0.0460 (8)
H3	0.3860	0.2327	0.0042	0.055*
C4	0.5288 (3)	0.3285 (3)	0.0250 (3)	0.0554 (9)
H4	0.5186	0.3782	−0.0301	0.066*
C5	0.6204 (3)	0.3410 (3)	0.0844 (3)	0.0557 (9)
H5	0.6729	0.3999	0.0703	0.067*
C6	0.6377 (2)	0.2655 (3)	0.1679 (2)	0.0461 (8)
C7	0.7348 (3)	0.2733 (4)	0.2298 (3)	0.0634 (11)
H7	0.7889	0.3306	0.2160	0.076*
C8	0.7505 (3)	0.1995 (4)	0.3082 (3)	0.0733 (13)
H8	0.8158	0.2047	0.3470	0.088*
C9	0.6694 (3)	0.1152 (4)	0.3315 (2)	0.0648 (11)
H9	0.6803	0.0666	0.3872	0.078*
C10	0.5742 (3)	0.1026 (3)	0.2744 (2)	0.0511 (8)
H10	0.5215	0.0450	0.2907	0.061*
C11	0.5558 (2)	0.1775 (3)	0.1901 (2)	0.0383 (7)
C12	0.3038 (3)	−0.0296 (3)	−0.0065 (2)	0.0491 (8)
H12	0.3614	−0.0850	−0.0132	0.059*
C13	0.2143 (3)	−0.0156 (3)	−0.0703 (2)	0.0475 (8)
H13	0.1984	−0.0585	−0.1282	0.057*
C14	0.1521 (2)	0.0764 (3)	−0.0301 (2)	0.0348 (7)
C15	0.0460 (2)	0.1310 (3)	−0.0620 (2)	0.0359 (7)
C16	−0.0163 (3)	0.0922 (3)	−0.1437 (2)	0.0472 (8)
H16	0.0084	0.0291	−0.1829	0.057*
C17	−0.1174 (3)	0.1499 (3)	−0.1659 (2)	0.0541 (9)
H17	−0.1614	0.1253	−0.2203	0.065*
C18	−0.1514 (3)	0.2421 (3)	−0.1078 (3)	0.0553 (9)
H18	−0.2187	0.2811	−0.1219	0.066*
C19	−0.0850 (2)	0.2770 (3)	−0.0280 (3)	0.0485 (8)
H19	−0.1082	0.3411	0.0109	0.058*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0406 (2)	0.0404 (2)	0.0348 (2)	0.00353 (16)	−0.00087 (14)	−0.00799 (16)
Cl1	0.0731 (6)	0.0930 (8)	0.0437 (5)	−0.0062 (5)	0.0168 (4)	−0.0042 (5)
Cl2	0.0793 (6)	0.0408 (5)	0.0524 (5)	−0.0079 (4)	−0.0084 (4)	−0.0040 (4)
N1	0.0338 (13)	0.0375 (14)	0.0440 (15)	0.0029 (11)	0.0055 (11)	−0.0011 (11)
N2	0.0326 (12)	0.0311 (13)	0.0375 (13)	−0.0001 (10)	0.0042 (10)	−0.0028 (10)
N3	0.0336 (13)	0.0432 (15)	0.0353 (13)	−0.0015 (11)	−0.0005 (10)	0.0008 (11)
C1	0.0388 (17)	0.0491 (19)	0.0409 (17)	0.0051 (14)	0.0003 (14)	0.0091 (14)
C2	0.0321 (15)	0.0385 (17)	0.0356 (16)	0.0067 (13)	0.0036 (12)	−0.0018 (13)
C3	0.0401 (17)	0.051 (2)	0.0463 (18)	0.0010 (15)	−0.0032 (14)	0.0073 (15)
C4	0.064 (2)	0.049 (2)	0.053 (2)	−0.0014 (18)	0.0043 (18)	0.0124 (16)
C5	0.057 (2)	0.048 (2)	0.063 (2)	−0.0116 (17)	0.0121 (18)	−0.0066 (17)
C6	0.0394 (17)	0.051 (2)	0.0480 (18)	0.0022 (15)	0.0041 (14)	−0.0226 (16)
C7	0.046 (2)	0.082 (3)	0.062 (2)	−0.0041 (19)	0.0001 (18)	−0.035 (2)
C8	0.052 (2)	0.108 (3)	0.058 (3)	0.020 (2)	−0.0153 (19)	−0.042 (2)
C9	0.067 (2)	0.087 (3)	0.0384 (19)	0.031 (2)	−0.0111 (18)	−0.0100 (18)
C10	0.054 (2)	0.061 (2)	0.0379 (18)	0.0166 (17)	−0.0013 (15)	−0.0043 (15)
C11	0.0362 (16)	0.0444 (18)	0.0345 (16)	0.0085 (14)	0.0038 (13)	−0.0113 (13)
C12	0.051 (2)	0.0397 (19)	0.057 (2)	0.0072 (15)	0.0144 (17)	−0.0105 (16)
C13	0.061 (2)	0.0406 (18)	0.0415 (18)	−0.0003 (16)	0.0081 (16)	−0.0126 (14)
C14	0.0411 (16)	0.0339 (16)	0.0297 (14)	−0.0093 (13)	0.0052 (13)	−0.0033 (12)
C15	0.0399 (16)	0.0370 (17)	0.0306 (15)	−0.0126 (13)	0.0009 (13)	0.0030 (12)
C16	0.060 (2)	0.0465 (19)	0.0340 (16)	−0.0136 (16)	−0.0032 (15)	0.0026 (14)
C17	0.055 (2)	0.063 (2)	0.0422 (19)	−0.0263 (18)	−0.0177 (16)	0.0178 (18)
C18	0.0400 (18)	0.071 (3)	0.054 (2)	−0.0074 (17)	−0.0097 (15)	0.018 (2)
C19	0.0384 (17)	0.052 (2)	0.055 (2)	0.0029 (15)	−0.0005 (15)	0.0057 (15)

Geometric parameters (Å, º)

Zn1—N2	2.070 (2)	C6—C11	1.422 (4)
Zn1—N3	2.074 (2)	C7—C8	1.345 (6)
Zn1—Cl1	2.1924 (10)	C7—H7	0.93
Zn1—Cl2	2.2016 (9)	C8—C9	1.392 (5)
N1—C12	1.340 (4)	C8—H8	0.93
N1—N2	1.344 (3)	C9—C10	1.363 (4)
N1—C1	1.450 (3)	C9—H9	0.93
N2—C14	1.338 (3)	C10—C11	1.420 (4)
N3—C19	1.337 (4)	C10—H10	0.93
N3—C15	1.352 (4)	C12—C13	1.363 (4)
C1—C2	1.518 (4)	C12—H12	0.93
C1—H1A	0.97	C13—C14	1.384 (4)
C1—H1B	0.97	C13—H13	0.93
C2—C3	1.359 (4)	C14—C15	1.461 (4)
C2—C11	1.417 (4)	C15—C16	1.380 (4)
C3—C4	1.404 (4)	C16—C17	1.395 (4)
C3—H3	0.93	C16—H16	0.93
C4—C5	1.345 (4)	C17—C18	1.358 (5)
C4—H4	0.93	C17—H17	0.93
C5—C6	1.413 (5)	C18—C19	1.374 (5)
C5—H5	0.93	C18—H18	0.93
C6—C7	1.414 (5)	C19—H19	0.93
N2—Zn1—N3	79.77 (9)	C6—C7—H7	119.4
N2—Zn1—Cl1	115.27 (7)	C7—C8—C9	120.3 (3)
N3—Zn1—Cl1	114.91 (7)	C7—C8—H8	119.9
N2—Zn1—Cl2	113.51 (7)	C9—C8—H8	119.9
N3—Zn1—Cl2	113.93 (7)	C10—C9—C8	121.3 (4)
Cl1—Zn1—Cl2	114.83 (4)	C10—C9—H9	119.3
C12—N1—N2	110.3 (2)	C8—C9—H9	119.3
C12—N1—C1	127.6 (3)	C9—C10—C11	119.9 (3)
N2—N1—C1	122.0 (2)	C9—C10—H10	120.1
C14—N2—N1	106.1 (2)	C11—C10—H10	120.1
C14—N2—Zn1	113.01 (18)	C2—C11—C10	122.7 (3)
N1—N2—Zn1	140.77 (18)	C2—C11—C6	118.7 (3)
C19—N3—C15	118.5 (3)	C10—C11—C6	118.6 (3)
C19—N3—Zn1	127.3 (2)	N1—C12—C13	108.3 (3)
C15—N3—Zn1	114.23 (18)	N1—C12—H12	125.9
N1—C1—C2	112.8 (2)	C13—C12—H12	125.9
N1—C1—H1A	109.0	C12—C13—C14	105.0 (3)
C2—C1—H1A	109.0	C12—C13—H13	127.5
N1—C1—H1B	109.0	C14—C13—H13	127.5
C2—C1—H1B	109.0	N2—C14—C13	110.3 (3)
H1A—C1—H1B	107.8	N2—C14—C15	118.1 (2)
C3—C2—C11	119.5 (3)	C13—C14—C15	131.6 (3)
C3—C2—C1	121.8 (3)	N3—C15—C16	121.8 (3)
C11—C2—C1	118.7 (2)	N3—C15—C14	114.7 (2)
C2—C3—C4	121.7 (3)	C16—C15—C14	123.4 (3)
C2—C3—H3	119.1	C15—C16—C17	118.3 (3)
C4—C3—H3	119.1	C15—C16—H16	120.9
C5—C4—C3	120.1 (3)	C17—C16—H16	120.9
C5—C4—H4	119.9	C18—C17—C16	119.7 (3)
C3—C4—H4	119.9	C18—C17—H17	120.2
C4—C5—C6	120.7 (3)	C16—C17—H17	120.2
C4—C5—H5	119.7	C17—C18—C19	119.1 (3)
C6—C5—H5	119.7	C17—C18—H18	120.4
C5—C6—C7	122.1 (3)	C19—C18—H18	120.4
C5—C6—C11	119.3 (3)	N3—C19—C18	122.6 (3)
C7—C6—C11	118.6 (3)	N3—C19—H19	118.7
C8—C7—C6	121.2 (4)	C18—C19—H19	118.7
C8—C7—H7	119.4
C12—N1—N2—C14	0.8 (3)	C3—C2—C11—C6	−0.2 (4)
C1—N1—N2—C14	177.3 (2)	C1—C2—C11—C6	179.3 (3)
C12—N1—N2—Zn1	−175.0 (2)	C9—C10—C11—C2	178.3 (3)
C1—N1—N2—Zn1	1.6 (4)	C9—C10—C11—C6	−0.6 (4)
N3—Zn1—N2—C14	3.88 (18)	C5—C6—C11—C2	1.2 (4)
Cl1—Zn1—N2—C14	116.72 (18)	C7—C6—C11—C2	−177.9 (3)
Cl2—Zn1—N2—C14	−107.90 (18)	C5—C6—C11—C10	−179.8 (3)
N3—Zn1—N2—N1	179.4 (3)	C7—C6—C11—C10	1.1 (4)
Cl1—Zn1—N2—N1	−67.7 (3)	N2—N1—C12—C13	−0.5 (3)
Cl2—Zn1—N2—N1	67.7 (3)	C1—N1—C12—C13	−176.8 (3)
N2—Zn1—N3—C19	178.1 (3)	N1—C12—C13—C14	0.0 (3)
Cl1—Zn1—N3—C19	64.9 (3)	N1—N2—C14—C13	−0.8 (3)
Cl2—Zn1—N3—C19	−70.6 (2)	Zn1—N2—C14—C13	176.28 (19)
N2—Zn1—N3—C15	−2.49 (19)	N1—N2—C14—C15	178.2 (2)
Cl1—Zn1—N3—C15	−115.73 (18)	Zn1—N2—C14—C15	−4.8 (3)
Cl2—Zn1—N3—C15	108.82 (18)	C12—C13—C14—N2	0.5 (3)
C12—N1—C1—C2	88.0 (4)	C12—C13—C14—C15	−178.3 (3)
N2—N1—C1—C2	−87.9 (3)	C19—N3—C15—C16	−0.9 (4)
N1—C1—C2—C3	13.6 (4)	Zn1—N3—C15—C16	179.7 (2)
N1—C1—C2—C11	−166.0 (2)	C19—N3—C15—C14	−179.8 (2)
C11—C2—C3—C4	−0.6 (5)	Zn1—N3—C15—C14	0.8 (3)
C1—C2—C3—C4	179.9 (3)	N2—C14—C15—N3	2.7 (4)
C2—C3—C4—C5	0.5 (5)	C13—C14—C15—N3	−178.6 (3)
C3—C4—C5—C6	0.6 (5)	N2—C14—C15—C16	−176.2 (3)
C4—C5—C6—C7	177.7 (3)	C13—C14—C15—C16	2.5 (5)
C4—C5—C6—C11	−1.4 (5)	N3—C15—C16—C17	0.0 (4)
C5—C6—C7—C8	−179.0 (3)	C14—C15—C16—C17	178.8 (3)
C11—C6—C7—C8	0.1 (5)	C15—C16—C17—C18	0.4 (4)
C6—C7—C8—C9	−1.6 (5)	C16—C17—C18—C19	0.1 (5)
C7—C8—C9—C10	2.1 (5)	C15—N3—C19—C18	1.4 (4)
C8—C9—C10—C11	−0.9 (5)	Zn1—N3—C19—C18	−179.2 (2)
C3—C2—C11—C10	−179.2 (3)	C17—C18—C19—N3	−1.0 (5)
C1—C2—C11—C10	0.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···Cg1^i	0.93	2.55	3.400 (4)	152
C13—H13···Cg2^i	0.93	2.87	3.536 (3)	129

Symmetry code: (i) −x+1, −y, −z.