Dichlorido{2-[3-(2-pyrid­yl)pyrazol-1-yl­meth­yl]pyridine}zinc(II)

In the title complex, [ZnCl₂(C₁₄H₁₂N₄)], Zn^II is penta­coordinated by three N-atom donors from one 2-[3-(2-pyrid­yl)pyrazol-1-ylmeth­yl]pyridine (L) ligand and by two Cl⁻ anions in a distorted trigonal–bipyramidal geometry. Adjacent mononuclear Zn^II complexes form π–π stacking inter­actions between pyridine and pyrazole rings of neighbouring L ligands, with centroid–centroid separations of 3.671 (1) and 3.681 (1) Å, generating one-dimensional chains.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.073
• Data-to-parameter ratio = 16.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   N3      ..       7.79 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zn1    -   N4      ..       5.71 su

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.84

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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

Nowadays, much attention is focused on the synthetic approach and the structural control of metal-organic coordination architectures with such ligands based on pyrazolyl-pyridine chelating units (Steel, 2005; Ward et al., 2001). In this field, Ward et al. have reported many novel functional complexes through the use of 3-(2-pyridyl)pyrazole and/or 3-(2-pyridyl)pyrazole-based ligands (Bell et al., 2003; Paul et al., 2004; Singh et al., 2003; Ward et al., 2001; Zou et al., 2004). In this paper, we present a zinc chloride complex of the ligand 2-[3-(2-pyridyl)pyrazol-1-ylmethyl]pyridine (denoted L).

In the title complex, Zn^II is five-coordinated by three N donors from one L ligand and two Cl^- anions (Figure 1). The coordination geometry around each Zn^II center can be described as distorted trigonal bipyramidal. The coordinated tridentate L ligand gives rise to one five-membered chelate ring [Zn1/N2/C6/C5/N3], with the N2—Zn1—N3 angle equal to 72.73 (3)°, and one six-membered chelate ring [Zn1/N2/N1/C9/C10/N4], with the N2—Zn1—N4 angle equal to 82.34 (8)°. Distortions from ideal trigonal bipyramidal geometry are evident from the bond lengths and bond angles (Table 1).

The mononuclear Zn^II complexes form π···π stacking interactions between adjacent pyridine and pyrazole rings of the L ligands, with centroid-centroid separations of 3.671 (1) Å (dashed open lines in Figure 2) and 3.681 (1) Å (dashed solid lines in Figure 2), and with a dihedral angle of 4.0° between the planes of the rings (Janiak, 2000; Khlobystov et al., 2001). These interactions generate one-dimensional chains along the a axis.

Related literature

For related literature, see: Bell et al. (2003); Janiak (2000); Khlobystov et al. (2001); Paul et al. (2004); Singh et al. (2003); Song et al. (2005); Steel (2005); Ward et al. (2001); Zou et al. (2004).

S2. Experimental

The ligand 2-[3-(2-pyridyl)pyrazol-1-ylmethyl]pyridine (L) was synthesized according to a general literature procedure (Singh et al., 2003; Song et al., 2005). Reaction of L (0.1 mmol) with ZnCl₂ (0.1 mmol) in the mixed solution of MeOH (15 ml) and CH₃CN (5 ml) for a few minutes afforded the yellow solid, which was filtered. The resulting solution was kept at room temperature and yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent after several days. Yield: 30%. Elemental analysis calculated: C, 45.13; H, 3.25; N, 15.04%; found: C, 45.26; H, 3.14; N, 15.11%.

S3. Refinement

H atoms were included in calculated positions and treated in subsequent refinement as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (methylene), and with U_iso(H) = 1.2 or 1.5 U_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 complex. Displacement ellipsoids are drawn at the 30% probability level for non-H atoms.
	Fig. 2. Part of the crystal packing in the title complex, showing a chain based on π···π stacking (dashed solid and open lines).

Dichlorido{2-[3-(2-pyridyl)pyrazol-1-ylmethyl]pyridine}zinc(II)

Crystal data

[ZnCl2(C14H12N4)]	F(000) = 752
Mr = 372.55	Dx = 1.651 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2602 reflections
a = 7.2813 (10) Å	θ = 2.7–24.8°
b = 15.248 (2) Å	µ = 1.99 mm^−1
c = 13.5034 (19) Å	T = 294 K
β = 90.967 (2)°	Block, yellow
V = 1499.0 (4) Å^3	0.20 × 0.18 × 0.14 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	3037 independent reflections
Radiation source: fine-focus sealed tube	2174 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
φ and ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→5
Tmin = 0.692, Tmax = 0.768	k = −19→16
8317 measured reflections	l = −16→16

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.073	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0275P)^2 + 0.3375P] where P = (Fo^2 + 2Fc^2)/3
3037 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.35 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	0.16259 (4)	1.08055 (2)	0.29567 (3)	0.03662 (12)
C1	0.1757 (4)	1.1774 (2)	0.5136 (2)	0.0449 (8)
H1A	0.1377	1.2270	0.4786	0.054*
C2	0.2070 (4)	1.1849 (2)	0.6138 (2)	0.0480 (8)
H2A	0.1902	1.2381	0.6460	0.058*
C3	0.2636 (4)	1.1118 (2)	0.6654 (2)	0.0452 (8)
H3A	0.2894	1.1155	0.7330	0.054*
C4	0.2820 (4)	1.0326 (2)	0.6165 (2)	0.0391 (7)
H4A	0.3173	0.9822	0.6506	0.047*
C5	0.2467 (3)	1.03049 (17)	0.51566 (19)	0.0306 (6)
C6	0.2617 (3)	0.95185 (18)	0.4549 (2)	0.0318 (6)
C7	0.3003 (4)	0.86392 (19)	0.4753 (2)	0.0417 (7)
H7A	0.3237	0.8387	0.5369	0.050*
C8	0.2963 (4)	0.82293 (19)	0.3856 (2)	0.0432 (7)
H8A	0.3184	0.7637	0.3745	0.052*
C9	0.2510 (4)	0.8755 (2)	0.2084 (2)	0.0445 (8)
H9A	0.2684	0.8145	0.1905	0.053*
H9B	0.3528	0.9087	0.1820	0.053*
C10	0.0750 (4)	0.90799 (19)	0.1612 (2)	0.0404 (7)
C11	−0.0245 (5)	0.8540 (2)	0.0987 (3)	0.0576 (9)
H11A	0.0123	0.7962	0.0891	0.069*
C12	−0.1790 (5)	0.8857 (3)	0.0502 (3)	0.0659 (10)
H12A	−0.2462	0.8502	0.0068	0.079*
C13	−0.2310 (5)	0.9702 (3)	0.0671 (2)	0.0580 (9)
H13A	−0.3342	0.9935	0.0353	0.070*
C14	−0.1280 (4)	1.0205 (2)	0.1322 (2)	0.0477 (8)
H14A	−0.1660	1.0776	0.1442	0.057*
N1	0.2550 (3)	0.88307 (15)	0.31618 (18)	0.0361 (5)
N2	0.2340 (3)	0.96230 (14)	0.35770 (16)	0.0337 (5)
N3	0.1972 (3)	1.10258 (14)	0.46378 (17)	0.0353 (6)
N4	0.0236 (3)	0.99150 (15)	0.17893 (16)	0.0379 (6)
Cl1	0.41903 (11)	1.12397 (6)	0.21749 (7)	0.0648 (3)
Cl2	−0.05580 (10)	1.18623 (5)	0.29099 (6)	0.0433 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0335 (2)	0.03112 (19)	0.0450 (2)	0.00138 (15)	−0.00478 (14)	0.00854 (16)
C1	0.0465 (19)	0.0372 (17)	0.051 (2)	0.0021 (14)	−0.0064 (15)	−0.0050 (15)
C2	0.0441 (19)	0.0449 (19)	0.055 (2)	−0.0030 (15)	−0.0004 (15)	−0.0192 (16)
C3	0.0386 (18)	0.062 (2)	0.0355 (18)	−0.0093 (15)	−0.0015 (14)	−0.0085 (16)
C4	0.0308 (16)	0.0507 (19)	0.0356 (17)	−0.0045 (14)	−0.0016 (12)	0.0059 (14)
C5	0.0225 (14)	0.0349 (15)	0.0344 (15)	−0.0004 (12)	−0.0024 (11)	0.0026 (12)
C6	0.0222 (14)	0.0364 (15)	0.0367 (16)	−0.0003 (12)	−0.0006 (12)	0.0046 (12)
C7	0.0471 (19)	0.0393 (17)	0.0389 (18)	0.0061 (14)	0.0026 (14)	0.0126 (14)
C8	0.0466 (19)	0.0278 (15)	0.055 (2)	0.0045 (13)	0.0026 (15)	0.0056 (14)
C9	0.0493 (19)	0.0441 (18)	0.0400 (18)	0.0106 (15)	−0.0011 (14)	−0.0105 (14)
C10	0.0410 (18)	0.0443 (19)	0.0360 (16)	−0.0022 (14)	0.0014 (13)	−0.0047 (14)
C11	0.062 (2)	0.053 (2)	0.057 (2)	−0.0007 (17)	−0.0059 (18)	−0.0208 (17)
C12	0.064 (3)	0.077 (3)	0.056 (2)	−0.004 (2)	−0.0168 (19)	−0.023 (2)
C13	0.049 (2)	0.076 (3)	0.049 (2)	0.0038 (19)	−0.0168 (16)	−0.0018 (19)
C14	0.0442 (19)	0.0478 (19)	0.051 (2)	0.0022 (15)	−0.0100 (15)	0.0033 (16)
N1	0.0386 (14)	0.0296 (12)	0.0400 (14)	0.0050 (11)	−0.0006 (11)	−0.0008 (11)
N2	0.0390 (14)	0.0282 (13)	0.0339 (13)	0.0030 (10)	−0.0045 (10)	0.0008 (10)
N3	0.0363 (14)	0.0324 (13)	0.0371 (14)	0.0032 (10)	−0.0065 (10)	−0.0021 (10)
N4	0.0403 (15)	0.0385 (14)	0.0346 (13)	0.0011 (11)	−0.0060 (11)	0.0008 (11)
Cl1	0.0379 (5)	0.0673 (6)	0.0895 (7)	−0.0021 (4)	0.0071 (4)	0.0308 (5)
Cl2	0.0409 (4)	0.0365 (4)	0.0521 (5)	0.0065 (3)	−0.0077 (3)	0.0077 (3)

Geometric parameters (Å, º)

Zn1—Cl1	2.2596 (9)	C7—H7A	0.930
Zn1—Cl2	2.2640 (8)	C8—N1	1.342 (4)
Zn1—N2	2.051 (2)	C8—H8A	0.930
Zn1—N3	2.304 (2)	C9—N1	1.459 (4)
Zn1—N4	2.302 (2)	C9—C10	1.505 (4)
C1—N3	1.335 (3)	C9—H9A	0.970
C1—C2	1.374 (4)	C9—H9B	0.970
C1—H1A	0.930	C10—N4	1.350 (4)
C2—C3	1.374 (4)	C10—C11	1.377 (4)
C2—H2A	0.930	C11—C12	1.379 (5)
C3—C4	1.384 (4)	C11—H11A	0.930
C3—H3A	0.930	C12—C13	1.363 (5)
C4—C5	1.382 (4)	C12—H12A	0.930
C4—H4A	0.930	C13—C14	1.378 (4)
C5—N3	1.349 (3)	C13—H13A	0.930
C5—C6	1.458 (4)	C14—N4	1.337 (3)
C6—N2	1.334 (3)	C14—H14A	0.930
C6—C7	1.396 (4)	N1—N2	1.342 (3)
C7—C8	1.363 (4)
Cl1—Zn1—Cl2	111.34 (3)	N1—C9—C10	113.5 (2)
Cl1—Zn1—N2	104.04 (7)	N1—C9—H9A	108.9
Cl1—Zn1—N3	109.88 (6)	C10—C9—H9A	108.9
Cl1—Zn1—N4	102.14 (7)	N1—C9—H9B	108.9
Cl2—Zn1—N2	144.09 (7)	C10—C9—H9B	108.9
Cl2—Zn1—N3	89.36 (6)	H9A—C9—H9B	107.7
Cl2—Zn1—N4	95.75 (6)	N4—C10—C11	121.9 (3)
N2—Zn1—N3	72.73 (8)	N4—C10—C9	118.2 (3)
N2—Zn1—N4	82.34 (8)	C11—C10—C9	119.9 (3)
N3—Zn1—N4	143.13 (8)	C10—C11—C12	119.9 (3)
N3—C1—C2	123.2 (3)	C10—C11—H11A	120.1
N3—C1—H1A	118.4	C12—C11—H11A	120.1
C2—C1—H1A	118.4	C13—C12—C11	118.6 (3)
C1—C2—C3	118.5 (3)	C13—C12—H12A	120.7
C1—C2—H2A	120.8	C11—C12—H12A	120.7
C3—C2—H2A	120.8	C12—C13—C14	118.9 (3)
C2—C3—C4	119.7 (3)	C12—C13—H13A	120.6
C2—C3—H3A	120.1	C14—C13—H13A	120.6
C4—C3—H3A	120.1	N4—C14—C13	123.6 (3)
C5—C4—C3	118.3 (3)	N4—C14—H14A	118.2
C5—C4—H4A	120.9	C13—C14—H14A	118.2
C3—C4—H4A	120.9	N2—N1—C8	110.4 (2)
N3—C5—C4	122.4 (3)	N2—N1—C9	119.1 (2)
N3—C5—C6	113.6 (2)	C8—N1—C9	130.0 (3)
C4—C5—C6	124.0 (3)	C6—N2—N1	106.7 (2)
N2—C6—C7	109.6 (3)	C6—N2—Zn1	122.67 (18)
N2—C6—C5	116.4 (2)	N1—N2—Zn1	130.60 (17)
C7—C6—C5	134.1 (3)	C1—N3—C5	117.9 (2)
C8—C7—C6	105.3 (3)	C1—N3—Zn1	127.5 (2)
C8—C7—H7A	127.3	C5—N3—Zn1	114.62 (17)
C6—C7—H7A	127.3	C14—N4—C10	117.2 (3)
N1—C8—C7	108.0 (3)	C14—N4—Zn1	118.6 (2)
N1—C8—H8A	126.0	C10—N4—Zn1	123.89 (19)
C7—C8—H8A	126.0
N3—C1—C2—C3	0.2 (5)	N3—Zn1—N2—C6	1.1 (2)
C1—C2—C3—C4	−2.0 (5)	Cl1—Zn1—N2—N1	−75.0 (2)
C2—C3—C4—C5	1.6 (4)	Cl2—Zn1—N2—N1	114.9 (2)
C3—C4—C5—N3	0.7 (4)	N4—Zn1—N2—N1	25.6 (2)
C3—C4—C5—C6	179.7 (2)	N3—Zn1—N2—N1	178.2 (2)
N3—C5—C6—N2	3.1 (3)	C2—C1—N3—C5	2.1 (4)
C4—C5—C6—N2	−175.9 (2)	C2—C1—N3—Zn1	−177.2 (2)
N3—C5—C6—C7	−177.0 (3)	C4—C5—N3—C1	−2.5 (4)
C4—C5—C6—C7	4.0 (5)	C6—C5—N3—C1	178.5 (2)
N2—C6—C7—C8	0.7 (3)	C4—C5—N3—Zn1	176.8 (2)
C5—C6—C7—C8	−179.2 (3)	C6—C5—N3—Zn1	−2.2 (3)
C6—C7—C8—N1	−0.9 (3)	N2—Zn1—N3—C1	−180.0 (3)
N1—C9—C10—N4	57.2 (4)	Cl1—Zn1—N3—C1	80.9 (2)
N1—C9—C10—C11	−125.4 (3)	Cl2—Zn1—N3—C1	−31.6 (2)
N4—C10—C11—C12	1.7 (5)	N4—Zn1—N3—C1	−130.3 (2)
C9—C10—C11—C12	−175.6 (3)	N2—Zn1—N3—C5	0.73 (18)
C10—C11—C12—C13	−1.1 (6)	Cl1—Zn1—N3—C5	−98.34 (18)
C11—C12—C13—C14	−0.3 (6)	Cl2—Zn1—N3—C5	149.14 (18)
C12—C13—C14—N4	1.2 (5)	N4—Zn1—N3—C5	50.4 (2)
C7—C8—N1—N2	0.7 (3)	C13—C14—N4—C10	−0.7 (5)
C7—C8—N1—C9	173.4 (3)	C13—C14—N4—Zn1	−174.5 (3)
C10—C9—N1—N2	−58.7 (4)	C11—C10—N4—C14	−0.8 (4)
C10—C9—N1—C8	129.1 (3)	C9—C10—N4—C14	176.6 (3)
C7—C6—N2—N1	−0.3 (3)	C11—C10—N4—Zn1	172.6 (2)
C5—C6—N2—N1	179.6 (2)	C9—C10—N4—Zn1	−10.0 (4)
C7—C6—N2—Zn1	177.39 (18)	N2—Zn1—N4—C14	149.3 (2)
C5—C6—N2—Zn1	−2.7 (3)	Cl1—Zn1—N4—C14	−107.9 (2)
C8—N1—N2—C6	−0.3 (3)	Cl2—Zn1—N4—C14	5.4 (2)
C9—N1—N2—C6	−173.9 (2)	N3—Zn1—N4—C14	102.0 (2)
C8—N1—N2—Zn1	−177.7 (2)	N2—Zn1—N4—C10	−24.0 (2)
C9—N1—N2—Zn1	8.7 (4)	Cl1—Zn1—N4—C10	78.8 (2)
Cl1—Zn1—N2—C6	107.9 (2)	Cl2—Zn1—N4—C10	−167.9 (2)
Cl2—Zn1—N2—C6	−62.2 (3)	N3—Zn1—N4—C10	−71.3 (3)
N4—Zn1—N2—C6	−151.4 (2)