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Acta Cryst. (2008). E64, m1374    [ doi:10.1107/S1600536808031152 ]

Dichlorido(2,6-dipyrazol-1-ylpyridine)zinc(II)

Z. N. Yang and T. T. Sun

Abstract top

In the title complex, [ZnCl2(C11H9N5)], the ZnII ion assumes a distorted trigonal-bipyramidal ZnN3Cl2 coordination geometry [Zn-N = 2.1397 (16)-2.2117 (17) Å, Zn-Cl = 2.2470 (6) and 2.2564 (6) Å]. The crystal packing exhibits [pi]-[pi] stacking interactions between the 2,6-dipyrazol-1-ylpyridine ligands of neighbouring molecules.

Comment top

2,6-Dipyrazol-1-ylpyridine and the relevant homologues as a tridentate ligand play an important role in modern coordination chemistry (Balamurugan et al., 2004), and the interest in complexes with 2,6-dipyrazol-1-ylpyridine ligand stimulted us to prepare the title complex, (I). Herein we report its crystal structure.

In (I) (Fig. 1), each ZnII ion has a distorted trigonal-bipyramidal coordination environment. In the crystal, there exist π-π stacking interactions involving symmetry related 2,6-dipyrazol-1-ylpyridine ligands (Talbe 1).

Related literature top

For the related crystal structure of dichloro[dichlorido?][2,6-bis(pyrazolylmethyl)pyridine]zinc(II), see Balamurugan et al. (2004).

Experimental top

15 ml me thanol solution containing 2,6-dipyrazol-1-ylpyridine (0.0522 g, 0.247 mmol) and pyrazine-1,4-dioxide (0.0414 g, 0.369 mmol) was added into 5 ml H2O solution of ZnCl2 (0.0783 g, 0.575 mmol), and the mixed solution was stirred for a few minutes. Colorless single crystals were obtained after the filtrate was allowed to stand at room temperature for 40 days.

Refinement top

All H atoms were placed in calculated positions with C—H = 0.93 Å and refined as riding with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atomic numbering and 30% probability displacement ellipsoids.
Dichlorido(2,6-dipyrazol-1-ylpyridine)zinc(II) top
Crystal data top
[ZnCl2(C11H9N5)]F(000) = 696
Mr = 347.50Dx = 1.758 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3889 reflections
a = 10.9630 (17) Åθ = 2.4–28.2°
b = 8.0263 (13) ŵ = 2.27 mm−1
c = 14.943 (2) ÅT = 298 K
β = 93.079 (2)°Block, colourless
V = 1313.0 (4) Å30.48 × 0.42 × 0.29 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer		2848 independent reflections
Radiation source: fine-focus sealed tube2431 reflections with I > 2σ(I)
graphiteRint = 0.030
φ and ω scansθmax = 27.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→14
Tmin = 0.409, Tmax = 0.559k = −9→10
7375 measured reflectionsl = −16→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.078 w = 1/[σ2(Fo2) + (0.0445P)2 + 0.0869P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.002
2848 reflectionsΔρmax = 0.28 e Å−3
173 parametersΔρmin = −0.32 e Å−3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0167 (11)
Crystal data top
[ZnCl2(C11H9N5)]V = 1313.0 (4) Å3
Mr = 347.50Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.9630 (17) ŵ = 2.27 mm−1
b = 8.0263 (13) ÅT = 298 K
c = 14.943 (2) Å0.48 × 0.42 × 0.29 mm
β = 93.079 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer		2848 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2431 reflections with I > 2σ(I)
Tmin = 0.409, Tmax = 0.559Rint = 0.030
7375 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.078Δρmax = 0.28 e Å−3
S = 1.05Δρmin = −0.32 e Å−3
2848 reflectionsAbsolute structure: ?
173 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
C10.47097 (18)0.3058 (2)0.04770 (16)0.0447 (5)
H10.44650.35250.10080.054*
C20.40961 (19)0.3275 (3)−0.03549 (17)0.0478 (5)
H20.33890.3891−0.04810.057*
C30.47479 (18)0.2396 (2)−0.09475 (16)0.0440 (5)
H30.45720.2292−0.15610.053*
C40.66172 (17)0.0609 (2)−0.07399 (13)0.0349 (4)
C50.66885 (19)0.0026 (3)−0.16015 (14)0.0448 (5)
H50.61470.0387−0.20620.054*
C60.7591 (2)−0.1111 (3)−0.17553 (16)0.0487 (5)
H60.7663−0.1533−0.23300.058*
C70.8394 (2)−0.1637 (3)−0.10659 (15)0.0442 (5)
H70.8998−0.2423−0.11600.053*
C80.82578 (17)−0.0944 (2)−0.02369 (14)0.0357 (4)
C90.99689 (18)−0.2410 (2)0.06325 (16)0.0454 (5)
H91.0275−0.30880.01920.054*
C101.0387 (2)−0.2314 (3)0.14943 (17)0.0502 (6)
H101.1036−0.29030.17670.060*
C110.9647 (2)−0.1152 (3)0.18931 (17)0.0491 (6)
H110.9730−0.08370.24920.059*
Cl10.65199 (5)0.06053 (7)0.25184 (4)0.05045 (17)
Cl20.83525 (5)0.37392 (6)0.12155 (4)0.04545 (15)
N10.74008 (13)0.01621 (18)−0.00710 (10)0.0327 (3)
N20.90163 (15)−0.13336 (19)0.05243 (12)0.0374 (4)
N30.88095 (15)−0.0554 (2)0.13084 (11)0.0417 (4)
N40.57069 (14)0.1699 (2)−0.04655 (11)0.0366 (4)
N50.56823 (14)0.2105 (2)0.04169 (11)0.0385 (4)
Zn10.73202 (2)0.13073 (3)0.121755 (15)0.03696 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0377 (11)0.0347 (10)0.0624 (14)−0.0040 (8)0.0090 (10)−0.0009 (10)
C20.0347 (10)0.0363 (10)0.0721 (16)−0.0005 (9)−0.0004 (10)0.0102 (10)
C30.0360 (10)0.0439 (11)0.0512 (13)−0.0045 (9)−0.0066 (9)0.0124 (9)
C40.0329 (10)0.0332 (9)0.0386 (11)−0.0072 (7)0.0014 (8)0.0020 (8)
C50.0441 (11)0.0538 (12)0.0361 (11)−0.0052 (10)−0.0025 (9)0.0023 (9)
C60.0539 (13)0.0570 (13)0.0357 (12)−0.0052 (10)0.0062 (10)−0.0076 (10)
C70.0428 (12)0.0470 (11)0.0435 (12)0.0032 (9)0.0071 (9)−0.0029 (9)
C80.0338 (10)0.0337 (9)0.0400 (11)−0.0062 (8)0.0054 (8)0.0026 (8)
C90.0392 (11)0.0374 (11)0.0599 (15)0.0031 (9)0.0064 (10)0.0053 (9)
C100.0414 (11)0.0469 (12)0.0613 (15)0.0030 (9)−0.0047 (10)0.0154 (11)
C110.0458 (12)0.0549 (13)0.0460 (14)0.0010 (10)−0.0036 (10)0.0090 (10)
Cl10.0523 (3)0.0611 (4)0.0389 (3)−0.0069 (2)0.0112 (2)−0.0012 (2)
Cl20.0431 (3)0.0428 (3)0.0500 (3)−0.0086 (2)−0.0017 (2)−0.0035 (2)
N10.0309 (8)0.0332 (8)0.0338 (9)−0.0042 (6)0.0000 (7)0.0014 (7)
N20.0348 (9)0.0376 (9)0.0400 (10)0.0006 (6)0.0034 (7)0.0025 (7)
N30.0413 (9)0.0486 (10)0.0351 (9)0.0030 (8)0.0022 (7)0.0011 (7)
N40.0316 (8)0.0370 (8)0.0407 (10)−0.0038 (7)−0.0015 (7)0.0037 (7)
N50.0359 (9)0.0376 (9)0.0419 (10)−0.0029 (7)0.0022 (7)−0.0007 (7)
Zn10.03632 (16)0.04045 (17)0.03418 (17)−0.00377 (9)0.00263 (10)−0.00260 (9)
Geometric parameters (Å, °) top
C1—N51.319 (3)C8—N11.325 (2)
C1—C21.392 (3)C8—N21.408 (3)
C1—H10.9300C9—C101.346 (3)
C2—C31.364 (3)C9—N21.358 (2)
C2—H20.9300C9—H90.9300
C3—N41.362 (2)C10—C111.391 (3)
C3—H30.9300C10—H100.9300
C4—N11.332 (2)C11—N31.323 (3)
C4—C51.376 (3)C11—H110.9300
C4—N41.405 (2)Cl1—Zn12.2470 (6)
C5—C61.374 (3)Cl2—Zn12.2564 (6)
C5—H50.9300N1—Zn12.1397 (16)
C6—C71.385 (3)N2—N31.358 (2)
C6—H60.9300N3—Zn12.2117 (17)
C7—C81.374 (3)N4—N51.360 (2)
C7—H70.9300N5—Zn12.1988 (16)
Cg1···Cg2i3.4087 (12)Cg2···Cg3i3.6253 (13)
N5—C1—C2111.4 (2)C11—C10—H10127.1
N5—C1—H1124.3N3—C11—C10111.1 (2)
C2—C1—H1124.3N3—C11—H11124.4
C3—C2—C1105.67 (19)C10—C11—H11124.4
C3—C2—H2127.2C8—N1—C4118.37 (17)
C1—C2—H2127.2C8—N1—Zn1121.33 (13)
N4—C3—C2106.6 (2)C4—N1—Zn1120.23 (13)
N4—C3—H3126.7C9—N2—N3110.69 (17)
C2—C3—H3126.7C9—N2—C8130.90 (18)
N1—C4—C5122.93 (18)N3—N2—C8118.41 (16)
N1—C4—N4112.86 (17)C11—N3—N2105.09 (18)
C5—C4—N4124.19 (18)C11—N3—Zn1140.30 (16)
C6—C5—C4117.4 (2)N2—N3—Zn1114.53 (12)
C6—C5—H5121.3N5—N4—C3111.07 (17)
C4—C5—H5121.3N5—N4—C4118.92 (16)
C5—C6—C7120.8 (2)C3—N4—C4129.90 (18)
C5—C6—H6119.6C1—N5—N4105.25 (17)
C7—C6—H6119.6C1—N5—Zn1140.46 (15)
C8—C7—C6116.84 (19)N4—N5—Zn1113.56 (11)
C8—C7—H7121.6N1—Zn1—N572.99 (6)
C6—C7—H7121.6N1—Zn1—N372.49 (6)
N1—C8—C7123.55 (19)N5—Zn1—N3143.97 (6)
N1—C8—N2113.06 (17)N1—Zn1—Cl1135.05 (4)
C7—C8—N2123.38 (18)N5—Zn1—Cl1101.44 (5)
C10—C9—N2107.3 (2)N3—Zn1—Cl195.67 (5)
C10—C9—H9126.3N1—Zn1—Cl2108.99 (4)
N2—C9—H9126.3N5—Zn1—Cl298.18 (5)
C9—C10—C11105.8 (2)N3—Zn1—Cl2102.45 (5)
C9—C10—H10127.1Cl1—Zn1—Cl2115.93 (2)
N5—C1—C2—C3−0.1 (2)C5—C4—N4—N5175.69 (18)
C1—C2—C3—N4−0.1 (2)N1—C4—N4—C3−178.85 (18)
N1—C4—C5—C62.3 (3)C5—C4—N4—C3−0.2 (3)
N4—C4—C5—C6−176.27 (18)C2—C1—N5—N40.2 (2)
C4—C5—C6—C7−0.2 (3)C2—C1—N5—Zn1169.07 (15)
C5—C6—C7—C8−1.3 (3)C3—N4—N5—C1−0.3 (2)
C6—C7—C8—N10.9 (3)C4—N4—N5—C1−176.86 (16)
C6—C7—C8—N2−178.97 (18)C3—N4—N5—Zn1−172.54 (12)
N2—C9—C10—C110.3 (2)C4—N4—N5—Zn110.85 (19)
C9—C10—C11—N30.0 (3)C8—N1—Zn1—N5−173.52 (14)
C7—C8—N1—C41.0 (3)C4—N1—Zn1—N59.64 (13)
N2—C8—N1—C4−179.07 (15)C8—N1—Zn1—N3−4.01 (13)
C7—C8—N1—Zn1−175.88 (15)C4—N1—Zn1—N3179.15 (15)
N2—C8—N1—Zn14.0 (2)C8—N1—Zn1—Cl1−84.26 (14)
C5—C4—N1—C8−2.7 (3)C4—N1—Zn1—Cl198.90 (13)
N4—C4—N1—C8176.00 (15)C8—N1—Zn1—Cl293.49 (13)
C5—C4—N1—Zn1174.24 (14)C4—N1—Zn1—Cl2−83.35 (13)
N4—C4—N1—Zn1−7.1 (2)C1—N5—Zn1—N1−178.6 (2)
C10—C9—N2—N3−0.4 (2)N4—N5—Zn1—N1−10.30 (11)
C10—C9—N2—C8179.88 (19)C1—N5—Zn1—N3164.27 (19)
N1—C8—N2—C9178.77 (18)N4—N5—Zn1—N3−27.46 (18)
C7—C8—N2—C9−1.3 (3)C1—N5—Zn1—Cl147.6 (2)
N1—C8—N2—N3−0.9 (2)N4—N5—Zn1—Cl1−144.18 (11)
C7—C8—N2—N3179.04 (18)C1—N5—Zn1—Cl2−71.1 (2)
C10—C11—N3—N2−0.3 (2)N4—N5—Zn1—Cl297.15 (12)
C10—C11—N3—Zn1−176.68 (16)C11—N3—Zn1—N1179.3 (2)
C9—N2—N3—C110.4 (2)N2—N3—Zn1—N13.17 (12)
C8—N2—N3—C11−179.84 (17)C11—N3—Zn1—N5−163.4 (2)
C9—N2—N3—Zn1177.92 (12)N2—N3—Zn1—N520.38 (19)
C8—N2—N3—Zn1−2.4 (2)C11—N3—Zn1—Cl1−45.1 (2)
C2—C3—N4—N50.2 (2)N2—N3—Zn1—Cl1138.76 (12)
C2—C3—N4—C4176.33 (18)C11—N3—Zn1—Cl273.1 (2)
N1—C4—N4—N5−3.0 (2)N2—N3—Zn1—Cl2−103.08 (12)
Symmetry codes: (i) −x+1, −y, −z.
Table 1
Selected geometric parameters (Å) top
Cg1···Cg2i3.4087 (12)Cg2···Cg3i3.6253 (13)
Symmetry codes: (i) −x+1, −y, −z.
Acknowledgements top

This work was supported by the Doctor's Foundation of Binzhou University.

references
References top

Balamurugan, V., Hundal, M. S. & Mukherjee, R. (2004). Chem. Eur. J. 10, 1683–1690.

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.