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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): m1374.
Published online 2008 October 9. doi:  10.1107/S1600536808031152
PMCID: PMC2959550

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

Abstract

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 π–π stacking inter­actions between the 2,6-dipyrazol-1-ylpyridine ligands of neighbouring mol­ecules.

Related literature

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

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Object name is e-64-m1374-scheme1.jpg

Experimental

Crystal data

  • [ZnCl2(C11H9N5)]
  • M r = 347.50
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-m1374-efi1.jpg
  • a = 10.9630 (17) Å
  • b = 8.0263 (13) Å
  • c = 14.943 (2) Å
  • β = 93.079 (2)°
  • V = 1313.0 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.27 mm−1
  • T = 298 (2) K
  • 0.48 × 0.42 × 0.29 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.409, T max = 0.559 (expected range = 0.379–0.518)
  • 7375 measured reflections
  • 2848 independent reflections
  • 2431 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.078
  • S = 1.05
  • 2848 reflections
  • 173 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.32 e Å−3

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

Table 1
Selected interatomic distances (Å)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031152/cv2454sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031152/cv2454Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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

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

Figures

Fig. 1.
The molecular structure of (I) showing the atomic numbering and 30% probability displacement ellipsoids.

Crystal data

[ZnCl2(C11H9N5)]F(000) = 696
Mr = 347.50Dx = 1.758 Mg m3
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 mm1
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

Bruker SMART APEX CCD diffractometer2848 independent reflections
Radiation source: fine-focus sealed tube2431 reflections with I > 2σ(I)
graphiteRint = 0.030
[var phi] 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

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) = 0.078w = 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 Å3
173 parametersΔρmin = −0.32 e Å3
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)

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 (Å2)

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)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2454).

References

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

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