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

Yang, Z.N.; Sun, T.T.

doi:10.1107/S1600536808031152

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1374

doi:10.1107/S1600536808031152

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

Zhong Nian Yang ^a ^* and Ting Ting Sun ^b

^aDepartment of Chemistry and Chemical Engineering, Binzhou University, Binzhou 256603, People's Republic of China, and ^bDepartment of Chemistry, Shandong Normal University, Jinan 250014, People's Republic of China
^*Correspondence e-mail: yangzhongnian1978@yahoo.com.cn

(Received 20 September 2008; accepted 26 September 2008; online 9 October 2008)

In the title complex, [ZnCl₂(C₁₁H₉N₅)], the Zn^II 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 ).

Experimental

Crystal data

[ZnCl₂(C₁₁H₉N₅)]
M_r = 347.50
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.029
wR(F²) = 0.078
S = 1.05
2848 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected interatomic distances (Å)

Cg1, Cg2 and Cg3 are the centroids of the C4/N1/N4/N5/Zn1, C1–C3/N4/N5 and C4–C8/N1 rings, respectively.

Cg1⋯Cg2ⁱ	3.4087 (12)
Cg2⋯Cg3ⁱ	3.6253 (13)
Symmetry code: (i) -x+1, -y, -z.

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

Supporting information

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

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

checkCIF report

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 Zn^II 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.

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

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
M_r = 347.50	D_x = 1.758 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3889 reflections
a = 10.9630 (17) Å	θ = 2.4–28.2°
b = 8.0263 (13) Å	µ = 2.27 mm⁻¹
c = 14.943 (2) Å	T = 298 K
β = 93.079 (2)°	Block, colourless
V = 1313.0 (4) Å³	0.48 × 0.42 × 0.29 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2848 independent reflections
Radiation source: fine-focus sealed tube	2431 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 27.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→14
T_min = 0.409, T_max = 0.559	k = −9→10
7375 measured reflections	l = −16→18

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0445P)² + 0.0869P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
2848 reflections	Δρ_max = 0.28 e Å⁻³
173 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0167 (11)

Crystal data top

[ZnCl₂(C₁₁H₉N₅)]	V = 1313.0 (4) Å³
M_r = 347.50	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.9630 (17) Å	µ = 2.27 mm⁻¹
b = 8.0263 (13) Å	T = 298 K
c = 14.943 (2) Å	0.48 × 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)
T_min = 0.409, T_max = 0.559	R_int = 0.030
7375 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.05	Δρ_max = 0.28 e Å⁻³
2848 reflections	Δρ_min = −0.32 e Å⁻³
173 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
C1	0.47097 (18)	0.3058 (2)	0.04770 (16)	0.0447 (5)
H1	0.4465	0.3525	0.1008	0.054*
C2	0.40961 (19)	0.3275 (3)	−0.03549 (17)	0.0478 (5)
H2	0.3389	0.3891	−0.0481	0.057*
C3	0.47479 (18)	0.2396 (2)	−0.09475 (16)	0.0440 (5)
H3	0.4572	0.2292	−0.1561	0.053*
C4	0.66172 (17)	0.0609 (2)	−0.07399 (13)	0.0349 (4)
C5	0.66885 (19)	0.0026 (3)	−0.16015 (14)	0.0448 (5)
H5	0.6147	0.0387	−0.2062	0.054*
C6	0.7591 (2)	−0.1111 (3)	−0.17553 (16)	0.0487 (5)
H6	0.7663	−0.1533	−0.2330	0.058*
C7	0.8394 (2)	−0.1637 (3)	−0.10659 (15)	0.0442 (5)
H7	0.8998	−0.2423	−0.1160	0.053*
C8	0.82578 (17)	−0.0944 (2)	−0.02369 (14)	0.0357 (4)
C9	0.99689 (18)	−0.2410 (2)	0.06325 (16)	0.0454 (5)
H9	1.0275	−0.3088	0.0192	0.054*
C10	1.0387 (2)	−0.2314 (3)	0.14943 (17)	0.0502 (6)
H10	1.1036	−0.2903	0.1767	0.060*
C11	0.9647 (2)	−0.1152 (3)	0.18931 (17)	0.0491 (6)
H11	0.9730	−0.0837	0.2492	0.059*
Cl1	0.65199 (5)	0.06053 (7)	0.25184 (4)	0.05045 (17)
Cl2	0.83525 (5)	0.37392 (6)	0.12155 (4)	0.04545 (15)
N1	0.74008 (13)	0.01621 (18)	−0.00710 (10)	0.0327 (3)
N2	0.90163 (15)	−0.13336 (19)	0.05243 (12)	0.0374 (4)
N3	0.88095 (15)	−0.0554 (2)	0.13084 (11)	0.0417 (4)
N4	0.57069 (14)	0.1699 (2)	−0.04655 (11)	0.0366 (4)
N5	0.56823 (14)	0.2105 (2)	0.04169 (11)	0.0385 (4)
Zn1	0.73202 (2)	0.13073 (3)	0.121755 (15)	0.03696 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0377 (11)	0.0347 (10)	0.0624 (14)	−0.0040 (8)	0.0090 (10)	−0.0009 (10)
C2	0.0347 (10)	0.0363 (10)	0.0721 (16)	−0.0005 (9)	−0.0004 (10)	0.0102 (10)
C3	0.0360 (10)	0.0439 (11)	0.0512 (13)	−0.0045 (9)	−0.0066 (9)	0.0124 (9)
C4	0.0329 (10)	0.0332 (9)	0.0386 (11)	−0.0072 (7)	0.0014 (8)	0.0020 (8)
C5	0.0441 (11)	0.0538 (12)	0.0361 (11)	−0.0052 (10)	−0.0025 (9)	0.0023 (9)
C6	0.0539 (13)	0.0570 (13)	0.0357 (12)	−0.0052 (10)	0.0062 (10)	−0.0076 (10)
C7	0.0428 (12)	0.0470 (11)	0.0435 (12)	0.0032 (9)	0.0071 (9)	−0.0029 (9)
C8	0.0338 (10)	0.0337 (9)	0.0400 (11)	−0.0062 (8)	0.0054 (8)	0.0026 (8)
C9	0.0392 (11)	0.0374 (11)	0.0599 (15)	0.0031 (9)	0.0064 (10)	0.0053 (9)
C10	0.0414 (11)	0.0469 (12)	0.0613 (15)	0.0030 (9)	−0.0047 (10)	0.0154 (11)
C11	0.0458 (12)	0.0549 (13)	0.0460 (14)	0.0010 (10)	−0.0036 (10)	0.0090 (10)
Cl1	0.0523 (3)	0.0611 (4)	0.0389 (3)	−0.0069 (2)	0.0112 (2)	−0.0012 (2)
Cl2	0.0431 (3)	0.0428 (3)	0.0500 (3)	−0.0086 (2)	−0.0017 (2)	−0.0035 (2)
N1	0.0309 (8)	0.0332 (8)	0.0338 (9)	−0.0042 (6)	0.0000 (7)	0.0014 (7)
N2	0.0348 (9)	0.0376 (9)	0.0400 (10)	0.0006 (6)	0.0034 (7)	0.0025 (7)
N3	0.0413 (9)	0.0486 (10)	0.0351 (9)	0.0030 (8)	0.0022 (7)	0.0011 (7)
N4	0.0316 (8)	0.0370 (8)	0.0407 (10)	−0.0038 (7)	−0.0015 (7)	0.0037 (7)
N5	0.0359 (9)	0.0376 (9)	0.0419 (10)	−0.0029 (7)	0.0022 (7)	−0.0007 (7)
Zn1	0.03632 (16)	0.04045 (17)	0.03418 (17)	−0.00377 (9)	0.00263 (10)	−0.00260 (9)

Geometric parameters (Å, º) top

C1—N5	1.319 (3)	C8—N1	1.325 (2)
C1—C2	1.392 (3)	C8—N2	1.408 (3)
C1—H1	0.9300	C9—C10	1.346 (3)
C2—C3	1.364 (3)	C9—N2	1.358 (2)
C2—H2	0.9300	C9—H9	0.9300
C3—N4	1.362 (2)	C10—C11	1.391 (3)
C3—H3	0.9300	C10—H10	0.9300
C4—N1	1.332 (2)	C11—N3	1.323 (3)
C4—C5	1.376 (3)	C11—H11	0.9300
C4—N4	1.405 (2)	Cl1—Zn1	2.2470 (6)
C5—C6	1.374 (3)	Cl2—Zn1	2.2564 (6)
C5—H5	0.9300	N1—Zn1	2.1397 (16)
C6—C7	1.385 (3)	N2—N3	1.358 (2)
C6—H6	0.9300	N3—Zn1	2.2117 (17)
C7—C8	1.374 (3)	N4—N5	1.360 (2)
C7—H7	0.9300	N5—Zn1	2.1988 (16)

Cg1···Cg2ⁱ	3.4087 (12)	Cg2···Cg3ⁱ	3.6253 (13)

N5—C1—C2	111.4 (2)	C11—C10—H10	127.1
N5—C1—H1	124.3	N3—C11—C10	111.1 (2)
C2—C1—H1	124.3	N3—C11—H11	124.4
C3—C2—C1	105.67 (19)	C10—C11—H11	124.4
C3—C2—H2	127.2	C8—N1—C4	118.37 (17)
C1—C2—H2	127.2	C8—N1—Zn1	121.33 (13)
N4—C3—C2	106.6 (2)	C4—N1—Zn1	120.23 (13)
N4—C3—H3	126.7	C9—N2—N3	110.69 (17)
C2—C3—H3	126.7	C9—N2—C8	130.90 (18)
N1—C4—C5	122.93 (18)	N3—N2—C8	118.41 (16)
N1—C4—N4	112.86 (17)	C11—N3—N2	105.09 (18)
C5—C4—N4	124.19 (18)	C11—N3—Zn1	140.30 (16)
C6—C5—C4	117.4 (2)	N2—N3—Zn1	114.53 (12)
C6—C5—H5	121.3	N5—N4—C3	111.07 (17)
C4—C5—H5	121.3	N5—N4—C4	118.92 (16)
C5—C6—C7	120.8 (2)	C3—N4—C4	129.90 (18)
C5—C6—H6	119.6	C1—N5—N4	105.25 (17)
C7—C6—H6	119.6	C1—N5—Zn1	140.46 (15)
C8—C7—C6	116.84 (19)	N4—N5—Zn1	113.56 (11)
C8—C7—H7	121.6	N1—Zn1—N5	72.99 (6)
C6—C7—H7	121.6	N1—Zn1—N3	72.49 (6)
N1—C8—C7	123.55 (19)	N5—Zn1—N3	143.97 (6)
N1—C8—N2	113.06 (17)	N1—Zn1—Cl1	135.05 (4)
C7—C8—N2	123.38 (18)	N5—Zn1—Cl1	101.44 (5)
C10—C9—N2	107.3 (2)	N3—Zn1—Cl1	95.67 (5)
C10—C9—H9	126.3	N1—Zn1—Cl2	108.99 (4)
N2—C9—H9	126.3	N5—Zn1—Cl2	98.18 (5)
C9—C10—C11	105.8 (2)	N3—Zn1—Cl2	102.45 (5)
C9—C10—H10	127.1	Cl1—Zn1—Cl2	115.93 (2)

N5—C1—C2—C3	−0.1 (2)	C5—C4—N4—N5	175.69 (18)
C1—C2—C3—N4	−0.1 (2)	N1—C4—N4—C3	−178.85 (18)
N1—C4—C5—C6	2.3 (3)	C5—C4—N4—C3	−0.2 (3)
N4—C4—C5—C6	−176.27 (18)	C2—C1—N5—N4	0.2 (2)
C4—C5—C6—C7	−0.2 (3)	C2—C1—N5—Zn1	169.07 (15)
C5—C6—C7—C8	−1.3 (3)	C3—N4—N5—C1	−0.3 (2)
C6—C7—C8—N1	0.9 (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—C11	0.3 (2)	C4—N4—N5—Zn1	10.85 (19)
C9—C10—C11—N3	0.0 (3)	C8—N1—Zn1—N5	−173.52 (14)
C7—C8—N1—C4	1.0 (3)	C4—N1—Zn1—N5	9.64 (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—N3	179.15 (15)
N2—C8—N1—Zn1	4.0 (2)	C8—N1—Zn1—Cl1	−84.26 (14)
C5—C4—N1—C8	−2.7 (3)	C4—N1—Zn1—Cl1	98.90 (13)
N4—C4—N1—C8	176.00 (15)	C8—N1—Zn1—Cl2	93.49 (13)
C5—C4—N1—Zn1	174.24 (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—C8	179.88 (19)	C1—N5—Zn1—N3	164.27 (19)
N1—C8—N2—C9	178.77 (18)	N4—N5—Zn1—N3	−27.46 (18)
C7—C8—N2—C9	−1.3 (3)	C1—N5—Zn1—Cl1	47.6 (2)
N1—C8—N2—N3	−0.9 (2)	N4—N5—Zn1—Cl1	−144.18 (11)
C7—C8—N2—N3	179.04 (18)	C1—N5—Zn1—Cl2	−71.1 (2)
C10—C11—N3—N2	−0.3 (2)	N4—N5—Zn1—Cl2	97.15 (12)
C10—C11—N3—Zn1	−176.68 (16)	C11—N3—Zn1—N1	179.3 (2)
C9—N2—N3—C11	0.4 (2)	N2—N3—Zn1—N1	3.17 (12)
C8—N2—N3—C11	−179.84 (17)	C11—N3—Zn1—N5	−163.4 (2)
C9—N2—N3—Zn1	177.92 (12)	N2—N3—Zn1—N5	20.38 (19)
C8—N2—N3—Zn1	−2.4 (2)	C11—N3—Zn1—Cl1	−45.1 (2)
C2—C3—N4—N5	0.2 (2)	N2—N3—Zn1—Cl1	138.76 (12)
C2—C3—N4—C4	176.33 (18)	C11—N3—Zn1—Cl2	73.1 (2)
N1—C4—N4—N5	−3.0 (2)	N2—N3—Zn1—Cl2	−103.08 (12)

Symmetry code: (i) −x+1, −y, −z.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₁H₉N₅)]
M_r	347.50
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.9630 (17), 8.0263 (13), 14.943 (2)
β (°)	93.079 (2)
V (Å³)	1313.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.27
Crystal size (mm)	0.48 × 0.42 × 0.29

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.409, 0.559
No. of measured, independent and observed [I > 2σ(I)] reflections	7375, 2848, 2431
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.078, 1.05
No. of reflections	2848
No. of parameters	173
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXTL (Sheldrick, 2008) and local programs.

Selected interatomic distances (Å) top

Cg1···Cg2ⁱ

3.4087 (12)

Cg2···Cg3ⁱ

3.6253 (13)

Symmetry code: (i) −x+1, −y, −z.

Acknowledgements

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

References

Balamurugan, V., Hundal, M. S. & Mukherjee, R. (2004). Chem. Eur. J. 10, 1683–1690. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar