Dibromido(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)zinc(II)

Zhao, Q.-L.; Li, G.-P.

doi:10.1107/S1600536809019266

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page m693

doi:10.1107/S1600536809019266

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Dibromido(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)zinc(II)

Qing-Lan Zhao ^a and Guo-Peng Li ^b ^*

^aCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, Henan, People's Republic of China, and ^bInstitute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, Henan, People's Republic of China
^*Correspondence e-mail: imce18@163.com

(Received 5 May 2009; accepted 21 May 2009; online 29 May 2009)

In the title compound, [ZnBr₂(C₁₅H₁₁N₃)], the Zn^II ion is five-coordinated by the three N atoms from a 2,2′:6′,2′′-terpyridine ligand (terpy) and two bromide anions in a distorted trigonal bipyramidal configuration. Each molecule is situated on a twofold rotational axis that passes through the Zn^II ion and the central ring of the terpy ligand. In the crystal structure, aromatic π–π interactions between terpy ligands [centroid–centroid distances = 3.6265 (9) Å] link molecules into stacks propagated in the [001] direction.

Related literature

For related structures, see: Alizadeh et al. (2009 ); Mahmoudi et al. (2009 ); Huang et al. (2009 ); Ma et al. (2009 ); Bai et al. (2009 ).

Experimental

Crystal data

[ZnBr₂(C₁₅H₁₁N₃)]
M_r = 458.46
Monoclinic, C 2/c
a = 17.0972 (5) Å
b = 9.3528 (3) Å
c = 11.5334 (4) Å
β = 126.051 (1)°
V = 1491.08 (8) Å³
Z = 4
Mo Kα radiation
μ = 7.00 mm⁻¹
T = 296 K
0.20 × 0.18 × 0.16 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.335, T_max = 0.401 (expected range = 0.273–0.326)
9665 measured reflections
1457 independent reflections
1371 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.015
wR(F²) = 0.039
S = 1.08
1457 reflections
97 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019266/cv2561sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019266/cv2561Isup2.hkl

checkCIF report

Comment top

As a contribution to structural characterization of 2,2':6',2''-terpyridine complexes (Alizadeh et al., 2009; Huang et al., 2009; Ma et al., 2009; Bai et al., 2009) we present here the title complex (I).

In (I) (Fig. 1), the Zn^II ion is five-coordinated in a distorted trigonal bipyramidal configuration by three N atoms from a 2,2':6',2''-terpyridine ligand and by two Br anions. The Zn–Br and Zn–N bond lengths are within normal ranges (Mahmoudi et al., 2009).

In the crystal structure, the π–π stacking interactions between aromatic rings of Cg1 and Cg2 [Cg1 and Cg2 are (N1, C6 — C8, C7ⁱ, C6ⁱ) and (N2, C1 — C5) ring centroids, respectively, symmetry code: (i) -x + 1, y, -z + 1/2] are observed, with a centroid–centroid distances of 3.6265 (9) Å.

Related literature top

For related structures, see: Alizadeh et al. (2009); Mahmoudi et al. (2009); Huang et al. (2009); Ma et al. (2009); Bai et al. (2009).

Experimental top

The title compound was synthesized hydrothermally in a Teflon-lined autoclave (25 mL) by heating a mixture of 2,2':6',2''-terpyridine (0.2 mmol), ZnBr₂ (0.2 mmol) and one drop of Et₃N (pH ≈ 8–9) in water (10 mL) at 393 K for 3 d. Crystals suitable for X-ray analysis were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom-labelling scheme [symmetry code: (A) -x, + 1, y, -z + 1/2]. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A portion of the crystal packing showing the π–π interactions (dashed lines) between the aromatic rings.

Dibromido(2,2':6',2''-terpyridine-κ³N,N',N'')zinc(II) top

Crystal data top

[ZnBr₂(C₁₅H₁₁N₃)]	F(000) = 888
M_r = 458.46	D_x = 2.042 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1580 reflections
a = 17.0972 (5) Å	θ = 2.5–26.3°
b = 9.3528 (3) Å	µ = 7.00 mm⁻¹
c = 11.5334 (4) Å	T = 296 K
β = 126.051 (1)°	Block, colourless
V = 1491.08 (8) Å³	0.20 × 0.18 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD diffractometer	1457 independent reflections
Radiation source: fine-focus sealed tube	1371 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −21→21
T_min = 0.335, T_max = 0.401	k = −11→11
9665 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.015	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.039	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0184P)² + 1.2604P] where P = (F_o² + 2F_c²)/3
1457 reflections	(Δ/σ)_max < 0.001
97 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[ZnBr₂(C₁₅H₁₁N₃)]	V = 1491.08 (8) Å³
M_r = 458.46	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.0972 (5) Å	µ = 7.00 mm⁻¹
b = 9.3528 (3) Å	T = 296 K
c = 11.5334 (4) Å	0.20 × 0.18 × 0.16 mm
β = 126.051 (1)°

Data collection top

Bruker SMART APEXII CCD diffractometer	1457 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1371 reflections with I > 2σ(I)
T_min = 0.335, T_max = 0.401	R_int = 0.019
9665 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.015	0 restraints
wR(F²) = 0.039	H-atom parameters constrained
S = 1.08	Δρ_max = 0.27 e Å⁻³
1457 reflections	Δρ_min = −0.29 e Å⁻³
97 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
Br1	0.380531 (15)	0.11870 (2)	0.03979 (2)	0.04022 (8)
Zn1	0.5000	0.25499 (3)	0.2500	0.02736 (8)
N1	0.5000	0.4802 (2)	0.2500	0.0253 (4)
N2	0.58982 (11)	0.31649 (16)	0.18054 (15)	0.0288 (3)
C1	0.63375 (14)	0.2248 (2)	0.1474 (2)	0.0352 (4)
H1	0.6256	0.1272	0.1525	0.042*
C2	0.69093 (14)	0.2696 (2)	0.1056 (2)	0.0392 (4)
H2	0.7210	0.2033	0.0838	0.047*
C3	0.70254 (14)	0.4137 (2)	0.0970 (2)	0.0394 (4)
H3	0.7411	0.4461	0.0700	0.047*
C4	0.65606 (13)	0.5102 (2)	0.12890 (18)	0.0346 (4)
H4	0.6620	0.6081	0.1219	0.042*
C5	0.60056 (12)	0.45792 (18)	0.17152 (16)	0.0268 (4)
C6	0.54892 (12)	0.55136 (18)	0.21013 (16)	0.0263 (3)
C7	0.54910 (13)	0.69976 (19)	0.20701 (19)	0.0337 (4)
H7	0.5815	0.7485	0.1767	0.040*
C8	0.5000	0.7736 (3)	0.2500	0.0367 (6)
H8	0.5000	0.8730	0.2500	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04910 (14)	0.03300 (12)	0.03959 (12)	−0.01116 (8)	0.02667 (10)	−0.00711 (7)
Zn1	0.03545 (17)	0.01984 (14)	0.03395 (16)	0.000	0.02441 (14)	0.000
N1	0.0293 (10)	0.0231 (10)	0.0253 (9)	0.000	0.0170 (9)	0.000
N2	0.0322 (8)	0.0264 (8)	0.0335 (7)	−0.0007 (6)	0.0224 (7)	0.0004 (6)
C1	0.0407 (11)	0.0311 (10)	0.0417 (10)	0.0025 (8)	0.0285 (9)	−0.0011 (8)
C2	0.0372 (11)	0.0487 (12)	0.0398 (10)	0.0025 (9)	0.0271 (9)	−0.0038 (9)
C3	0.0354 (10)	0.0545 (12)	0.0380 (10)	−0.0069 (9)	0.0271 (9)	−0.0022 (9)
C4	0.0367 (10)	0.0359 (10)	0.0339 (9)	−0.0072 (8)	0.0222 (8)	0.0005 (8)
C5	0.0268 (9)	0.0287 (9)	0.0235 (7)	−0.0027 (7)	0.0139 (7)	0.0004 (7)
C6	0.0274 (9)	0.0247 (8)	0.0237 (7)	−0.0027 (7)	0.0133 (7)	0.0007 (6)
C7	0.0360 (10)	0.0268 (9)	0.0351 (9)	−0.0042 (8)	0.0193 (8)	0.0030 (7)
C8	0.0426 (16)	0.0201 (12)	0.0409 (14)	0.000	0.0210 (13)	0.000

Geometric parameters (Å, º) top

Br1—Zn1	2.4179 (2)	C2—H2	0.9300
Zn1—N1	2.106 (2)	C3—C4	1.388 (3)
Zn1—N2ⁱ	2.1861 (14)	C3—H3	0.9300
Zn1—N2	2.1861 (14)	C4—C5	1.389 (2)
Zn1—Br1ⁱ	2.4179 (2)	C4—H4	0.9300
N1—C6ⁱ	1.3441 (19)	C5—C6	1.485 (2)
N1—C6	1.3441 (19)	C6—C7	1.388 (3)
N2—C1	1.336 (2)	C7—C8	1.385 (2)
N2—C5	1.348 (2)	C7—H7	0.9300
C1—C2	1.385 (3)	C8—C7ⁱ	1.385 (2)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.374 (3)

N1—Zn1—N2ⁱ	74.75 (4)	C3—C2—H2	120.5
N1—Zn1—N2	74.75 (4)	C1—C2—H2	120.5
N2ⁱ—Zn1—N2	149.49 (8)	C2—C3—C4	119.27 (17)
N1—Zn1—Br1	121.815 (7)	C2—C3—H3	120.4
N2ⁱ—Zn1—Br1	98.34 (4)	C4—C3—H3	120.4
N2—Zn1—Br1	97.60 (4)	C3—C4—C5	118.78 (18)
N1—Zn1—Br1ⁱ	121.815 (7)	C3—C4—H4	120.6
N2ⁱ—Zn1—Br1ⁱ	97.60 (4)	C5—C4—H4	120.6
N2—Zn1—Br1ⁱ	98.34 (4)	N2—C5—C4	121.69 (16)
Br1—Zn1—Br1ⁱ	116.370 (14)	N2—C5—C6	114.99 (14)
C6ⁱ—N1—C6	120.6 (2)	C4—C5—C6	123.32 (16)
C6ⁱ—N1—Zn1	119.68 (10)	N1—C6—C7	121.01 (16)
C6—N1—Zn1	119.68 (10)	N1—C6—C5	114.25 (15)
C1—N2—C5	118.88 (15)	C7—C6—C5	124.74 (15)
C1—N2—Zn1	124.80 (12)	C8—C7—C6	118.57 (17)
C5—N2—Zn1	116.32 (11)	C8—C7—H7	120.7
N2—C1—C2	122.43 (18)	C6—C7—H7	120.7
N2—C1—H1	118.8	C7ⁱ—C8—C7	120.2 (2)
C2—C1—H1	118.8	C7ⁱ—C8—H8	119.9
C3—C2—C1	118.93 (18)	C7—C8—H8	119.9

N2ⁱ—Zn1—N1—C6ⁱ	0.68 (9)	C1—C2—C3—C4	−0.6 (3)
N2—Zn1—N1—C6ⁱ	−179.32 (9)	C2—C3—C4—C5	1.3 (3)
Br1—Zn1—N1—C6ⁱ	91.12 (8)	C1—N2—C5—C4	−0.1 (2)
Br1ⁱ—Zn1—N1—C6ⁱ	−88.88 (8)	Zn1—N2—C5—C4	179.88 (12)
N2ⁱ—Zn1—N1—C6	−179.32 (9)	C1—N2—C5—C6	179.87 (15)
N2—Zn1—N1—C6	0.68 (9)	Zn1—N2—C5—C6	−0.19 (18)
Br1—Zn1—N1—C6	−88.88 (8)	C3—C4—C5—N2	−0.9 (3)
Br1ⁱ—Zn1—N1—C6	91.12 (8)	C3—C4—C5—C6	179.12 (16)
N1—Zn1—N2—C1	179.71 (15)	C6ⁱ—N1—C6—C7	−0.96 (12)
N2ⁱ—Zn1—N2—C1	179.71 (15)	Zn1—N1—C6—C7	179.04 (12)
Br1—Zn1—N2—C1	−59.30 (14)	C6ⁱ—N1—C6—C5	179.02 (15)
Br1ⁱ—Zn1—N2—C1	58.90 (14)	Zn1—N1—C6—C5	−0.98 (15)
N1—Zn1—N2—C5	−0.23 (11)	N2—C5—C6—N1	0.74 (19)
N2ⁱ—Zn1—N2—C5	−0.23 (11)	C4—C5—C6—N1	−179.33 (14)
Br1—Zn1—N2—C5	120.76 (11)	N2—C5—C6—C7	−179.29 (16)
Br1ⁱ—Zn1—N2—C5	−121.05 (11)	C4—C5—C6—C7	0.6 (3)
C5—N2—C1—C2	0.8 (3)	N1—C6—C7—C8	1.9 (2)
Zn1—N2—C1—C2	−179.16 (14)	C5—C6—C7—C8	−178.10 (13)
N2—C1—C2—C3	−0.4 (3)	C6—C7—C8—C7ⁱ	−0.91 (11)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[ZnBr₂(C₁₅H₁₁N₃)]
M_r	458.46
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	17.0972 (5), 9.3528 (3), 11.5334 (4)
β (°)	126.051 (1)
V (Å³)	1491.08 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	7.00
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.335, 0.401
No. of measured, independent and observed [I > 2σ(I)] reflections	9665, 1457, 1371
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.039, 1.08
No. of reflections	1457
No. of parameters	97
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.29

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors are grateful to the Henan Administration of Science and Technology for financial support (grant No. 092300410031).

References

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