Dibromido{2-[(4-bromo­phen­yl)imino­meth­yl]pyridine-κ2N,N′}zinc(II)

Khalaj, M.; Dehghanpour, S.; Mahmoudi, A.; Seyedidarzam, S.

doi:10.1107/S1600536809025653

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m890

doi:10.1107/S1600536809025653

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Dibromido{2-[(4-bromophenyl)iminomethyl]pyridine-κ²N,N′}zinc(II)

Mehdi Khalaj,^a ^* Saeed Dehghanpour,^b Ali Mahmoudi ^a and Shila Seyedidarzam ^a

^aDepartment of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran, and ^bDepartment of Chemistry, Alzahra University, PO Box 1993891176, Vanak, Tehran, Iran
^*Correspondence e-mail: Khalaj_mehdi@yahoo.com

(Received 11 June 2009; accepted 2 July 2009; online 11 July 2009)

In the title complex, [ZnBr₂(C₁₂H₉BrN₂)], the Zn^II ion is in a distorted tetrahedral coordination environment formed by two imine N atoms of the bis-chelating N-heterocyclic ligand and two Br atoms. The dihedral angle between the pyridine and benzene rings is 8.04 (17)°.

Related literature

For background information on diimine complexes, see: Small et al. (1998 ). For the use of iminopyridine complexes as olefin polymerization catalysts, see: Ittel et al. (2000 ); Britovsek et al. (1999 ). For related structures, see Dehghanpour & Mahmoudi (2007 ); Dehghanpour et al. (2007 ).

Experimental

Crystal data

[ZnBr₂(C₁₂H₉BrN₂)]
M_r = 486.31
Triclinic, $[P \overline 1]$
a = 7.7506 (13) Å
b = 8.7413 (16) Å
c = 10.9846 (18) Å
α = 89.966 (5)°
β = 72.182 (6)°
γ = 88.665 (6)°
V = 708.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 10.18 mm⁻¹
T = 100 K
0.28 × 0.16 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2005 ) T_min = 0.153, T_max = 0.293
7668 measured reflections
3230 independent reflections
2703 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.095
S = 1.00
3230 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 2.06 e Å⁻³
Δρ_min = −1.70 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—N1	2.062 (5)
Zn1—N2	2.094 (4)
Zn1—Br1	2.3310 (8)
Zn1—Br2	2.3507 (9)

N1—Zn1—N2	80.62 (18)
N1—Zn1—Br1	119.57 (13)
N2—Zn1—Br1	119.19 (13)
N1—Zn1—Br2	110.14 (13)
N2—Zn1—Br2	108.91 (12)
Br1—Zn1—Br2	113.95 (3)

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025653/lh2845sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025653/lh2845Isup2.hkl

checkCIF report

Comment top

Complexes of iminopyridines with late transition metals have recently found a renewal of interest (Small et al., 1998). The unexpected and recent discovery that such complexes in particular the imiopyridine iron(II) and cobalt (II) complexes, may act as active catalysts for olefine polymerization render them more attractive for chemists (Ittel et al., 2000; Britovsek et al., 1999). The title complex, (I), Fig. 1, was prepared by the reaction of ZnBr₂ with the potentially bidentate ligand (4-bromophenyl)pyridin-2-ylmethyleneamine.

As might be expected for a four-coordinated zinc(II) complex, the metal center has a tetrahedral coordination environment. However, there are signficant distortions mainly due to the presence of the 5-membered chelate cycle: the endocyclic N1—Zn1—N2 angle [80.62 (18)°] is much narrower than the ideal tetrahedral angle of 109.5°, whereas the N1—Zn1—Br1 angle [119.57 (13)°] is much wider than the ideal tetrahedral angle. The Zn—Br and Zn—N bond dimensions compare well with the values found in other tetrahedral diimine complexes of zinc bromide (Dehghanpour & Mahmoudi, 2007; Dehghanpour et al., 2007).

Related literature top

For background information on diimine complexes, see: Small et al. (1998). For the use of iminopyridine complexes as olefin polymerization catalysts, see: Ittel et al. (2000); Britovsek et al. (1999). For related structures, see Dehghanpour & Mahmoudi (2007); Dehghanpour et al. (2007).

Experimental top

The title complex was prepared by the reaction of ZnBr₂ and (4-bromophenyl)pyridin-2-ylmethyleneamine (molar ratio 1:1) in acetonitrile at room temperature. The solution was then concentrated under vacuum, and diffusion of diethyl ether vapor into the concentrated solution gave colourless crystals of (I) in 84% yield. Calc. for C₁₂H₉Br₃N₂Zn: C 29.64, H 1.87, N 5.76%; found: C 29.68, H 1.89, N 5.74%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); 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).

Figures top

Fig. 1. Molecular structure of (I) showing the atom-labelling scheme with thermal ellipsoids drawn at the 50% probability level.

Dibromido{2-[(4-bromophenyl)iminomethyl]pyridine- κ²N,N'}zinc(II) top

Crystal data top

[ZnBr₂(C₁₂H₉BrN₂)]	Z = 2
M_r = 486.31	F(000) = 460
Triclinic, P1	D_x = 2.280 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7506 (13) Å	Cell parameters from 469 reflections
b = 8.7413 (16) Å	θ = 2.1–21.4°
c = 10.9846 (18) Å	µ = 10.18 mm⁻¹
α = 89.966 (5)°	T = 100 K
β = 72.182 (6)°	Prism, colourless
γ = 88.665 (6)°	0.28 × 0.16 × 0.12 mm
V = 708.3 (2) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	3230 independent reflections
Radiation source: fine-focus sealed tube	2703 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
Detector resolution: 0 pixels mm^-1	θ_max = 27.5°, θ_min = 2.0°
ω scans	h = −10→10
Absorption correction: multi-scan (APEX2; Bruker, 2005)	k = −11→11
T_min = 0.153, T_max = 0.293	l = −14→14
7668 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.02P)² + 5.8P] where P = (F_o² + 2F_c²)/3
3230 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 2.06 e Å⁻³
0 restraints	Δρ_min = −1.70 e Å⁻³

Crystal data top

[ZnBr₂(C₁₂H₉BrN₂)]	γ = 88.665 (6)°
M_r = 486.31	V = 708.3 (2) Å³
Triclinic, P1	Z = 2
a = 7.7506 (13) Å	Mo Kα radiation
b = 8.7413 (16) Å	µ = 10.18 mm⁻¹
c = 10.9846 (18) Å	T = 100 K
α = 89.966 (5)°	0.28 × 0.16 × 0.12 mm
β = 72.182 (6)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3230 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2005)	2703 reflections with I > 2σ(I)
T_min = 0.153, T_max = 0.293	R_int = 0.066
7668 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	Δρ_max = 2.06 e Å⁻³
3230 reflections	Δρ_min = −1.70 e Å⁻³
163 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
Zn1	0.60716 (8)	0.80440 (7)	0.65671 (6)	0.01457 (15)
Br1	0.37048 (7)	0.65625 (6)	0.63756 (5)	0.01697 (13)
Br2	0.81619 (8)	0.67009 (7)	0.73568 (6)	0.02353 (15)
Br3	1.15053 (7)	0.69529 (6)	−0.03171 (5)	0.01971 (14)
N1	0.5509 (6)	1.0180 (5)	0.7411 (4)	0.0161 (9)
N2	0.7495 (6)	0.9383 (5)	0.5020 (4)	0.0135 (9)
C1	0.6485 (7)	1.1285 (6)	0.6650 (5)	0.0142 (10)
C2	0.6414 (7)	1.2794 (6)	0.7039 (5)	0.0175 (11)
H2	0.7116	1.3522	0.6505	0.021*
C3	0.5270 (8)	1.3201 (7)	0.8248 (5)	0.0193 (11)
H3	0.5181	1.4212	0.8530	0.023*
C4	0.4275 (7)	1.2091 (7)	0.9018 (6)	0.0205 (12)
H4	0.3510	1.2339	0.9830	0.025*
C5	0.4428 (7)	1.0584 (7)	0.8567 (5)	0.0188 (11)
H5	0.3752	0.9836	0.9093	0.023*
C6	0.7597 (7)	1.0777 (6)	0.5374 (5)	0.0154 (10)
H6	0.8369	1.1452	0.4824	0.018*
C7	0.8461 (7)	0.8856 (6)	0.3766 (5)	0.0150 (10)
C8	0.9339 (7)	0.9837 (7)	0.2784 (5)	0.0181 (11)
H8	0.9309	1.0884	0.2941	0.022*
C9	1.0255 (7)	0.9271 (6)	0.1580 (5)	0.0164 (11)
H9	1.0858	0.9929	0.0931	0.020*
C10	1.0264 (7)	0.7708 (6)	0.1348 (5)	0.0156 (11)
C11	0.9348 (7)	0.6706 (6)	0.2296 (5)	0.0173 (11)
H11	0.9336	0.5666	0.2125	0.021*
C12	0.8446 (7)	0.7298 (6)	0.3514 (5)	0.0171 (11)
H12	0.7829	0.6644	0.4160	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0158 (3)	0.0090 (3)	0.0168 (3)	−0.0017 (2)	−0.0018 (2)	−0.0003 (2)
Br1	0.0164 (3)	0.0128 (3)	0.0203 (3)	−0.00344 (19)	−0.0032 (2)	−0.0010 (2)
Br2	0.0240 (3)	0.0125 (3)	0.0378 (4)	−0.0022 (2)	−0.0148 (2)	0.0031 (2)
Br3	0.0235 (3)	0.0160 (3)	0.0157 (3)	−0.0026 (2)	0.0000 (2)	−0.0042 (2)
N1	0.016 (2)	0.013 (2)	0.018 (2)	0.0013 (17)	−0.0022 (17)	−0.0008 (18)
N2	0.014 (2)	0.010 (2)	0.015 (2)	0.0001 (16)	−0.0027 (17)	0.0004 (17)
C1	0.014 (2)	0.009 (2)	0.020 (3)	−0.0001 (19)	−0.006 (2)	0.001 (2)
C2	0.019 (3)	0.011 (3)	0.023 (3)	0.000 (2)	−0.007 (2)	−0.001 (2)
C3	0.027 (3)	0.011 (3)	0.020 (3)	0.000 (2)	−0.007 (2)	−0.006 (2)
C4	0.019 (3)	0.022 (3)	0.018 (3)	0.001 (2)	−0.002 (2)	−0.008 (2)
C5	0.017 (3)	0.017 (3)	0.019 (3)	−0.001 (2)	0.000 (2)	0.000 (2)
C6	0.014 (2)	0.014 (3)	0.017 (3)	−0.001 (2)	−0.004 (2)	0.000 (2)
C7	0.012 (2)	0.015 (3)	0.017 (3)	−0.0015 (19)	−0.0029 (19)	−0.001 (2)
C8	0.019 (3)	0.014 (3)	0.018 (3)	−0.004 (2)	0.000 (2)	−0.002 (2)
C9	0.021 (3)	0.011 (3)	0.015 (3)	−0.004 (2)	−0.002 (2)	0.002 (2)
C10	0.016 (2)	0.016 (3)	0.012 (2)	0.000 (2)	−0.0002 (19)	−0.003 (2)
C11	0.019 (3)	0.010 (3)	0.023 (3)	−0.001 (2)	−0.005 (2)	−0.001 (2)
C12	0.021 (3)	0.014 (3)	0.013 (2)	−0.005 (2)	−0.001 (2)	0.002 (2)

Geometric parameters (Å, º) top

Zn1—N1	2.062 (5)	C4—C5	1.397 (8)
Zn1—N2	2.094 (4)	C4—H4	0.9300
Zn1—Br1	2.3310 (8)	C5—H5	0.9300
Zn1—Br2	2.3507 (9)	C6—H6	0.9300
Br3—C10	1.898 (5)	C7—C12	1.391 (8)
N1—C5	1.333 (7)	C7—C8	1.392 (8)
N1—C1	1.361 (7)	C8—C9	1.382 (7)
N2—C6	1.291 (7)	C8—H8	0.9300
N2—C7	1.422 (7)	C9—C10	1.389 (8)
C1—C2	1.381 (7)	C9—H9	0.9300
C1—C6	1.466 (8)	C10—C11	1.389 (8)
C2—C3	1.394 (8)	C11—C12	1.399 (8)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.374 (8)	C12—H12	0.9300
C3—H3	0.9300

N1—Zn1—N2	80.62 (18)	N1—C5—C4	122.3 (5)
N1—Zn1—Br1	119.57 (13)	N1—C5—H5	118.9
N2—Zn1—Br1	119.19 (13)	C4—C5—H5	118.9
N1—Zn1—Br2	110.14 (13)	N2—C6—C1	119.3 (5)
N2—Zn1—Br2	108.91 (12)	N2—C6—H6	120.3
Br1—Zn1—Br2	113.95 (3)	C1—C6—H6	120.3
C5—N1—C1	118.2 (5)	C12—C7—C8	119.4 (5)
C5—N1—Zn1	129.7 (4)	C12—C7—N2	117.7 (5)
C1—N1—Zn1	112.0 (3)	C8—C7—N2	122.8 (5)
C6—N2—C7	121.6 (5)	C9—C8—C7	120.7 (5)
C6—N2—Zn1	111.2 (4)	C9—C8—H8	119.6
C7—N2—Zn1	126.7 (4)	C7—C8—H8	119.6
N1—C1—C2	122.5 (5)	C8—C9—C10	119.2 (5)
N1—C1—C6	115.5 (5)	C8—C9—H9	120.4
C2—C1—C6	121.9 (5)	C10—C9—H9	120.4
C1—C2—C3	118.6 (5)	C9—C10—C11	121.4 (5)
C1—C2—H2	120.7	C9—C10—Br3	118.7 (4)
C3—C2—H2	120.7	C11—C10—Br3	119.9 (4)
C4—C3—C2	119.1 (5)	C10—C11—C12	118.5 (5)
C4—C3—H3	120.4	C10—C11—H11	120.7
C2—C3—H3	120.4	C12—C11—H11	120.7
C3—C4—C5	119.2 (5)	C7—C12—C11	120.6 (5)
C3—C4—H4	120.4	C7—C12—H12	119.7
C5—C4—H4	120.4	C11—C12—H12	119.7

N2—Zn1—N1—C5	175.0 (5)	Zn1—N1—C5—C4	176.4 (4)
Br1—Zn1—N1—C5	56.7 (5)	C3—C4—C5—N1	0.0 (9)
Br2—Zn1—N1—C5	−78.2 (5)	C7—N2—C6—C1	176.2 (5)
N2—Zn1—N1—C1	−8.2 (4)	Zn1—N2—C6—C1	−11.5 (6)
Br1—Zn1—N1—C1	−126.5 (3)	N1—C1—C6—N2	4.8 (7)
Br2—Zn1—N1—C1	98.6 (4)	C2—C1—C6—N2	−174.1 (5)
N1—Zn1—N2—C6	10.6 (4)	C6—N2—C7—C12	172.5 (5)
Br1—Zn1—N2—C6	129.4 (3)	Zn1—N2—C7—C12	1.4 (7)
Br2—Zn1—N2—C6	−97.6 (4)	C6—N2—C7—C8	−10.4 (8)
N1—Zn1—N2—C7	−177.5 (4)	Zn1—N2—C7—C8	178.5 (4)
Br1—Zn1—N2—C7	−58.8 (4)	C12—C7—C8—C9	−2.7 (8)
Br2—Zn1—N2—C7	74.3 (4)	N2—C7—C8—C9	−179.7 (5)
C5—N1—C1—C2	0.9 (8)	C7—C8—C9—C10	1.2 (8)
Zn1—N1—C1—C2	−176.3 (4)	C8—C9—C10—C11	1.0 (8)
C5—N1—C1—C6	−177.9 (5)	C8—C9—C10—Br3	179.3 (4)
Zn1—N1—C1—C6	4.8 (6)	C9—C10—C11—C12	−1.7 (8)
N1—C1—C2—C3	−1.3 (8)	Br3—C10—C11—C12	−180.0 (4)
C6—C1—C2—C3	177.5 (5)	C8—C7—C12—C11	1.9 (8)
C1—C2—C3—C4	1.0 (8)	N2—C7—C12—C11	179.2 (5)
C2—C3—C4—C5	−0.4 (9)	C10—C11—C12—C7	0.2 (8)
C1—N1—C5—C4	−0.2 (8)

Experimental details

Crystal data
Chemical formula	[ZnBr₂(C₁₂H₉BrN₂)]
M_r	486.31
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.7506 (13), 8.7413 (16), 10.9846 (18)
α, β, γ (°)	89.966 (5), 72.182 (6), 88.665 (6)
V (Å³)	708.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	10.18
Crystal size (mm)	0.28 × 0.16 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (APEX2; Bruker, 2005)
T_min, T_max	0.153, 0.293
No. of measured, independent and observed [I > 2σ(I)] reflections	7668, 3230, 2703
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.095, 1.00
No. of reflections	3230
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.06, −1.70

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

Selected geometric parameters (Å, º) top

Zn1—N1	2.062 (5)	Zn1—Br1	2.3310 (8)
Zn1—N2	2.094 (4)	Zn1—Br2	2.3507 (9)

N1—Zn1—N2	80.62 (18)	N1—Zn1—Br2	110.14 (13)
N1—Zn1—Br1	119.57 (13)	N2—Zn1—Br2	108.91 (12)
N2—Zn1—Br1	119.19 (13)	Br1—Zn1—Br2	113.95 (3)

Acknowledgements

MK acknowledges the Islamic Azad University Research Council for partial support of this work.

References

Britovsek, G. J. P., Bruce, M., Gibson, V. C., Kimberley, B. S., Maddox, P. J., Mastroianni, S., Mctavish, S. J., Redshaw, C., Solan, G. A., Stromberg, S., White, A. J. P. & Williams, D. J. (1999). J. Am. Chem. Soc. 121, 8728–8740. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dehghanpour, S. & Mahmoudi, A. (2007). Synth. React. Inorg. Met. Org. Chem. 37, 35–40. Web of Science CSD CrossRef CAS Google Scholar
Dehghanpour, S., Mahmoudi, A., Khalaj, M. & Salmanpour, S. (2007). Acta Cryst. E63, m2840. Web of Science CSD CrossRef IUCr Journals Google Scholar
Ittel, S. D., Johnson, L. K. & Brookhart, M. (2000). Chem. Rev. 100, 1169–1205. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Small, B. L., Brookhart, M. & Bennett, A. M. A. (1998). J. Am. Chem. Soc. 120, 4049–4050. Web of Science CSD CrossRef CAS Google Scholar