{2-[(4-Bromo­phen­yl)imino­meth­yl]pyridine-κ2N,N′}diiodidozinc(II)

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

doi:10.1107/S1600536808020680

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page m1018

doi:10.1107/S1600536808020680

Open

access

{2-[(4-Bromophenyl)iminomethyl]pyridine-κ²N,N′}diiodidozinc(II)

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

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

(Received 11 June 2008; accepted 4 July 2008; online 9 July 2008)

In the title compound, [ZnI₂(C₁₂H₉BrN₂)], the metal centre displays a moderately distorted tetrahedral coordination geometry defined by two iodide anions and two N atoms of the organic ligand. The dihedral angle between the pyridine and benzene rings is 15.15 (13)°.

Related literature

For the crystal structure of similar iminopyridine complexes, see: Dehghanpour, Mahmoudi, Khalaj & Salmanpour (2007 ); Dehghanpour, Mahmoudi, Khalaj, Salmanpour & Adib (2007 ). For related structures see: Lee et al. (2008 ); Wriedt et al. (2008 ).

Experimental

Crystal data

[ZnI₂(C₁₂H₉BrN₂)]
M_r = 580.29
Triclinic, $[P \overline 1]$
a = 8.0749 (9) Å
b = 9.7323 (11) Å
c = 11.1884 (13) Å
α = 79.157 (2)°
β = 71.178 (3)°
γ = 67.325 (2)°
V = 765.87 (15) Å³
Z = 2
Mo Kα radiation
μ = 8.23 mm⁻¹
T = 100 (2) K
0.45 × 0.21 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2005 ) T_min = 0.135, T_max = 0.378
9814 measured reflections
4449 independent reflections
3983 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.084
S = 1.01
4449 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 1.94 e Å⁻³
Δρ_min = −1.96 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

I1—Zn1	2.5201 (5)
I2—Zn1	2.5389 (5)
Zn1—N1	2.062 (3)
Zn1—N2	2.094 (3)

N1—Zn1—N2	80.30 (11)
N1—Zn1—I1	117.81 (8)
N2—Zn1—I1	117.60 (8)
N1—Zn1—I2	109.45 (8)
N2—Zn1—I2	110.18 (8)
I1—Zn1—I2	116.210 (17)

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/S1600536808020680/rz2225sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808020680/rz2225Isup2.hkl

checkCIF report

Comment top

Iminopyridines derivatives are common ligands and many complexes containing these ligands have been reported. Recently, the crystal structure of zinc(II)-complexes similar to the title compound has been reported by our group (Dehghanpour, Mahmoudi, Khalaj & Salmanpour, 2007; Dehghanpour, Mahmoudi, Khalaj, Salmanpour & Adib, 2007).

The molecular structure of the title compound and the atom numbering scheme are shown in Fig. 1. The structure consists of discrete [ZnI₂(C₁₂H₉BrN₂)] complex molecules where the metal centre has a tetrahedral coordination geometry which shows significant distortion, mainly due to the presence of the five-membered chelate ring. The endocyclic N1—Zn1—N2 angle (Table 1) is much narrower than the ideal tetrahedral angle of 109.5^°, whereas the opposite I1—Zn1—I2 angle is much wider. Bond lengths involving the Zn atom are in good agreement with the values found in the literature for tetrahedral zinc(II) complexes (Lee et al., 2008; Wriedt et al., 2008). The dihedral angle formed by the pyridine and benzene ring is 15.15 (13)°. The crystal structure is enforced by van der Waals interactions only.

Related literature top

For the crystal structure of similar iminopyridine complexes, see: Dehghanpour, Mahmoudi, Khalaj & Salmanpour (2007); Dehghanpour, Mahmoudi, Khalaj, Salmanpour & Adib (2007). For related structures see: Lee et al. (2008); Wriedt et al. (2008).

Experimental top

To a solution of (4-bromo-phenyl)-pyridin-2-ylmethylene-amine (26.1 mg, 0.1 mmol) in acetonitrile (20 ml) was added zinc iodide (31.9 mg, 0.1 mmol). The mixture was heated to dissolve the reactants. The solution was filtered and the volume of solvent removed under vacuum to about 5 ml. The diffusion of diethyl ether vapor into the solution gave yellow crystals. The crystals were collected and washed with diethylether-dichloromethane (9:1 v/v); yield 81%. Calc. for C₁₂H₉BrI₂N₂Zn: C 24.84, H 1.56, N 4.83%; found: C 24.86, H 1.55, N 4.82%.

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. The molecular structure of the title compound showing the atom-labelling scheme and thermal ellipsoids drawn at the 50% probability level.

{2-[(4-Bromophenyl)iminomethyl]pyridine-κ²N,N'}diiodidozinc(II) top

Crystal data top

[ZnI₂(C₁₂H₉BrN₂)]	Z = 2
M_r = 580.29	F(000) = 532
Triclinic, P1	D_x = 2.516 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0749 (9) Å	Cell parameters from 1953 reflections
b = 9.7323 (11) Å	θ = 2.8–34.4°
c = 11.1884 (13) Å	µ = 8.23 mm⁻¹
α = 79.157 (2)°	T = 100 K
β = 71.178 (3)°	Plate, yellow
γ = 67.325 (2)°	0.45 × 0.21 × 0.12 mm
V = 765.87 (15) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	4449 independent reflections
Radiation source: fine-focus sealed tube	3983 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 30.0°, θ_min = 1.9°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −11→11
T_min = 0.135, T_max = 0.378	k = −13→13
9814 measured reflections	l = −15→15

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.04P)²] where P = (F_o² + 2F_c²)/3
4449 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 1.94 e Å⁻³
0 restraints	Δρ_min = −1.96 e Å⁻³

Crystal data top

[ZnI₂(C₁₂H₉BrN₂)]	γ = 67.325 (2)°
M_r = 580.29	V = 765.87 (15) Å³
Triclinic, P1	Z = 2
a = 8.0749 (9) Å	Mo Kα radiation
b = 9.7323 (11) Å	µ = 8.23 mm⁻¹
c = 11.1884 (13) Å	T = 100 K
α = 79.157 (2)°	0.45 × 0.21 × 0.12 mm
β = 71.178 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4449 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2005)	3983 reflections with I > 2σ(I)
T_min = 0.135, T_max = 0.378	R_int = 0.040
9814 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.01	Δρ_max = 1.94 e Å⁻³
4449 reflections	Δρ_min = −1.96 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
I1	−0.28834 (3)	0.85145 (2)	0.60583 (2)	0.01640 (7)
I2	0.16700 (3)	0.84434 (2)	0.72880 (2)	0.01874 (7)
Br1	0.51281 (5)	0.79618 (4)	−0.04600 (3)	0.02005 (9)
Zn1	0.02685 (5)	0.70420 (4)	0.64300 (4)	0.01456 (9)
N1	0.0641 (4)	0.4960 (3)	0.7379 (3)	0.0178 (6)
N2	0.2315 (4)	0.5720 (3)	0.4997 (3)	0.0154 (5)
C1	0.2115 (5)	0.3877 (4)	0.6720 (3)	0.0159 (6)
C2	0.2711 (5)	0.2407 (4)	0.7206 (3)	0.0195 (7)
H2A	0.3754	0.1671	0.6722	0.023*
C3	0.1746 (6)	0.2034 (4)	0.8421 (4)	0.0234 (7)
H3A	0.2130	0.1039	0.8786	0.028*
C4	0.0213 (5)	0.3136 (4)	0.9090 (4)	0.0240 (8)
H4A	−0.0483	0.2900	0.9913	0.029*
C5	−0.0296 (5)	0.4594 (4)	0.8543 (3)	0.0225 (7)
H5A	−0.1335	0.5349	0.9010	0.027*
C6	0.3009 (5)	0.4359 (4)	0.5426 (3)	0.0158 (6)
H6A	0.4084	0.3675	0.4913	0.019*
C7	0.3033 (4)	0.6193 (4)	0.3715 (3)	0.0147 (6)
C8	0.4198 (5)	0.5200 (4)	0.2790 (3)	0.0169 (6)
H8A	0.4551	0.4155	0.3005	0.020*
C9	0.4848 (5)	0.5734 (4)	0.1550 (3)	0.0185 (7)
H9A	0.5671	0.5061	0.0920	0.022*
C10	0.4275 (5)	0.7263 (4)	0.1250 (3)	0.0165 (6)
C11	0.3091 (5)	0.8267 (4)	0.2146 (3)	0.0204 (7)
H11A	0.2710	0.9311	0.1921	0.024*
C12	0.2468 (5)	0.7728 (4)	0.3380 (3)	0.0195 (7)
H12A	0.1649	0.8407	0.4006	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01523 (11)	0.01337 (11)	0.02111 (12)	−0.00533 (8)	−0.00547 (8)	−0.00085 (8)
I2	0.01755 (12)	0.01407 (12)	0.02641 (13)	−0.00646 (9)	−0.00745 (9)	−0.00117 (9)
Br1	0.02369 (18)	0.01625 (17)	0.01622 (17)	−0.00571 (14)	−0.00288 (13)	0.00060 (13)
Zn1	0.01415 (18)	0.01008 (17)	0.01727 (19)	−0.00385 (14)	−0.00195 (14)	−0.00109 (14)
N1	0.0177 (13)	0.0139 (13)	0.0216 (14)	−0.0076 (11)	−0.0031 (11)	−0.0002 (11)
N2	0.0181 (13)	0.0132 (13)	0.0162 (13)	−0.0079 (11)	−0.0027 (10)	−0.0022 (10)
C1	0.0166 (14)	0.0140 (15)	0.0186 (15)	−0.0073 (12)	−0.0050 (12)	−0.0003 (12)
C2	0.0230 (16)	0.0138 (15)	0.0218 (16)	−0.0058 (13)	−0.0077 (13)	0.0001 (13)
C3	0.0318 (19)	0.0139 (16)	0.0265 (18)	−0.0090 (14)	−0.0136 (15)	0.0058 (14)
C4	0.0275 (19)	0.0201 (17)	0.0220 (17)	−0.0116 (15)	−0.0035 (14)	0.0056 (14)
C5	0.0230 (17)	0.0223 (18)	0.0200 (17)	−0.0092 (14)	−0.0034 (13)	0.0023 (14)
C6	0.0156 (14)	0.0111 (14)	0.0197 (16)	−0.0043 (12)	−0.0038 (12)	−0.0016 (12)
C7	0.0148 (14)	0.0123 (14)	0.0170 (15)	−0.0053 (12)	−0.0039 (11)	−0.0008 (12)
C8	0.0194 (15)	0.0097 (14)	0.0201 (16)	−0.0041 (12)	−0.0035 (12)	−0.0032 (12)
C9	0.0189 (15)	0.0138 (15)	0.0199 (16)	−0.0040 (13)	−0.0020 (12)	−0.0040 (12)
C10	0.0167 (14)	0.0178 (16)	0.0155 (15)	−0.0080 (13)	−0.0032 (12)	0.0001 (12)
C11	0.0248 (17)	0.0126 (15)	0.0206 (17)	−0.0055 (13)	−0.0031 (13)	−0.0018 (13)
C12	0.0210 (16)	0.0089 (14)	0.0213 (17)	−0.0034 (12)	0.0013 (13)	−0.0013 (12)

Geometric parameters (Å, º) top

I1—Zn1	2.5201 (5)	C3—H3A	0.9500
I2—Zn1	2.5389 (5)	C4—C5	1.394 (5)
Zn1—N1	2.062 (3)	C4—H4A	0.9500
Zn1—N2	2.094 (3)	C5—H5A	0.9500
Br1—C10	1.902 (3)	C6—H6A	0.9500
Zn1—N1	2.062 (3)	C7—C8	1.391 (5)
Zn1—N2	2.094 (3)	C7—C12	1.398 (5)
N1—C5	1.339 (4)	C8—C9	1.392 (5)
N1—C1	1.353 (4)	C8—H8A	0.9500
N2—C6	1.289 (4)	C9—C10	1.387 (5)
N2—C7	1.424 (4)	C9—H9A	0.9500
C1—C2	1.385 (5)	C10—C11	1.381 (5)
C1—C6	1.473 (5)	C11—C12	1.385 (5)
C2—C3	1.391 (5)	C11—H11A	0.9500
C2—H2A	0.9500	C12—H12A	0.9500
C3—C4	1.387 (6)

N1—Zn1—N2	80.30 (11)	N1—C5—C4	121.8 (3)
N1—Zn1—I1	117.81 (8)	N1—C5—H5A	119.1
N2—Zn1—I1	117.60 (8)	C4—C5—H5A	119.1
N1—Zn1—I2	109.45 (8)	N2—C6—C1	119.2 (3)
N2—Zn1—I2	110.18 (8)	N2—C6—H6A	120.4
I1—Zn1—I2	116.210 (17)	C1—C6—H6A	120.4
C5—N1—C1	118.8 (3)	C8—C7—C12	119.5 (3)
C5—N1—Zn1	128.7 (3)	C8—C7—N2	123.0 (3)
C1—N1—Zn1	112.4 (2)	C12—C7—N2	117.5 (3)
C6—N2—C7	120.8 (3)	C7—C8—C9	120.2 (3)
C6—N2—Zn1	111.5 (2)	C7—C8—H8A	119.9
C7—N2—Zn1	127.5 (2)	C9—C8—H8A	119.9
N1—C1—C2	122.7 (3)	C10—C9—C8	118.9 (3)
N1—C1—C6	115.2 (3)	C10—C9—H9A	120.5
C2—C1—C6	122.1 (3)	C8—C9—H9A	120.5
C1—C2—C3	118.4 (3)	C11—C10—C9	121.8 (3)
C1—C2—H2A	120.8	C11—C10—Br1	120.0 (3)
C3—C2—H2A	120.8	C9—C10—Br1	118.1 (3)
C4—C3—C2	119.0 (3)	C10—C11—C12	118.9 (3)
C4—C3—H3A	120.5	C10—C11—H11A	120.6
C2—C3—H3A	120.5	C12—C11—H11A	120.6
C3—C4—C5	119.3 (3)	C11—C12—C7	120.6 (3)
C3—C4—H4A	120.3	C11—C12—H12A	119.7
C5—C4—H4A	120.3	C7—C12—H12A	119.7

N2—Zn1—N1—C5	−175.2 (3)	Zn1—N1—C5—C4	−175.4 (3)
I1—Zn1—N1—C5	−59.0 (3)	C3—C4—C5—N1	0.9 (6)
I2—Zn1—N1—C5	76.7 (3)	C7—N2—C6—C1	−174.2 (3)
N2—Zn1—N1—C1	9.0 (2)	Zn1—N2—C6—C1	10.1 (4)
I1—Zn1—N1—C1	125.1 (2)	N1—C1—C6—N2	−2.6 (5)
I2—Zn1—N1—C1	−99.1 (2)	C2—C1—C6—N2	175.4 (3)
N1—Zn1—N2—C6	−10.3 (2)	C6—N2—C7—C8	14.4 (5)
I1—Zn1—N2—C6	−126.7 (2)	Zn1—N2—C7—C8	−170.5 (3)
I2—Zn1—N2—C6	97.0 (2)	C6—N2—C7—C12	−168.0 (3)
N1—Zn1—N2—C7	174.3 (3)	Zn1—N2—C7—C12	7.0 (4)
I1—Zn1—N2—C7	57.9 (3)	C12—C7—C8—C9	2.2 (5)
I2—Zn1—N2—C7	−78.4 (3)	N2—C7—C8—C9	179.7 (3)
C5—N1—C1—C2	−0.8 (5)	C7—C8—C9—C10	−1.7 (5)
Zn1—N1—C1—C2	175.5 (3)	C8—C9—C10—C11	0.5 (5)
C5—N1—C1—C6	177.2 (3)	C8—C9—C10—Br1	−178.3 (3)
Zn1—N1—C1—C6	−6.5 (4)	C9—C10—C11—C12	0.3 (6)
N1—C1—C2—C3	0.2 (5)	Br1—C10—C11—C12	179.0 (3)
C6—C1—C2—C3	−177.6 (3)	C10—C11—C12—C7	0.2 (6)
C1—C2—C3—C4	0.9 (6)	C8—C7—C12—C11	−1.5 (5)
C2—C3—C4—C5	−1.5 (6)	N2—C7—C12—C11	−179.1 (3)
C1—N1—C5—C4	0.2 (5)

Experimental details

Crystal data
Chemical formula	[ZnI₂(C₁₂H₉BrN₂)]
M_r	580.29
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.0749 (9), 9.7323 (11), 11.1884 (13)
α, β, γ (°)	79.157 (2), 71.178 (3), 67.325 (2)
V (Å³)	765.87 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	8.23
Crystal size (mm)	0.45 × 0.21 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (APEX2; Bruker, 2005)
T_min, T_max	0.135, 0.378
No. of measured, independent and observed [I > 2σ(I)] reflections	9814, 4449, 3983
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.084, 1.01
No. of reflections	4449
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.94, −1.96

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

Selected geometric parameters (Å, º) top

I1—Zn1	2.5201 (5)	Zn1—N2	2.094 (3)
I2—Zn1	2.5389 (5)	Zn1—N1	2.062 (3)
Zn1—N1	2.062 (3)	Zn1—N2	2.094 (3)

N1—Zn1—N2	80.30 (11)	N1—Zn1—I2	109.45 (8)
N1—Zn1—I1	117.81 (8)	N2—Zn1—I2	110.18 (8)
N2—Zn1—I1	117.60 (8)	I1—Zn1—I2	116.210 (17)

Acknowledgements

SD acknowledges the Alzahra University Research Council for partial support of this work.

References

Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dehghanpour, S., Mahmoudi, A., Khalaj, M. & Salmanpour, S. (2007). Acta Cryst. E63, m2840. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dehghanpour, S., Mahmoudi, A., Khalaj, M., Salmanpour, S. & Adib, M. (2007). Acta Cryst. E63, m2841. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lee, S. H., Kim, S.-H., Kim, P.-G., Kim, C. & Kim, Y. (2008). Acta Cryst. E64, m511. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wriedt, M., Jess, I. & Näther, C. (2008). Acta Cryst. E64, m11. Web of Science CSD CrossRef IUCr Journals Google Scholar