Dichlorido{2-[(4-iodo­phen­yl)imino­meth­yl]pyridine-κ2N,N′}copper(II)

Mahmoudi, A.; Khalaj, M.; Gao, S.; Ng, S.W.; Mohammadgholiha, M.

doi:10.1107/S1600536809011684

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page m555

doi:10.1107/S1600536809011684

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Dichlorido{2-[(4-iodophenyl)iminomethyl]pyridine-κ²N,N′}copper(II)

Ali Mahmoudi,^a ^* Mehdi Khalaj,^b Shan Gao,^c Seik Weng Ng ^d and Mahmoud Mohammadgholiha ^a

^aDepartment of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran, ^bDepartment of Chemistry, Islamic Azad University, Buinzahra Branch, Qazvin, Iran, ^cSchool of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: mahmoudi_ali@yahoo.com

(Received 22 March 2009; accepted 30 March 2009; online 22 April 2009)

The Cu^II atom in the title complex, [CuCl₂(C₁₂H₉IN₂)], has a square-planar coordination being N,N′-chelated by the Schiff base ligand, and by two Cl atoms. The geometry is distorted towards square pyramidal owing to a long Cu⋯Cl interaction of 2.941 (1) Å. This results in the formation of a zigzag chain structure propagating in the c-axis direction.

Related literature

For background to the synthesis and structure of metal complexes of diimines, see: Yamada (1999 ). For the structure of the zinc chloride complex of the same ligand, see: Dehghanpour et al. (2007 ).

Experimental

Crystal data

[CuCl₂(C₁₂H₉IN₂)]
M_r = 442.55
Monoclinic, P 2₁ /c
a = 12.2721 (5) Å
b = 15.2159 (5) Å
c = 7.4709 (2) Å
β = 94.8913 (10)°
V = 1389.97 (8) Å³
Z = 4
Mo Kα radiation
μ = 4.16 mm⁻¹
T = 295 K
0.31 × 0.25 × 0.17 mm

Data collection

Rigaku RAXIS-RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.359, T_max = 0.538 (expected range = 0.329–0.493)
21713 measured reflections
3166 independent reflections
2650 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.079
S = 1.05
3166 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.88 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, 9R. DOI: 10.1107/S1600536809011684/su2104sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011684/su2104Isup2.hkl

checkCIF report

Comment top

The structure of the title complex is illustrated in Fig. 1, and the geometrical parameters are available in the archived CIF. The complex was prepared by the reaction of copper chloride with the Schiff base ligand 2-[(4-iodophenyl)iminomethyl]pyridine (Yamada, 1999). The ligand is slightly twisted with the benzene ring and pyridine ring being inclined to one another by 26.07813)°.

A long Cu···Cl2ⁱ [symmetry operation (i) = x, 1.5-y, 0.5+z] interaction of 2.941 (1) Å, leads the formation of a zigzag chain propagating in the c direction (Fig. 2). This situation is different to that observed in the ZnCl₂ complex of the same ligand, which is mononuclear (Dehghanpour et al., 2007).

Related literature top

For background to the synthesis and structure of metal complexes of diimines, see: Yamada, (1999). For the structure of the zinc chloride complex of the same ligand, see: Dehghanpour et al. (2007).

Experimental top

To a solution of 2-[(4-iodophenyl)iminomethyl]pyridine (30.8 mg, 0.1 mmol) in 20 ml acetonitrile was added copper(II) chloride (13.4 mg, 0.1 mmol). The mixture was heated to dissolve the reactants and then the solution was filtered and the volume reduced under vacuum to ca. 5 ml. Diffusion of diethyl ether vapor into the solution gave green crystals of the title complex. The crystals were collected and washed with diethylether-dichloromethane (9:1 v/v). Yield 75%. CHN elemental analysis: Calc. for C₁₂H₉Cl₂CuIN₂: C 32.57, H 2.05, N 6.33%; found: C 32.54, H 2.07, N 6.35%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the structure of the title complex, with displacement ellipsoids drawn at the 50% probability level [H atoms are represented as spheres of arbitrary radius].
	Fig. 2. A view of the Cu···Cl2ⁱ bridged zigzag bridged chain structure of the title compound [Symmetry operations (i) = x, 1.5-y, -0.5+z]

Dichlorido{2-[(4-iodophenyl)iminomethyl]pyridine- κ²N,N'}copper(II) top

Crystal data top

[CuCl₂(C₁₂H₉IN₂)]	F(000) = 844
M_r = 442.55	D_x = 2.115 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13838 reflections
a = 12.2721 (5) Å	θ = 3.1–27.5°
b = 15.2159 (5) Å	µ = 4.16 mm⁻¹
c = 7.4709 (2) Å	T = 295 K
β = 94.8913 (10)°	Block, green
V = 1389.97 (8) Å³	0.31 × 0.25 × 0.17 mm
Z = 4

Data collection top

Rigaku RAXIS-RAPID diffractometer	3166 independent reflections
Radiation source: fine-focus sealed tube	2650 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −15→15
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −19→19
T_min = 0.359, T_max = 0.538	l = −9→9
21713 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0447P)² + 0.6865P] where P = (F_o² + 2F_c²)/3
3166 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.88 e Å⁻³
0 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

[CuCl₂(C₁₂H₉IN₂)]	V = 1389.97 (8) Å³
M_r = 442.55	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.2721 (5) Å	µ = 4.16 mm⁻¹
b = 15.2159 (5) Å	T = 295 K
c = 7.4709 (2) Å	0.31 × 0.25 × 0.17 mm
β = 94.8913 (10)°

Data collection top

Rigaku RAXIS-RAPID diffractometer	3166 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2650 reflections with I > 2σ(I)
T_min = 0.359, T_max = 0.538	R_int = 0.037
21713 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.079	H-atom parameters constrained
S = 1.05	Δρ_max = 0.88 e Å⁻³
3166 reflections	Δρ_min = −0.51 e Å⁻³
163 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	−0.001646 (16)	0.649922 (16)	0.55181 (3)	0.05798 (10)
Cu1	0.60873 (3)	0.72391 (2)	0.87653 (5)	0.03844 (11)
Cl1	0.72032 (6)	0.82416 (5)	1.01818 (12)	0.05137 (19)
Cl2	0.51519 (6)	0.82558 (5)	0.71178 (11)	0.04616 (18)
N1	0.70612 (18)	0.62040 (15)	0.9438 (3)	0.0375 (5)
N2	0.50252 (17)	0.62295 (15)	0.7935 (3)	0.0334 (4)
C1	0.8056 (2)	0.6212 (2)	1.0289 (4)	0.0469 (7)
H1	0.8344	0.6738	1.0752	0.056*
C2	0.8676 (2)	0.5448 (2)	1.0503 (5)	0.0520 (8)
H2	0.9368	0.5463	1.1114	0.062*
C3	0.8259 (3)	0.4672 (2)	0.9809 (5)	0.0489 (7)
H3	0.8677	0.4162	0.9895	0.059*
C4	0.7210 (3)	0.4657 (2)	0.8980 (4)	0.0443 (6)
H4	0.6902	0.4135	0.8530	0.053*
C5	0.6629 (2)	0.54354 (18)	0.8832 (4)	0.0365 (6)
C6	0.5499 (2)	0.54841 (18)	0.8064 (4)	0.0378 (6)
H6	0.5128	0.4977	0.7672	0.045*
C7	0.3893 (2)	0.62851 (18)	0.7297 (4)	0.0350 (5)
C8	0.3398 (2)	0.5679 (2)	0.6095 (4)	0.0446 (6)
H8	0.3814	0.5233	0.5643	0.054*
C9	0.2287 (2)	0.5736 (2)	0.5565 (4)	0.0479 (7)
H9	0.1957	0.5323	0.4775	0.057*
C10	0.1677 (2)	0.64099 (19)	0.6219 (4)	0.0417 (6)
C11	0.2166 (2)	0.70219 (19)	0.7420 (4)	0.0422 (6)
H11	0.1753	0.7475	0.7852	0.051*
C12	0.3266 (2)	0.69542 (18)	0.7964 (4)	0.0385 (6)
H12	0.3591	0.7357	0.8781	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.02714 (12)	0.06908 (18)	0.07514 (18)	0.00149 (8)	−0.01061 (10)	0.00131 (11)
Cu1	0.02850 (18)	0.03088 (18)	0.0536 (2)	0.00103 (12)	−0.00989 (14)	−0.00045 (14)
Cl1	0.0377 (4)	0.0440 (4)	0.0702 (5)	−0.0064 (3)	−0.0082 (3)	−0.0106 (4)
Cl2	0.0382 (4)	0.0366 (3)	0.0624 (4)	0.0042 (3)	−0.0032 (3)	0.0115 (3)
N1	0.0270 (11)	0.0373 (11)	0.0472 (12)	0.0010 (9)	−0.0036 (9)	0.0017 (11)
N2	0.0265 (11)	0.0321 (10)	0.0404 (11)	0.0000 (8)	−0.0033 (8)	0.0008 (9)
C1	0.0306 (14)	0.0500 (16)	0.0578 (17)	0.0032 (12)	−0.0087 (12)	−0.0016 (15)
C2	0.0279 (14)	0.0624 (19)	0.0640 (19)	0.0063 (13)	−0.0055 (13)	0.0086 (16)
C3	0.0358 (16)	0.0470 (16)	0.0640 (18)	0.0124 (12)	0.0054 (13)	0.0129 (15)
C4	0.0390 (15)	0.0367 (14)	0.0570 (17)	0.0040 (11)	0.0022 (13)	0.0056 (13)
C5	0.0287 (13)	0.0353 (13)	0.0449 (14)	0.0019 (10)	−0.0002 (10)	0.0041 (12)
C6	0.0315 (13)	0.0325 (13)	0.0484 (15)	−0.0023 (10)	−0.0027 (11)	0.0010 (12)
C7	0.0264 (12)	0.0349 (12)	0.0429 (13)	0.0000 (10)	−0.0022 (10)	0.0020 (12)
C8	0.0304 (14)	0.0513 (17)	0.0513 (16)	0.0015 (12)	−0.0014 (11)	−0.0108 (14)
C9	0.0331 (15)	0.0581 (18)	0.0507 (16)	−0.0033 (13)	−0.0069 (12)	−0.0096 (15)
C10	0.0244 (13)	0.0492 (16)	0.0503 (16)	−0.0011 (11)	−0.0046 (11)	0.0049 (13)
C11	0.0320 (14)	0.0387 (14)	0.0556 (16)	0.0054 (11)	0.0017 (11)	0.0012 (13)
C12	0.0326 (14)	0.0360 (13)	0.0457 (14)	−0.0010 (11)	−0.0036 (11)	−0.0015 (12)

Geometric parameters (Å, º) top

I1—C10	2.104 (3)	C4—C5	1.383 (4)
Cu1—N1	2.015 (2)	C4—H4	0.9300
Cu1—N2	2.075 (2)	C5—C6	1.457 (4)
Cu1—Cl1	2.253 (1)	C6—H6	0.9300
Cu1—Cl2	2.233 (1)	C7—C8	1.390 (4)
N1—C1	1.328 (4)	C7—C12	1.393 (4)
N1—C5	1.346 (4)	C8—C9	1.389 (4)
N2—C6	1.274 (4)	C8—H8	0.9300
N2—C7	1.433 (3)	C9—C10	1.384 (4)
C1—C2	1.391 (4)	C9—H9	0.9300
C1—H1	0.9300	C10—C11	1.393 (4)
C2—C3	1.371 (5)	C11—C12	1.380 (4)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.380 (4)	C12—H12	0.9300
C3—H3	0.9300

N1—Cu1—N2	80.79 (9)	N1—C5—C4	122.1 (3)
N1—Cu1—Cl2	160.96 (7)	N1—C5—C6	115.0 (2)
N1—Cu1—Cl1	95.07 (7)	C4—C5—C6	122.8 (3)
N2—Cu1—Cl1	169.40 (7)	N2—C6—C5	119.2 (2)
N2—Cu1—Cl2	93.89 (6)	N2—C6—H6	120.4
Cl1—Cu2—Cl1	93.05 (3)	C5—C6—H6	120.4
C1—N1—C5	119.3 (2)	C8—C7—C12	119.5 (2)
C1—N1—Cu1	127.9 (2)	C8—C7—N2	122.2 (2)
C5—N1—Cu1	112.76 (17)	C12—C7—N2	118.3 (2)
C6—N2—C7	120.1 (2)	C7—C8—C9	120.5 (3)
C6—N2—Cu1	111.44 (18)	C7—C8—H8	119.8
C7—N2—Cu1	128.50 (17)	C9—C8—H8	119.8
N1—C1—C2	121.2 (3)	C10—C9—C8	119.5 (3)
N1—C1—H1	119.4	C10—C9—H9	120.3
C2—C1—H1	119.4	C8—C9—H9	120.3
C3—C2—C1	119.6 (3)	C9—C10—C11	120.4 (3)
C3—C2—H2	120.2	C9—C10—I1	120.9 (2)
C1—C2—H2	120.2	C11—C10—I1	118.7 (2)
C2—C3—C4	119.2 (3)	C12—C11—C10	119.8 (3)
C2—C3—H3	120.4	C12—C11—H11	120.1
C4—C3—H3	120.4	C10—C11—H11	120.1
C3—C4—C5	118.5 (3)	C11—C12—C7	120.3 (3)
C3—C4—H4	120.8	C11—C12—H12	119.8
C5—C4—H4	120.8	C7—C12—H12	119.8

N2—Cu1—N1—C1	−175.5 (3)	C3—C4—C5—N1	1.4 (5)
Cl2—Cu1—N1—C1	109.5 (3)	C3—C4—C5—C6	−176.8 (3)
Cl1—Cu1—N1—C1	−5.4 (3)	C7—N2—C6—C5	−175.7 (2)
N2—Cu1—N1—C5	8.14 (19)	Cu1—N2—C6—C5	3.6 (3)
Cl2—Cu1—N1—C5	−66.8 (3)	N1—C5—C6—N2	3.3 (4)
Cl1—Cu1—N1—C5	178.30 (18)	C4—C5—C6—N2	−178.3 (3)
N1—Cu1—N2—C6	−6.3 (2)	C6—N2—C7—C8	−29.4 (4)
Cl2—Cu1—N2—C6	155.25 (19)	Cu1—N2—C7—C8	151.3 (2)
Cl1—Cu1—N2—C6	−74.0 (4)	C6—N2—C7—C12	148.2 (3)
N1—Cu1—N2—C7	172.9 (2)	Cu1—N2—C7—C12	−31.0 (3)
Cl2—Cu1—N2—C7	−25.5 (2)	C12—C7—C8—C9	−0.2 (4)
Cl1—Cu1—N2—C7	105.3 (4)	N2—C7—C8—C9	177.4 (3)
C5—N1—C1—C2	2.6 (5)	C7—C8—C9—C10	1.1 (5)
Cu1—N1—C1—C2	−173.5 (2)	C8—C9—C10—C11	−0.8 (5)
N1—C1—C2—C3	0.6 (5)	C8—C9—C10—I1	−178.1 (2)
C1—C2—C3—C4	−2.9 (5)	C9—C10—C11—C12	−0.2 (5)
C2—C3—C4—C5	1.9 (5)	I1—C10—C11—C12	177.1 (2)
C1—N1—C5—C4	−3.7 (4)	C10—C11—C12—C7	1.0 (4)
Cu1—N1—C5—C4	173.0 (2)	C8—C7—C12—C11	−0.8 (4)
C1—N1—C5—C6	174.7 (3)	N2—C7—C12—C11	−178.6 (3)
Cu1—N1—C5—C6	−8.6 (3)

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₂H₉IN₂)]
M_r	442.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	12.2721 (5), 15.2159 (5), 7.4709 (2)
β (°)	94.8913 (10)
V (Å³)	1389.97 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.16
Crystal size (mm)	0.31 × 0.25 × 0.17

Data collection
Diffractometer	Rigaku RAXIS-RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.359, 0.538
No. of measured, independent and observed [I > 2σ(I)] reflections	21713, 3166, 2650
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.079, 1.05
No. of reflections	3166
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.88, −0.51

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001).

Acknowledgements

We thank the Islamic Azad University Research Council and the University of Malaya for supporting this study.

References

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