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

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 CuII 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[Yamada, S. (1999). Coord. Chem. Rev. 190, 537-555.]). For the structure of the zinc chloride complex of the same ligand, see: Dehghanpour et al. (2007[Dehghanpour, S., Mahmoudi, A., Khalaj, M., Salmanpour, S. & Adib, M. (2007). Acta Cryst. E63, m2841.]).

[Scheme 1]

Experimental

Crystal data
  • [CuCl2(C12H9IN2)]

  • Mr = 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[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.359, Tmax = 0.538 (expected range = 0.329–0.493)

  • 21713 measured reflections

  • 3166 independent reflections

  • 2650 reflections with I > 2σ(I)

  • Rint = 0.037

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.079

  • S = 1.05

  • 3166 reflections

  • 163 parameters

  • H-atom parameters constrained

  • Δρmax = 0.88 e Å−3

  • Δρmin = −0.51 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998[Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002[Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: SHELXL97.

Supporting information


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%.

Refinement top

The H-atoms were placed in calculated positions [C—H 0.93 Å] and treated as riding atoms [Uiso(H) = 1.2Ueq(C)].

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
[Figure 1] 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].
[Figure 2] 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
Mr = 442.55Dx = 2.115 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 13838 reflections
a = 12.2721 (5) Åθ = 3.1–27.5°
b = 15.2159 (5) ŵ = 4.16 mm1
c = 7.4709 (2) ÅT = 295 K
β = 94.8913 (10)°Block, green
V = 1389.97 (8) Å30.31 × 0.25 × 0.17 mm
Z = 4
Data collection top
Rigaku RAXIS-RAPID
diffractometer
3166 independent reflections
Radiation source: fine-focus sealed tube2650 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Detector resolution: 10.000 pixels mm-1θmax = 27.5°, θmin = 3.1°
ω scansh = 1515
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
k = 1919
Tmin = 0.359, Tmax = 0.538l = 99
21713 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0447P)2 + 0.6865P]
where P = (Fo2 + 2Fc2)/3
3166 reflections(Δ/σ)max = 0.001
163 parametersΔρmax = 0.88 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
[CuCl2(C12H9IN2)]V = 1389.97 (8) Å3
Mr = 442.55Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.2721 (5) ŵ = 4.16 mm1
b = 15.2159 (5) ÅT = 295 K
c = 7.4709 (2) Å0.31 × 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)
Tmin = 0.359, Tmax = 0.538Rint = 0.037
21713 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.079H-atom parameters constrained
S = 1.05Δρmax = 0.88 e Å3
3166 reflectionsΔρmin = 0.51 e Å3
163 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.001646 (16)0.649922 (16)0.55181 (3)0.05798 (10)
Cu10.60873 (3)0.72391 (2)0.87653 (5)0.03844 (11)
Cl10.72032 (6)0.82416 (5)1.01818 (12)0.05137 (19)
Cl20.51519 (6)0.82558 (5)0.71178 (11)0.04616 (18)
N10.70612 (18)0.62040 (15)0.9438 (3)0.0375 (5)
N20.50252 (17)0.62295 (15)0.7935 (3)0.0334 (4)
C10.8056 (2)0.6212 (2)1.0289 (4)0.0469 (7)
H10.83440.67381.07520.056*
C20.8676 (2)0.5448 (2)1.0503 (5)0.0520 (8)
H20.93680.54631.11140.062*
C30.8259 (3)0.4672 (2)0.9809 (5)0.0489 (7)
H30.86770.41620.98950.059*
C40.7210 (3)0.4657 (2)0.8980 (4)0.0443 (6)
H40.69020.41350.85300.053*
C50.6629 (2)0.54354 (18)0.8832 (4)0.0365 (6)
C60.5499 (2)0.54841 (18)0.8064 (4)0.0378 (6)
H60.51280.49770.76720.045*
C70.3893 (2)0.62851 (18)0.7297 (4)0.0350 (5)
C80.3398 (2)0.5679 (2)0.6095 (4)0.0446 (6)
H80.38140.52330.56430.054*
C90.2287 (2)0.5736 (2)0.5565 (4)0.0479 (7)
H90.19570.53230.47750.057*
C100.1677 (2)0.64099 (19)0.6219 (4)0.0417 (6)
C110.2166 (2)0.70219 (19)0.7420 (4)0.0422 (6)
H110.17530.74750.78520.051*
C120.3266 (2)0.69542 (18)0.7964 (4)0.0385 (6)
H120.35910.73570.87810.046*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.02714 (12)0.06908 (18)0.07514 (18)0.00149 (8)0.01061 (10)0.00131 (11)
Cu10.02850 (18)0.03088 (18)0.0536 (2)0.00103 (12)0.00989 (14)0.00045 (14)
Cl10.0377 (4)0.0440 (4)0.0702 (5)0.0064 (3)0.0082 (3)0.0106 (4)
Cl20.0382 (4)0.0366 (3)0.0624 (4)0.0042 (3)0.0032 (3)0.0115 (3)
N10.0270 (11)0.0373 (11)0.0472 (12)0.0010 (9)0.0036 (9)0.0017 (11)
N20.0265 (11)0.0321 (10)0.0404 (11)0.0000 (8)0.0033 (8)0.0008 (9)
C10.0306 (14)0.0500 (16)0.0578 (17)0.0032 (12)0.0087 (12)0.0016 (15)
C20.0279 (14)0.0624 (19)0.0640 (19)0.0063 (13)0.0055 (13)0.0086 (16)
C30.0358 (16)0.0470 (16)0.0640 (18)0.0124 (12)0.0054 (13)0.0129 (15)
C40.0390 (15)0.0367 (14)0.0570 (17)0.0040 (11)0.0022 (13)0.0056 (13)
C50.0287 (13)0.0353 (13)0.0449 (14)0.0019 (10)0.0002 (10)0.0041 (12)
C60.0315 (13)0.0325 (13)0.0484 (15)0.0023 (10)0.0027 (11)0.0010 (12)
C70.0264 (12)0.0349 (12)0.0429 (13)0.0000 (10)0.0022 (10)0.0020 (12)
C80.0304 (14)0.0513 (17)0.0513 (16)0.0015 (12)0.0014 (11)0.0108 (14)
C90.0331 (15)0.0581 (18)0.0507 (16)0.0033 (13)0.0069 (12)0.0096 (15)
C100.0244 (13)0.0492 (16)0.0503 (16)0.0011 (11)0.0046 (11)0.0049 (13)
C110.0320 (14)0.0387 (14)0.0556 (16)0.0054 (11)0.0017 (11)0.0012 (13)
C120.0326 (14)0.0360 (13)0.0457 (14)0.0010 (11)0.0036 (11)0.0015 (12)
Geometric parameters (Å, º) top
I1—C102.104 (3)C4—C51.383 (4)
Cu1—N12.015 (2)C4—H40.9300
Cu1—N22.075 (2)C5—C61.457 (4)
Cu1—Cl12.253 (1)C6—H60.9300
Cu1—Cl22.233 (1)C7—C81.390 (4)
N1—C11.328 (4)C7—C121.393 (4)
N1—C51.346 (4)C8—C91.389 (4)
N2—C61.274 (4)C8—H80.9300
N2—C71.433 (3)C9—C101.384 (4)
C1—C21.391 (4)C9—H90.9300
C1—H10.9300C10—C111.393 (4)
C2—C31.371 (5)C11—C121.380 (4)
C2—H20.9300C11—H110.9300
C3—C41.380 (4)C12—H120.9300
C3—H30.9300
N1—Cu1—N280.79 (9)N1—C5—C4122.1 (3)
N1—Cu1—Cl2160.96 (7)N1—C5—C6115.0 (2)
N1—Cu1—Cl195.07 (7)C4—C5—C6122.8 (3)
N2—Cu1—Cl1169.40 (7)N2—C6—C5119.2 (2)
N2—Cu1—Cl293.89 (6)N2—C6—H6120.4
Cl1—Cu2—Cl193.05 (3)C5—C6—H6120.4
C1—N1—C5119.3 (2)C8—C7—C12119.5 (2)
C1—N1—Cu1127.9 (2)C8—C7—N2122.2 (2)
C5—N1—Cu1112.76 (17)C12—C7—N2118.3 (2)
C6—N2—C7120.1 (2)C7—C8—C9120.5 (3)
C6—N2—Cu1111.44 (18)C7—C8—H8119.8
C7—N2—Cu1128.50 (17)C9—C8—H8119.8
N1—C1—C2121.2 (3)C10—C9—C8119.5 (3)
N1—C1—H1119.4C10—C9—H9120.3
C2—C1—H1119.4C8—C9—H9120.3
C3—C2—C1119.6 (3)C9—C10—C11120.4 (3)
C3—C2—H2120.2C9—C10—I1120.9 (2)
C1—C2—H2120.2C11—C10—I1118.7 (2)
C2—C3—C4119.2 (3)C12—C11—C10119.8 (3)
C2—C3—H3120.4C12—C11—H11120.1
C4—C3—H3120.4C10—C11—H11120.1
C3—C4—C5118.5 (3)C11—C12—C7120.3 (3)
C3—C4—H4120.8C11—C12—H12119.8
C5—C4—H4120.8C7—C12—H12119.8
N2—Cu1—N1—C1175.5 (3)C3—C4—C5—N11.4 (5)
Cl2—Cu1—N1—C1109.5 (3)C3—C4—C5—C6176.8 (3)
Cl1—Cu1—N1—C15.4 (3)C7—N2—C6—C5175.7 (2)
N2—Cu1—N1—C58.14 (19)Cu1—N2—C6—C53.6 (3)
Cl2—Cu1—N1—C566.8 (3)N1—C5—C6—N23.3 (4)
Cl1—Cu1—N1—C5178.30 (18)C4—C5—C6—N2178.3 (3)
N1—Cu1—N2—C66.3 (2)C6—N2—C7—C829.4 (4)
Cl2—Cu1—N2—C6155.25 (19)Cu1—N2—C7—C8151.3 (2)
Cl1—Cu1—N2—C674.0 (4)C6—N2—C7—C12148.2 (3)
N1—Cu1—N2—C7172.9 (2)Cu1—N2—C7—C1231.0 (3)
Cl2—Cu1—N2—C725.5 (2)C12—C7—C8—C90.2 (4)
Cl1—Cu1—N2—C7105.3 (4)N2—C7—C8—C9177.4 (3)
C5—N1—C1—C22.6 (5)C7—C8—C9—C101.1 (5)
Cu1—N1—C1—C2173.5 (2)C8—C9—C10—C110.8 (5)
N1—C1—C2—C30.6 (5)C8—C9—C10—I1178.1 (2)
C1—C2—C3—C42.9 (5)C9—C10—C11—C120.2 (5)
C2—C3—C4—C51.9 (5)I1—C10—C11—C12177.1 (2)
C1—N1—C5—C43.7 (4)C10—C11—C12—C71.0 (4)
Cu1—N1—C5—C4173.0 (2)C8—C7—C12—C110.8 (4)
C1—N1—C5—C6174.7 (3)N2—C7—C12—C11178.6 (3)
Cu1—N1—C5—C68.6 (3)

Experimental details

Crystal data
Chemical formula[CuCl2(C12H9IN2)]
Mr442.55
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)12.2721 (5), 15.2159 (5), 7.4709 (2)
β (°) 94.8913 (10)
V3)1389.97 (8)
Z4
Radiation typeMo Kα
µ (mm1)4.16
Crystal size (mm)0.31 × 0.25 × 0.17
Data collection
DiffractometerRigaku RAXIS-RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.359, 0.538
No. of measured, independent and
observed [I > 2σ(I)] reflections
21713, 3166, 2650
Rint0.037
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.079, 1.05
No. of reflections3166
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationDehghanpour, S., Mahmoudi, A., Khalaj, M., Salmanpour, S. & Adib, M. (2007). Acta Cryst. E63, m2841.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationHigashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationRigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYamada, S. (1999). Coord. Chem. Rev. 190, 537–555.  CrossRef Google Scholar

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