Dichlorido{2-[(3,4-dimethyl­phen­yl)imino­meth­yl]pyridine-κ2N,N′}copper(II)

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

doi:10.1107/S160053681104390X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1624

doi:10.1107/S160053681104390X

Open

access

Dichlorido{2-[(3,4-dimethylphenyl)iminomethyl]pyridine-κ²N,N′}copper(II)

Mehdi Khalaj,^a ^* Saeed Dehghanpour,^b Sadegh Salehzadeh ^c and Ali Mahmoudi ^d

^aDepartment of Chemistry, Islamic Azad University, Buinzahra Branch, Qazvin, Iran, ^bDepartment of Chemistry, Alzahra University, PO Box 1993891176, Vanak, Tehran, Iran, ^cFaculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran, and ^dDepartment of Chemistry, Islamic Azad University, Karaj Branch, Karaj, Iran
^*Correspondence e-mail: khalaj_mehdi@yahoo.com

(Received 11 October 2011; accepted 22 October 2011; online 29 October 2011)

In the title complex, [CuCl₂(C₁₄H₁₄N₂)], the Cu^II atom exhibits a very distorted tetrahedral coordination geometry involving two chloride ions and two N-atom donors from the Schiff base ligand. The range for the six bond angles about the Cu²⁺ cation is 81.49 (11)–145.95 (9)°. The chelate ring including the Cu^II atom is approximately planar, with a maximum deviation of 0.039 (4) Å for one of the C atoms; this plane forms a dihedral angle of 46.69 (9)° with the CuCl₂ plane.

Related literature

For related structures, see: Mahmoudi et al. (2009 ); Wang & Zhong (2009 ). For background information on diimine complexes, see: Khalaj et al. (2010 ); Salehzadeh et al. (2011 ).

Experimental

Crystal data

[CuCl₂(C₁₄H₁₄N₂)]
M_r = 344.71
Triclinic, $[P \overline 1]$
a = 8.1171 (4) Å
b = 9.5784 (4) Å
c = 10.0609 (5) Å
α = 67.236 (2)°
β = 88.513 (2)°
γ = 81.336 (2)°
V = 712.61 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.89 mm⁻¹
T = 150 K
0.18 × 0.16 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.725, T_max = 0.830
6451 measured reflections
3189 independent reflections
2256 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.126
S = 1.07
3189 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	1.988 (3)
Cu1—N2	2.025 (3)
Cu1—Cl2	2.2035 (10)
Cu1—Cl1	2.2204 (10)

Data collection: COLLECT (Nonius, 2002 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681104390X/zs2154sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681104390X/zs2154Isup2.hkl

checkCIF report

Comment top

Diimine ligands derived from 2-aminopyridine and aniline derivatives are useful bidentate terminal ligands and some complexes with them as ligand have already been published (Mahmoudi et al., 2009; Salehzadeh et al., 2011). We report herein the crystal structure of the title complex [CuCl₂(C₁₄H₁₄N₂)] which was prepared by the reaction of CuCl₂ with the bidentate ligand N-(3,4-dimethylphenyl)-pyridine-2-ylmethyleneamine.

The molecular structure of the title complex is shown in Fig. 1. The Cu^II ion is in a very distorted tetrahedral environment formed by a bis-chelating ligand and two Cl anions. The dihedral angle between the chelate plane Cu1–N1–C5–C6–N2 and the Cl1–Cu1–Cl2 plane is 46.69(9° and the range for the six bond angles about Cu1 is 81.49 (11)° (N1-Cu1-N2)–145.95 (9)° (N2-Cu1-Cl1). These values show an appreciable distortion towards square planar geometry. A comparison of the dihedral angles between the planes of the pyridine, chelate and the benzene rings indicate that the ligand is distorted from planarity, with a twist of 26.00 (17)° between the chelate (N1—C5—C6—N2) and the benzene (C7–C12) planes. The Cu—Cl and Cu—N bond dimensions compare well with the values found in other tetrahedral diimine complexes of copper(II) chloride (Mahmoudi et al., 2009; Wang & Zhong, 2009).

Related literature top

For related structures, see: Mahmoudi et al. (2009); Wang & Zhong (2009). For background information on diimine complexes, see: Khalaj et al. (2010); Salehzadeh et al. (2011).

Experimental top

The title complex was prepared by the reaction of CuCl₂ (13.4 mg, 0.1 mmol) and N-(3,4-dimethylphenyl)-(pyridine-2-ylmethylene)amine (21.0 mg, 0.1 mmol) in 10 ml acetonitrile at room temperature. The green single crystals were obtained after the solution had been allowed to stand at room temperature for two days.

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of the structure of the title complex, with displacement ellipsoids drawn at the 50% probability level.

Dichlorido{2-[(3,4-dimethylphenyl)iminomethyl]pyridine- κ²N,N'}copper(II) top

Crystal data top

[CuCl₂(C₁₄H₁₄N₂)]	Z = 2
M_r = 344.71	F(000) = 350
Triclinic, P1	D_x = 1.607 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1171 (4) Å	Cell parameters from 6451 reflections
b = 9.5784 (4) Å	θ = 3.2–27.4°
c = 10.0609 (5) Å	µ = 1.89 mm⁻¹
α = 67.236 (2)°	T = 150 K
β = 88.513 (2)°	Block, green
γ = 81.336 (2)°	0.18 × 0.16 × 0.10 mm
V = 712.61 (6) Å³

Data collection top

Nonius KappaCCD diffractometer	3189 independent reflections
Radiation source: fine-focus sealed tube	2256 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
Detector resolution: 9 pixels mm^-1	θ_max = 27.4°, θ_min = 3.2°
ϕ scans and ω scans with κ offsets	h = −10→10
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −11→12
T_min = 0.725, T_max = 0.830	l = −12→13
6451 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0585P)² + 0.324P] where P = (F_o² + 2F_c²)/3
3189 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.83 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

[CuCl₂(C₁₄H₁₄N₂)]	γ = 81.336 (2)°
M_r = 344.71	V = 712.61 (6) Å³
Triclinic, P1	Z = 2
a = 8.1171 (4) Å	Mo Kα radiation
b = 9.5784 (4) Å	µ = 1.89 mm⁻¹
c = 10.0609 (5) Å	T = 150 K
α = 67.236 (2)°	0.18 × 0.16 × 0.10 mm
β = 88.513 (2)°

Data collection top

Nonius KappaCCD diffractometer	3189 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	2256 reflections with I > 2σ(I)
T_min = 0.725, T_max = 0.830	R_int = 0.039
6451 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.07	Δρ_max = 0.83 e Å⁻³
3189 reflections	Δρ_min = −0.62 e Å⁻³
174 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
Cu1	0.78165 (5)	0.20424 (5)	0.33299 (5)	0.02388 (17)
Cl1	1.03716 (11)	0.14201 (11)	0.26876 (12)	0.0344 (3)
Cl2	0.82609 (12)	0.35601 (10)	0.44190 (11)	0.0285 (2)
N1	0.7024 (4)	0.0099 (3)	0.3557 (3)	0.0214 (7)
N2	0.5411 (4)	0.2901 (3)	0.2659 (3)	0.0210 (7)
C1	0.7928 (5)	−0.1295 (4)	0.3991 (4)	0.0246 (8)
H1A	0.9088	−0.1414	0.4200	0.030*
C2	0.7211 (5)	−0.2577 (4)	0.4146 (4)	0.0268 (9)
H2A	0.7879	−0.3557	0.4440	0.032*
C3	0.5523 (5)	−0.2417 (4)	0.3868 (4)	0.0276 (9)
H3A	0.5013	−0.3282	0.3973	0.033*
C4	0.4583 (5)	−0.0967 (4)	0.3432 (4)	0.0242 (8)
H4A	0.3416	−0.0824	0.3242	0.029*
C5	0.5375 (4)	0.0264 (4)	0.3280 (4)	0.0199 (7)
C6	0.4535 (5)	0.1850 (4)	0.2758 (4)	0.0226 (8)
H6A	0.3379	0.2099	0.2500	0.027*
C7	0.4663 (5)	0.4479 (4)	0.2081 (4)	0.0221 (8)
C8	0.5689 (5)	0.5567 (4)	0.1391 (4)	0.0239 (8)
H8A	0.6856	0.5271	0.1362	0.029*
C9	0.4977 (5)	0.7090 (4)	0.0747 (4)	0.0267 (8)
H9A	0.5672	0.7830	0.0249	0.032*
C10	0.3303 (5)	0.7572 (4)	0.0800 (4)	0.0281 (9)
C11	0.2260 (5)	0.6473 (4)	0.1520 (4)	0.0250 (8)
C12	0.2963 (5)	0.4939 (4)	0.2149 (4)	0.0265 (8)
H12A	0.2271	0.4191	0.2634	0.032*
C13	0.2548 (5)	0.9237 (4)	0.0073 (4)	0.0321 (9)
H13A	0.3406	0.9834	−0.0456	0.048*
H13B	0.2103	0.9620	0.0803	0.048*
H13C	0.1645	0.9337	−0.0601	0.048*
C14	0.0420 (5)	0.6938 (4)	0.1616 (5)	0.0363 (10)
H14A	−0.0082	0.6034	0.2197	0.054*
H14B	−0.0102	0.7396	0.0644	0.054*
H14C	0.0245	0.7687	0.2068	0.054*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0176 (3)	0.0229 (3)	0.0336 (3)	−0.00222 (18)	0.0004 (2)	−0.0139 (2)
Cl1	0.0182 (5)	0.0407 (6)	0.0514 (7)	−0.0050 (4)	0.0058 (4)	−0.0255 (5)
Cl2	0.0269 (5)	0.0226 (4)	0.0390 (6)	−0.0013 (4)	−0.0050 (4)	−0.0156 (4)
N1	0.0205 (16)	0.0209 (15)	0.0232 (17)	−0.0002 (12)	−0.0008 (13)	−0.0100 (13)
N2	0.0222 (16)	0.0190 (15)	0.0228 (16)	−0.0036 (12)	0.0033 (13)	−0.0092 (13)
C1	0.023 (2)	0.0270 (19)	0.023 (2)	0.0004 (15)	0.0001 (16)	−0.0107 (17)
C2	0.033 (2)	0.0204 (18)	0.028 (2)	−0.0005 (16)	0.0044 (18)	−0.0118 (17)
C3	0.038 (2)	0.0225 (19)	0.027 (2)	−0.0094 (17)	0.0055 (18)	−0.0130 (17)
C4	0.024 (2)	0.030 (2)	0.023 (2)	−0.0081 (16)	0.0011 (16)	−0.0129 (17)
C5	0.0194 (18)	0.0211 (17)	0.0207 (19)	−0.0042 (14)	0.0025 (15)	−0.0095 (15)
C6	0.0180 (18)	0.0235 (18)	0.027 (2)	−0.0008 (14)	0.0016 (16)	−0.0114 (17)
C7	0.026 (2)	0.0196 (17)	0.0217 (19)	−0.0018 (15)	0.0007 (16)	−0.0092 (15)
C8	0.0213 (19)	0.0262 (19)	0.026 (2)	−0.0054 (15)	0.0013 (16)	−0.0110 (17)
C9	0.031 (2)	0.0251 (19)	0.023 (2)	−0.0063 (16)	−0.0010 (17)	−0.0079 (17)
C10	0.040 (2)	0.0171 (17)	0.023 (2)	0.0025 (16)	0.0032 (18)	−0.0054 (16)
C11	0.024 (2)	0.027 (2)	0.024 (2)	−0.0012 (16)	0.0016 (16)	−0.0096 (17)
C12	0.025 (2)	0.0255 (19)	0.027 (2)	−0.0038 (16)	0.0050 (17)	−0.0090 (17)
C13	0.043 (3)	0.0233 (19)	0.029 (2)	−0.0015 (17)	−0.0030 (19)	−0.0103 (18)
C14	0.030 (2)	0.029 (2)	0.039 (3)	0.0047 (17)	0.0020 (19)	−0.0039 (19)

Geometric parameters (Å, º) top

Cu1—N1	1.988 (3)	C7—C8	1.391 (5)
Cu1—N2	2.025 (3)	C7—C12	1.392 (5)
Cu1—Cl2	2.2035 (10)	C8—C9	1.384 (5)
Cu1—Cl1	2.2204 (10)	C8—H8A	0.9500
N1—C1	1.335 (4)	C9—C10	1.374 (5)
N1—C5	1.348 (5)	C9—H9A	0.9500
N2—C6	1.290 (4)	C10—C11	1.413 (5)
N2—C7	1.433 (4)	C10—C13	1.510 (5)
C1—C2	1.391 (5)	C11—C12	1.390 (5)
C1—H1A	0.9500	C11—C14	1.505 (5)
C2—C3	1.379 (5)	C12—H12A	0.9500
C2—H2A	0.9500	C13—H13A	0.9800
C3—C4	1.390 (5)	C13—H13B	0.9800
C3—H3A	0.9500	C13—H13C	0.9800
C4—C5	1.383 (5)	C14—H14A	0.9800
C4—H4A	0.9500	C14—H14B	0.9800
C5—C6	1.462 (5)	C14—H14C	0.9800
C6—H6A	0.9500

N1—Cu1—N2	81.49 (11)	C8—C7—C12	119.9 (3)
N1—Cu1—Cl2	145.38 (9)	C8—C7—N2	117.6 (3)
N2—Cu1—Cl2	99.33 (8)	C12—C7—N2	122.5 (3)
N1—Cu1—Cl1	95.98 (9)	C9—C8—C7	118.7 (3)
N2—Cu1—Cl1	145.95 (9)	C9—C8—H8A	120.7
Cl2—Cu1—Cl1	101.41 (4)	C7—C8—H8A	120.7
C1—N1—C5	119.2 (3)	C10—C9—C8	122.5 (3)
C1—N1—Cu1	127.1 (3)	C10—C9—H9A	118.8
C5—N1—Cu1	113.6 (2)	C8—C9—H9A	118.8
C6—N2—C7	120.0 (3)	C9—C10—C11	119.0 (3)
C6—N2—Cu1	112.6 (2)	C9—C10—C13	121.6 (3)
C7—N2—Cu1	127.4 (2)	C11—C10—C13	119.4 (3)
N1—C1—C2	121.5 (3)	C12—C11—C10	118.8 (3)
N1—C1—H1A	119.2	C12—C11—C14	120.0 (3)
C2—C1—H1A	119.2	C10—C11—C14	121.2 (3)
C3—C2—C1	119.6 (3)	C11—C12—C7	121.1 (3)
C3—C2—H2A	120.2	C11—C12—H12A	119.4
C1—C2—H2A	120.2	C7—C12—H12A	119.4
C2—C3—C4	118.8 (3)	C10—C13—H13A	109.5
C2—C3—H3A	120.6	C10—C13—H13B	109.5
C4—C3—H3A	120.6	H13A—C13—H13B	109.5
C5—C4—C3	118.8 (3)	C10—C13—H13C	109.5
C5—C4—H4A	120.6	H13A—C13—H13C	109.5
C3—C4—H4A	120.6	H13B—C13—H13C	109.5
N1—C5—C4	122.1 (3)	C11—C14—H14A	109.5
N1—C5—C6	114.1 (3)	C11—C14—H14B	109.5
C4—C5—C6	123.7 (3)	H14A—C14—H14B	109.5
N2—C6—C5	118.0 (3)	C11—C14—H14C	109.5
N2—C6—H6A	121.0	H14A—C14—H14C	109.5
C5—C6—H6A	121.0	H14B—C14—H14C	109.5

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₁₄H₁₄N₂)]
M_r	344.71
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	8.1171 (4), 9.5784 (4), 10.0609 (5)
α, β, γ (°)	67.236 (2), 88.513 (2), 81.336 (2)
V (Å³)	712.61 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.89
Crystal size (mm)	0.18 × 0.16 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.725, 0.830
No. of measured, independent and observed [I > 2σ(I)] reflections	6451, 3189, 2256
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.126, 1.07
No. of reflections	3189
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.83, −0.62

Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	1.988 (3)	Cu1—Cl2	2.2035 (10)
Cu1—N2	2.025 (3)	Cu1—Cl1	2.2204 (10)

Acknowledgements

The authors would like to acknowledge the Islamic Azad University, Buinzahra Branch Research Council for partial support of this work

References

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Khalaj, M., Dehghanpour, S., Aleeshah, R. & Mahmoudi, A. (2010). Acta Cryst. E66, m1647. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mahmoudi, A., Khalaj, M., Gao, S., Ng, S. W. & Mohammadgholiha, M. (2009). Acta Cryst. E65, m555. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter & R. M. Sweet, pp. 307–326. London: Academic Press. Google Scholar
Salehzadeh, S., Dehghanpour, S., Khalaj, M. & Rahimishakiba, M. (2011). Acta Cryst. E67, m327. 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
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, B. S. & Zhong, H. (2009). Acta Cryst. E65, m1156. Web of Science CSD CrossRef IUCr Journals Google Scholar