[2,6-Bis(p-tol­ylimino­meth­yl)pyridine-κ3N,N′,N′′]dichloridocopper(II)

Li, X.-P.; Zhao, J.-S.; Ng, S.W.

doi:10.1107/S1600536810037025

metal-organic compounds

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Volume 66| Part 10| October 2010| Page m1297

doi:10.1107/S1600536810037025

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[2,6-Bis(p-tolyliminomethyl)pyridine-κ³N,N′,N′′]dichloridocopper(II)

Xiao-Ping Li,^a Jian-She Zhao ^a and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, Shaanxi Key Laboratory for Physico-Inorganic Chemistry, Northwest University, Xi'an 710069, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 15 September 2010; accepted 16 September 2010; online 25 September 2010)

The title compound, [CuCl₂(C₂₁H₁₉N₃)], lies on a twofold rotation axis that passes through the N_pyridyl—Cu bond; this symmetry element relates one half of the organic ligand to the other as well as one Cl ligand to the other. The three N atoms span the axial–equatorial–axial sites of the trigonal-bipyramidal coordination polyhedron; the geometry of the Cu^II atom is 31% distorted from trigonal-bipyramidal (towards square-pyramidal along the Berry pseudorotation pathway).

Related literature

For a chromium chloride adduct with a similar ligand, see: Li et al. (2010 ).

Experimental

Crystal data

[CuCl₂(C₂₁H₁₉N₃)]
M_r = 447.83
Orthorhombic, F d d 2
a = 11.5220 (13) Å
b = 35.522 (4) Å
c = 9.327 (1) Å
V = 3817.4 (7) Å³
Z = 8
Mo Kα radiation
μ = 1.44 mm⁻¹
T = 100 K
0.36 × 0.12 × 0.02 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.626, T_max = 0.972
8753 measured reflections
2190 independent reflections
2023 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.070
S = 1.04
2190 reflections
125 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ), 858 Friedel pairs
Flack parameter: 0.014 (14)

Table 1
Selected bond lengths (Å)

Cu1—N1	1.968 (3)
Cu1—N2	2.101 (2)
Cu1—Cl1	2.3187 (7)

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810037025/xu5030sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037025/xu5030Isup2.hkl

checkCIF report

Comment top

A recent study reported the chromium(III) chloride adduct of 2,6-bis(p-bromphenylimino)pyridine; the N-heterocycle chelates to the metal atom in a terdentate manner (Li et al., 2010). The copper dichlroide adduct of 2,6-bis(p-tolylimino)pyridine adopts a similar structure. The CuCl₂(C₂₁H₁₉N₃) molecule (Scheme I, Fig. 1) lies on a twofold rotation axis that passes through the N_pyridyl—Cu bond; this symmetry element relates one half of the organic ligand to the other. The three N atoms span the axial–equatorial-axial sites of the trigonal bipyramidal coordination polyhedron; the geometry of Cu is 31% distorted along the Berry pseudorotation pathway.

Related literature top

For a chromium chloride adduct with a similar ligand, see: Li et al. (2010).

Experimental top

2,6-Bis(p-tolylimino)pyridine (0.016 g, 0.05 mmol), and copper chloride dihydrate (0.01 g, 0.05 mmol) along with five drops of 1 M hydrochloric acid were dissolved in ethanol (10 ml). The mixture was heated in a Teflon-lined, stainless-steel Parr bomb at 363 K for 120 h. The bomb was cooled at 5 K per hour. Deep orange crystals were isolated.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of CuCl₂(C₂₁H₁₉N₃) at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

[2,6-Bis(p-tolyliminomethyl)pyridine- κ³N,N',N'']dichloridocopper(II) top

Crystal data top

[CuCl₂(C₂₁H₁₉N₃)]	F(000) = 1832
M_r = 447.83	D_x = 1.558 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 2394 reflections
a = 11.5220 (13) Å	θ = 2.3–26.1°
b = 35.522 (4) Å	µ = 1.44 mm⁻¹
c = 9.327 (1) Å	T = 100 K
V = 3817.4 (7) Å³	Prism, orange
Z = 8	0.36 × 0.12 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	2190 independent reflections
Radiation source: fine-focus sealed tube	2023 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→14
T_min = 0.626, T_max = 0.972	k = −46→46
8753 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0349P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
2190 reflections	Δρ_max = 0.29 e Å⁻³
125 parameters	Δρ_min = −0.30 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 858 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.014 (14)

Crystal data top

[CuCl₂(C₂₁H₁₉N₃)]	V = 3817.4 (7) Å³
M_r = 447.83	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 11.5220 (13) Å	µ = 1.44 mm⁻¹
b = 35.522 (4) Å	T = 100 K
c = 9.327 (1) Å	0.36 × 0.12 × 0.02 mm

Data collection top

Bruker SMART APEX diffractometer	2190 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2023 reflections with I > 2σ(I)
T_min = 0.626, T_max = 0.972	R_int = 0.050
8753 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.29 e Å⁻³
S = 1.04	Δρ_min = −0.30 e Å⁻³
2190 reflections	Absolute structure: Flack (1983), 858 Friedel pairs
125 parameters	Absolute structure parameter: 0.014 (14)
1 restraint

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

	x	y	z	U_iso*/U_eq
Cu1	1.0000	0.5000	0.50991 (4)	0.01349 (12)
Cl1	0.90550 (6)	0.543930 (17)	0.36785 (8)	0.01783 (15)
N1	1.0000	0.5000	0.7209 (3)	0.0136 (7)
N2	0.8670 (2)	0.46146 (6)	0.5570 (2)	0.0137 (5)
C1	1.0000	0.5000	1.0139 (7)	0.0233 (8)
H1	1.0000	0.5000	1.1158	0.028*
C2	0.9203 (3)	0.47824 (8)	0.9392 (3)	0.0197 (6)
H2	0.8648	0.4634	0.9889	0.024*
C3	0.9231 (2)	0.47860 (7)	0.7896 (3)	0.0148 (6)
C4	0.8502 (3)	0.45700 (8)	0.6925 (3)	0.0159 (6)
H4	0.7924	0.4403	0.7276	0.019*
C5	0.8043 (2)	0.43861 (7)	0.4590 (3)	0.0146 (5)
C6	0.7745 (2)	0.45364 (7)	0.3259 (3)	0.0162 (6)
H6	0.7996	0.4782	0.3003	0.019*
C7	0.7085 (2)	0.43273 (7)	0.2314 (3)	0.0155 (6)
H7	0.6854	0.4436	0.1429	0.019*
C8	0.6752 (2)	0.39602 (7)	0.2636 (3)	0.0184 (6)
C9	0.7099 (3)	0.38078 (8)	0.3943 (3)	0.0220 (6)
H9	0.6893	0.3556	0.4171	0.026*
C10	0.7736 (2)	0.40150 (8)	0.4910 (3)	0.0195 (6)
H10	0.7966	0.3906	0.5796	0.023*
C11	0.6078 (3)	0.37314 (8)	0.1571 (3)	0.0233 (6)
H11A	0.5523	0.3571	0.2079	0.035*
H11B	0.6613	0.3574	0.1017	0.035*
H11C	0.5659	0.3900	0.0921	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0124 (2)	0.0191 (2)	0.0089 (2)	−0.00124 (19)	0.000	0.000
Cl1	0.0175 (3)	0.0185 (3)	0.0175 (3)	0.0010 (3)	−0.0038 (3)	0.0027 (3)
N1	0.0098 (15)	0.0178 (15)	0.0131 (17)	0.0039 (13)	0.000	0.000
N2	0.0135 (12)	0.0152 (11)	0.0124 (11)	0.0023 (9)	0.0014 (9)	0.0001 (8)
C1	0.031 (2)	0.0271 (18)	0.0118 (18)	0.000 (2)	0.000	0.000
C2	0.0255 (16)	0.0207 (15)	0.0129 (14)	0.0006 (11)	0.0038 (11)	−0.0004 (11)
C3	0.0139 (14)	0.0179 (13)	0.0124 (16)	0.0031 (10)	0.0043 (11)	0.0007 (10)
C4	0.0180 (15)	0.0165 (13)	0.0133 (14)	0.0010 (11)	0.0023 (11)	0.0002 (11)
C5	0.0134 (13)	0.0177 (13)	0.0126 (13)	−0.0007 (11)	0.0018 (11)	−0.0017 (10)
C6	0.0166 (13)	0.0152 (12)	0.0168 (14)	0.0013 (11)	0.0016 (11)	0.0001 (11)
C7	0.0158 (13)	0.0211 (13)	0.0095 (14)	0.0048 (11)	0.0007 (10)	−0.0007 (10)
C8	0.0153 (13)	0.0215 (13)	0.0183 (14)	−0.0026 (10)	0.0005 (14)	−0.0032 (13)
C9	0.0271 (15)	0.0187 (14)	0.0201 (16)	−0.0057 (11)	0.0014 (13)	0.0012 (11)
C10	0.0212 (15)	0.0196 (13)	0.0177 (16)	−0.0026 (10)	−0.0009 (12)	0.0043 (12)
C11	0.0252 (16)	0.0243 (15)	0.0203 (16)	−0.0069 (13)	−0.0020 (12)	−0.0011 (12)

Geometric parameters (Å, º) top

Cu1—N1	1.968 (3)	C4—H4	0.9500
Cu1—N2ⁱ	2.101 (2)	C5—C6	1.394 (4)
Cu1—N2	2.101 (2)	C5—C10	1.397 (4)
Cu1—Cl1	2.3187 (7)	C6—C7	1.381 (4)
Cu1—Cl1ⁱ	2.3187 (7)	C6—H6	0.9500
N1—C3ⁱ	1.332 (3)	C7—C8	1.392 (4)
N1—C3	1.332 (3)	C7—H7	0.9500
N2—C4	1.288 (3)	C8—C9	1.392 (4)
N2—C5	1.421 (4)	C8—C11	1.500 (4)
C1—C2ⁱ	1.388 (5)	C9—C10	1.377 (4)
C1—C2	1.388 (5)	C9—H9	0.9500
C1—H1	0.9500	C10—H10	0.9500
C2—C3	1.396 (3)	C11—H11A	0.9800
C2—H2	0.9500	C11—H11B	0.9800
C3—C4	1.454 (4)	C11—H11C	0.9800

N1—Cu1—N2ⁱ	77.92 (7)	N2—C4—H4	121.3
N1—Cu1—N2	77.92 (7)	C3—C4—H4	121.3
N2ⁱ—Cu1—N2	155.85 (13)	C6—C5—C10	119.3 (3)
N1—Cu1—Cl1	124.85 (2)	C6—C5—N2	118.7 (2)
N2ⁱ—Cu1—Cl1	91.35 (6)	C10—C5—N2	122.0 (2)
N2—Cu1—Cl1	102.45 (7)	C7—C6—C5	119.8 (2)
N1—Cu1—Cl1ⁱ	124.85 (2)	C7—C6—H6	120.1
N2ⁱ—Cu1—Cl1ⁱ	102.45 (7)	C5—C6—H6	120.1
N2—Cu1—Cl1ⁱ	91.35 (6)	C6—C7—C8	121.2 (3)
Cl1—Cu1—Cl1ⁱ	110.30 (4)	C6—C7—H7	119.4
C3ⁱ—N1—C3	122.4 (3)	C8—C7—H7	119.4
C3ⁱ—N1—Cu1	118.78 (17)	C7—C8—C9	118.3 (3)
C3—N1—Cu1	118.78 (17)	C7—C8—C11	120.5 (3)
C4—N2—C5	119.0 (2)	C9—C8—C11	121.2 (2)
C4—N2—Cu1	113.3 (2)	C10—C9—C8	121.3 (3)
C5—N2—Cu1	127.49 (18)	C10—C9—H9	119.4
C2ⁱ—C1—C2	119.7 (5)	C8—C9—H9	119.4
C2ⁱ—C1—H1	120.1	C9—C10—C5	119.9 (3)
C2—C1—H1	120.1	C9—C10—H10	120.0
C1—C2—C3	118.8 (4)	C5—C10—H10	120.0
C1—C2—H2	120.6	C8—C11—H11A	109.5
C3—C2—H2	120.6	C8—C11—H11B	109.5
N1—C3—C2	120.2 (3)	H11A—C11—H11B	109.5
N1—C3—C4	112.7 (2)	C8—C11—H11C	109.5
C2—C3—C4	127.2 (3)	H11A—C11—H11C	109.5
N2—C4—C3	117.3 (3)	H11B—C11—H11C	109.5

N2ⁱ—Cu1—N1—C3ⁱ	−1.14 (14)	C1—C2—C3—N1	−1.1 (4)
N2—Cu1—N1—C3ⁱ	178.86 (14)	C1—C2—C3—C4	177.8 (2)
Cl1—Cu1—N1—C3ⁱ	−84.27 (13)	C5—N2—C4—C3	174.8 (2)
Cl1ⁱ—Cu1—N1—C3ⁱ	95.73 (13)	Cu1—N2—C4—C3	0.1 (3)
N2ⁱ—Cu1—N1—C3	178.86 (14)	N1—C3—C4—N2	−1.0 (4)
N2—Cu1—N1—C3	−1.14 (14)	C2—C3—C4—N2	−180.0 (3)
Cl1—Cu1—N1—C3	95.73 (13)	C4—N2—C5—C6	148.0 (3)
Cl1ⁱ—Cu1—N1—C3	−84.27 (13)	Cu1—N2—C5—C6	−38.1 (3)
N1—Cu1—N2—C4	0.5 (2)	C4—N2—C5—C10	−33.1 (4)
N2ⁱ—Cu1—N2—C4	0.5 (2)	Cu1—N2—C5—C10	140.8 (2)
Cl1—Cu1—N2—C4	−122.9 (2)	C10—C5—C6—C7	4.4 (4)
Cl1ⁱ—Cu1—N2—C4	126.0 (2)	N2—C5—C6—C7	−176.7 (2)
N1—Cu1—N2—C5	−173.7 (2)	C5—C6—C7—C8	−3.0 (4)
N2ⁱ—Cu1—N2—C5	−173.7 (2)	C6—C7—C8—C9	0.2 (4)
Cl1—Cu1—N2—C5	62.9 (2)	C6—C7—C8—C11	−177.4 (3)
Cl1ⁱ—Cu1—N2—C5	−48.3 (2)	C7—C8—C9—C10	1.3 (4)
C2ⁱ—C1—C2—C3	0.5 (2)	C11—C8—C9—C10	178.8 (3)
C3ⁱ—N1—C3—C2	0.6 (2)	C8—C9—C10—C5	0.1 (4)
Cu1—N1—C3—C2	−179.4 (2)	C6—C5—C10—C9	−3.0 (4)
C3ⁱ—N1—C3—C4	−178.5 (2)	N2—C5—C10—C9	178.2 (3)
Cu1—N1—C3—C4	1.5 (2)

Symmetry code: (i) −x+2, −y+1, z.

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₂₁H₁₉N₃)]
M_r	447.83
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	100
a, b, c (Å)	11.5220 (13), 35.522 (4), 9.327 (1)
V (Å³)	3817.4 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.44
Crystal size (mm)	0.36 × 0.12 × 0.02

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.626, 0.972
No. of measured, independent and observed [I > 2σ(I)] reflections	8753, 2190, 2023
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.070, 1.04
No. of reflections	2190
No. of parameters	125
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.30
Absolute structure	Flack (1983), 858 Friedel pairs
Absolute structure parameter	0.014 (14)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cu1—N1	1.968 (3)	Cu1—Cl1	2.3187 (7)
Cu1—N2	2.101 (2)

Acknowledgements

We thank the Graduate Experimental Research Fund of Northwest University (project No. 09YSY22), the National Natural Science Foundation of China (No. 20971104) and the University of Malaya for supporting this study.

References

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