metal-organic compounds
[2,6-Bis(p-tolyliminomethyl)pyridine-κ3N,N′,N′′]dichloridocopper(II)
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
The title compound, [CuCl2(C21H19N3)], lies on a twofold rotation axis that passes through the Npyridyl—Cu bond; this 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 the geometry of the CuII atom is 31% distorted from trigonal-bipyramidal (towards square-pyramidal along the pathway).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S1600536810037025/xu5030sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536810037025/xu5030Isup2.hkl
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.
Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the
in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).Data collection: APEX2 (Bruker, 2009); cell
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).Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of CuCl2(C21H19N3) at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. |
[CuCl2(C21H19N3)] | F(000) = 1832 |
Mr = 447.83 | Dx = 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 |
Bruker SMART APEX diffractometer | 2190 independent reflections |
Radiation source: fine-focus sealed tube | 2023 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→14 |
Tmin = 0.626, Tmax = 0.972 | k = −46→46 |
8753 measured reflections | l = −12→12 |
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(Fo2) + (0.0349P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
2190 reflections | Δρmax = 0.29 e Å−3 |
125 parameters | Δρmin = −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) |
[CuCl2(C21H19N3)] | V = 3817.4 (7) Å3 |
Mr = 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 |
Bruker SMART APEX diffractometer | 2190 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2023 reflections with I > 2σ(I) |
Tmin = 0.626, Tmax = 0.972 | Rint = 0.050 |
8753 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.070 | Δρmax = 0.29 e Å−3 |
S = 1.04 | Δρmin = −0.30 e Å−3 |
2190 reflections | Absolute structure: Flack (1983), 858 Friedel pairs |
125 parameters | Absolute structure parameter: 0.014 (14) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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)] |
Mr | 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) |
Tmin, Tmax | 0.626, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8753, 2190, 2023 |
Rint | 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 |
Δρmax, Δρmin (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).
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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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 Npyridyl—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.