Dichlorido[(R,R)-N1,N1,N2-tribenzyl­cyclo­hexane-1,2-diamine-κ2N1,N2]copper(II)

Nguyen, Q.T.; Jeong, J.H.

doi:10.1107/S1600536810014054

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page m565

https://doi.org/10.1107/S1600536810014054

Open

access

Dichlorido[(R,R)-N¹,N¹,N²-tribenzylcyclohexane-1,2-diamine-κ²N¹,N²]copper(II)

Quang Trung Nguyen ^a and Jong Hwa Jeong ^a ^*

^aDepartment of Chemistry, Kyungpook National University, Taegu 702-701, Republic of Korea
^*Correspondence e-mail: jeongjh@knu.ac.kr

(Received 26 March 2010; accepted 16 April 2010; online 24 April 2010)

In the title compound, [CuCl₂(C₂₇H₃₂N₂)], which bears a chiral diamine ligand, viz (R,R)-N,N,N′′- tribenzylcyclohexane-1,2-diamine, the Cu^II ion is ligated by two N and two Cl atoms in a distorted square-planar geometry. The coordination of the ligands to the Cu^II ion results in the formation of a five-membered heterocyclic ring and a chiral center at the monosubstituted nitrogen in an (S)-configuration. The catalytic capacity of the complex for the asymmetric nitroaldol reaction is promising (49% ee).

Related literature

For the synthesis of N,N,N′′-tribenzyl-(R,R)-1,2-diaminocyclohexane, see: Tye et al. (2002 ); Boyd et al. (2005 ). For related structures, see: Alexakis et al. (2001 ); Tye et al. (2002); Boyd et al. (2005, 2006 ); Arjan et al. (2005 ); Brethon et al. (2004 ); Jones & Mahon (2008 ); Evans & Seidel (2005 ); Evans et al. (2007 ); Roh et al. (2004 ); Nguyen & Jeong (2008a ,b ).

Experimental

Crystal data

[CuCl₂(C₂₇H₃₂N₂)]
M_r = 519.00
Orthorhombic, P 2₁ 2₁ 2₁
a = 10.5806 (7) Å
b = 15.4409 (8) Å
c = 16.2579 (12) Å
V = 2656.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 295 K
0.40 × 0.40 × 0.40 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: analytical (ABSCALC; McArdle & Daly, 1999 ) T_min = 0.660, T_max = 0.666
5793 measured reflections
4931 independent reflections
3885 reflections with I > 2σ(I)
R_int = 0.019
3 standard reflections every 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.083
S = 1.06
4931 reflections
292 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 )
Flack parameter: −0.017 (13)

Data collection: CAD4 (Enraf–Nonius, 1989 ); cell refinement: CAD4; data reduction: XCAD (McArdle, 1999 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810014054/rk2198sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810014054/rk2198Isup2.hkl

checkCIF report

Comment top

Disubstituted, trisubstituted and tetrasubstituted (R,R)-1,2- diaminocyclohexane were synthesized (Alexakis et al., 2001; Tye et al., 2002; Boyd et al., 2005, 2006; Arjan et al., 2005). Especially disubstituted chiral diamine ligands with Rh (Brethon et al., 2004; Jones & Mahon, 2008), Ni (Evans & Seidel, 2005; Evans et al., 2007), Zn (Roh et al., 2004; Nguyen & Jeong, 2008a), Cu (Nguyen & Jeong, 2008b) were extensively applied in asymmetric synthesis. However, the coordination chemistry and application of asymmetric trisubstituted chiral 1,2-diaminocyclohexanes containing a secondary and a tertiary amines had not attended much. In this study, a new complex of Cu(II) containing N,N,N'-tribenzyl-(R,R)-1,2- diaminocyclohexane (Tye et al., 2002; Boyd et al., 2005) was synthesized and its molecular and crystal structures were determined.

Also, capability of the complex as an enantioselective catalyst for asymmetric nitroaldol reaction was examined. The copper ion was ligated by two nitrogen and two chloride atoms in distorted square-planar geometry. The coordination of the ligands to the Cu ion induced a 5–membered heterocyclic ring and a chiral center at monosubstituted nitrogen in (S)-configuration. Catalytic capacity of the complex for asymmetric nitroaldol reaction was promising (49% ee {ee = [R - S/ R+S] x 100 or [S - R/ R+S] x 100}).

Related literature top

For the synthesis of N,N,N'-tribenzyl-(R,R)-1,2- diaminocyclohexane, see: Tye et al. (2002); Boyd et al. (2005). For related structures, see: Alexakis et al. (2001); Tye et al. (2002); Boyd et al. (2005, 2006); Arjan et al. (2005); Brethon et al. (2004); Jones & Mahon (2008); Evans & Seidel (2005); Evans et al. (2007); Roh et al. (2004); Nguyen & Jeong (2008a,b).

Experimental top

A solution of N,N,N'-tribenzyl-(R,R)- 1,2-diaminocyclohexane (1.57 g, 4.08 mmol) in ethanol (5 ml) was added slowly to a solution of CuCl₂^.2H₂O (0.69 g, 4.01 mmol) in ethanol (10 ml) Tye et al., (2002); Boyd et al., (2005). The mixture was stirred overnight at ambient temperature. The solvent was removed to yield blue solids. The product was re–crystallized from anhydrous ethanol to afford blue crystals (1.64 g, yield 79%). Anal. Calc. for C₂₇H₃₂Cl₂CuN₂: C 62.48, H 6.21, N 5.40 and found: C 62.20, H 6.30, N 5.46%.

Structure description top

Computing details top

Data collection: CAD4 (Enraf–Nonius, 1989); cell refinement: CAD4 (Enraf–Nonius, 1989); data reduction: XCAD (McArdle, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 [SHELXL97?] (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. A view of title compound molecule with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are presented as a small spheres of arbitrary radius.

Dichlorido[(R,R)-N¹,N¹,N²- tribenzylcyclohexane-1,2-diamine-κ²N¹,N²]copper(II) top

Crystal data top

[CuCl₂(C₂₇H₃₂N₂)]	F(000) = 1084
M_r = 519.00	D_x = 1.298 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 10.5806 (7) Å	θ = 10–13°
b = 15.4409 (8) Å	µ = 1.04 mm⁻¹
c = 16.2579 (12) Å	T = 295 K
V = 2656.1 (3) Å³	Block, blue
Z = 4	0.40 × 0.40 × 0.40 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	3885 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 25.5°, θ_min = 1.8°
ω/2θ scans	h = −12→12
Absorption correction: analytical (ABSCALC; McArdle & Daly, 1999)	k = −18→18
T_min = 0.660, T_max = 0.666	l = −19→19
5793 measured reflections	3 standard reflections every 60 min
4931 independent reflections	intensity decay: none

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0488P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
4931 reflections	Δρ_max = 0.33 e Å⁻³
292 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.017 (13)

Crystal data top

[CuCl₂(C₂₇H₃₂N₂)]	V = 2656.1 (3) Å³
M_r = 519.00	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 10.5806 (7) Å	µ = 1.04 mm⁻¹
b = 15.4409 (8) Å	T = 295 K
c = 16.2579 (12) Å	0.40 × 0.40 × 0.40 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	3885 reflections with I > 2σ(I)
Absorption correction: analytical (ABSCALC; McArdle & Daly, 1999)	R_int = 0.019
T_min = 0.660, T_max = 0.666	3 standard reflections every 60 min
5793 measured reflections	intensity decay: none
4931 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.083	Δρ_max = 0.33 e Å⁻³
S = 1.06	Δρ_min = −0.24 e Å⁻³
4931 reflections	Absolute structure: Flack (1983)
292 parameters	Absolute structure parameter: −0.017 (13)
0 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Cu	0.03338 (3)	0.43742 (2)	0.76295 (2)	0.03853 (10)
Cl1	−0.03484 (8)	0.33981 (5)	0.85529 (5)	0.05231 (19)
Cl2	−0.10262 (9)	0.40812 (6)	0.66326 (6)	0.0609 (2)
N1	0.0744 (2)	0.56146 (15)	0.72591 (14)	0.0361 (5)
N2	0.2032 (2)	0.43863 (17)	0.81961 (17)	0.0403 (5)
H2	0.193 (3)	0.438 (2)	0.871 (2)	0.048*
C1	0.1701 (3)	0.59164 (18)	0.78886 (17)	0.0352 (6)
H1	0.1234	0.5982	0.8406	0.042*
C2	0.2323 (3)	0.67928 (19)	0.7726 (2)	0.0476 (7)
H2A	0.2862	0.6755	0.7245	0.057*
H2B	0.1679	0.7226	0.7621	0.057*
C3	0.3099 (4)	0.7054 (2)	0.8468 (2)	0.0561 (9)
H3A	0.3490	0.7612	0.8368	0.067*
H3B	0.2552	0.7108	0.8944	0.067*
C4	0.4109 (3)	0.6388 (2)	0.8639 (2)	0.0602 (9)
H4A	0.4581	0.6556	0.9125	0.072*
H4B	0.4692	0.6366	0.8179	0.072*
C5	0.3532 (3)	0.5492 (2)	0.8772 (2)	0.0489 (8)
H5A	0.3028	0.5498	0.9271	0.059*
H5B	0.4204	0.5072	0.8845	0.059*
C6	0.2699 (3)	0.52161 (18)	0.8048 (2)	0.0373 (7)
H6	0.3229	0.5156	0.7557	0.045*
C7	−0.0463 (3)	0.61569 (18)	0.73180 (19)	0.0433 (7)
H7A	−0.0267	0.6739	0.7135	0.052*
H7B	−0.1075	0.5919	0.6936	0.052*
C8	−0.1073 (3)	0.62181 (19)	0.8143 (2)	0.0428 (7)
C9	−0.1934 (3)	0.5605 (2)	0.8410 (2)	0.0544 (8)
H9	−0.2095	0.5122	0.8085	0.065*
C10	−0.2553 (3)	0.5697 (3)	0.9143 (3)	0.0645 (10)
H10	−0.3108	0.5267	0.9317	0.077*
C11	−0.2371 (4)	0.6404 (3)	0.9621 (2)	0.0628 (10)
H11	−0.2812	0.6469	1.0112	0.075*
C12	−0.1515 (4)	0.7031 (3)	0.9366 (2)	0.0609 (10)
H12	−0.1373	0.7517	0.9692	0.073*
C13	−0.0880 (4)	0.6938 (2)	0.8638 (2)	0.0530 (9)
H13	−0.0312	0.7364	0.8473	0.064*
C14	0.1132 (3)	0.5719 (2)	0.63786 (17)	0.0465 (7)
H14A	0.1232	0.6333	0.6273	0.056*
H14B	0.0438	0.5518	0.6038	0.056*
C15	0.2318 (3)	0.5269 (2)	0.60886 (19)	0.0502 (8)
C16	0.2368 (4)	0.4375 (3)	0.59948 (19)	0.0564 (8)
H16	0.1669	0.4039	0.6127	0.068*
C17	0.3453 (4)	0.3988 (3)	0.5705 (3)	0.0759 (12)
H17	0.3495	0.3388	0.5664	0.091*
C18	0.4472 (5)	0.4482 (4)	0.5478 (3)	0.1003 (17)
H18	0.5202	0.4216	0.5284	0.120*
C19	0.4416 (5)	0.5367 (4)	0.5536 (3)	0.0976 (17)
H19	0.5098	0.5703	0.5368	0.117*
C20	0.3350 (4)	0.5754 (3)	0.5844 (2)	0.0744 (12)
H20	0.3320	0.6354	0.5888	0.089*
C21	0.2727 (3)	0.3570 (2)	0.7986 (2)	0.0551 (9)
H21A	0.2184	0.3082	0.8114	0.066*
H21B	0.2874	0.3562	0.7397	0.066*
C22	0.3962 (3)	0.34379 (19)	0.8410 (2)	0.0432 (7)
C23	0.4030 (4)	0.3147 (3)	0.9210 (2)	0.0631 (10)
H23	0.3292	0.3016	0.9495	0.076*
C24	0.5196 (5)	0.3048 (2)	0.9596 (2)	0.0737 (12)
H24	0.5238	0.2849	1.0135	0.088*
C25	0.6279 (4)	0.3247 (3)	0.9178 (3)	0.0705 (12)
H25	0.7056	0.3197	0.9440	0.085*
C26	0.6229 (3)	0.3515 (2)	0.8387 (3)	0.0621 (10)
H26	0.6970	0.3628	0.8099	0.075*
C27	0.5094 (3)	0.3617 (2)	0.8020 (2)	0.0517 (8)
H27	0.5073	0.3816	0.7480	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.03398 (17)	0.03603 (16)	0.04556 (19)	0.00039 (16)	−0.00646 (17)	−0.00163 (15)
Cl1	0.0463 (4)	0.0478 (4)	0.0629 (5)	−0.0078 (4)	−0.0052 (4)	0.0079 (3)
Cl2	0.0622 (5)	0.0594 (5)	0.0612 (5)	−0.0084 (4)	−0.0245 (4)	−0.0054 (4)
N1	0.0349 (11)	0.0387 (11)	0.0348 (12)	0.0045 (10)	−0.0041 (9)	−0.0005 (11)
N2	0.0347 (12)	0.0368 (12)	0.0494 (14)	0.0047 (12)	−0.0050 (11)	−0.0005 (13)
C1	0.0369 (15)	0.0370 (15)	0.0317 (15)	0.0021 (12)	−0.0037 (12)	−0.0027 (11)
C2	0.0491 (17)	0.0375 (15)	0.0563 (19)	−0.0031 (13)	−0.0058 (16)	−0.0004 (15)
C3	0.060 (2)	0.0404 (18)	0.068 (2)	−0.0031 (16)	−0.0085 (19)	−0.0075 (16)
C4	0.0491 (19)	0.056 (2)	0.075 (2)	−0.0027 (17)	−0.0152 (18)	−0.0130 (18)
C5	0.0405 (17)	0.046 (2)	0.060 (2)	0.0053 (14)	−0.0171 (15)	−0.0075 (15)
C6	0.0308 (15)	0.0376 (15)	0.0435 (17)	0.0020 (13)	−0.0003 (13)	−0.0048 (13)
C7	0.0416 (16)	0.0432 (15)	0.0452 (15)	0.0113 (13)	−0.0069 (16)	0.0001 (13)
C8	0.0360 (16)	0.0383 (16)	0.0540 (19)	0.0081 (14)	−0.0024 (15)	0.0009 (14)
C9	0.0398 (17)	0.0482 (18)	0.075 (2)	−0.0005 (17)	−0.0008 (17)	−0.0117 (19)
C10	0.0439 (19)	0.062 (2)	0.087 (3)	−0.0029 (19)	0.0155 (18)	0.007 (2)
C11	0.058 (2)	0.071 (3)	0.060 (2)	0.016 (2)	0.0131 (18)	0.004 (2)
C12	0.070 (2)	0.055 (2)	0.057 (2)	0.0071 (19)	0.0078 (19)	−0.0099 (17)
C13	0.061 (2)	0.0385 (17)	0.059 (2)	0.0054 (15)	0.0057 (17)	0.0001 (15)
C14	0.0547 (18)	0.0492 (18)	0.0357 (15)	0.0029 (17)	0.0005 (14)	0.0012 (14)
C15	0.061 (2)	0.058 (2)	0.0313 (16)	−0.0050 (17)	0.0085 (15)	−0.0060 (14)
C16	0.065 (2)	0.061 (2)	0.0434 (18)	−0.002 (2)	0.0110 (15)	−0.0125 (18)
C17	0.081 (3)	0.075 (3)	0.072 (3)	0.008 (2)	0.012 (2)	−0.027 (2)
C18	0.075 (3)	0.127 (4)	0.099 (3)	0.005 (3)	0.036 (3)	−0.035 (3)
C19	0.082 (3)	0.115 (4)	0.096 (3)	−0.022 (3)	0.047 (3)	−0.017 (3)
C20	0.085 (3)	0.076 (3)	0.062 (2)	−0.015 (2)	0.029 (2)	−0.006 (2)
C21	0.0438 (19)	0.0413 (18)	0.080 (2)	0.0136 (15)	−0.0093 (18)	−0.0090 (17)
C22	0.0367 (16)	0.0350 (15)	0.058 (2)	0.0057 (13)	0.0038 (15)	0.0010 (14)
C23	0.059 (2)	0.061 (2)	0.070 (3)	0.0144 (19)	0.020 (2)	0.0199 (19)
C24	0.096 (3)	0.071 (3)	0.055 (2)	0.030 (3)	−0.005 (2)	0.0129 (18)
C25	0.054 (2)	0.071 (3)	0.086 (3)	0.019 (2)	−0.017 (2)	−0.008 (2)
C26	0.0404 (19)	0.050 (2)	0.096 (3)	0.0027 (16)	0.008 (2)	−0.001 (2)
C27	0.046 (2)	0.0439 (17)	0.065 (2)	0.0104 (14)	0.0076 (16)	0.0028 (15)

Geometric parameters (Å, º) top

Cu—N2	2.019 (2)	C10—H10	0.9300
Cu—N1	2.054 (2)	C11—C12	1.389 (5)
Cu—Cl2	2.2141 (9)	C11—H11	0.9300
Cu—Cl1	2.2463 (8)	C12—C13	1.369 (5)
N1—C14	1.498 (4)	C12—H12	0.9300
N1—C1	1.513 (3)	C13—H13	0.9300
N1—C7	1.530 (3)	C14—C15	1.511 (5)
N2—C6	1.482 (4)	C14—H14A	0.9700
N2—C21	1.499 (4)	C14—H14B	0.9700
N2—H2	0.85 (3)	C15—C20	1.383 (5)
C1—C2	1.528 (4)	C15—C16	1.389 (5)
C1—C6	1.533 (4)	C16—C17	1.377 (5)
C1—H1	0.9800	C16—H16	0.9300
C2—C3	1.513 (5)	C17—C18	1.371 (6)
C2—H2A	0.9700	C17—H17	0.9300
C2—H2B	0.9700	C18—C19	1.371 (7)
C3—C4	1.509 (5)	C18—H18	0.9300
C3—H3A	0.9700	C19—C20	1.371 (6)
C3—H3B	0.9700	C19—H19	0.9300
C4—C5	1.528 (5)	C20—H20	0.9300
C4—H4A	0.9700	C21—C22	1.492 (5)
C4—H4B	0.9700	C21—H21A	0.9700
C5—C6	1.531 (4)	C21—H21B	0.9700
C5—H5A	0.9700	C22—C23	1.379 (5)
C5—H5B	0.9700	C22—C27	1.383 (4)
C6—H6	0.9800	C23—C24	1.392 (6)
C7—C8	1.492 (4)	C23—H23	0.9300
C7—H7A	0.9700	C24—C25	1.366 (6)
C7—H7B	0.9700	C24—H24	0.9300
C8—C9	1.383 (5)	C25—C26	1.352 (6)
C8—C13	1.388 (5)	C25—H25	0.9300
C9—C10	1.368 (5)	C26—C27	1.350 (5)
C9—H9	0.9300	C26—H26	0.9300
C10—C11	1.354 (6)	C27—H27	0.9300

N2—Cu—N1	86.39 (10)	C10—C9—C8	121.2 (4)
N2—Cu—Cl2	156.09 (8)	C10—C9—H9	119.4
N1—Cu—Cl2	96.50 (7)	C8—C9—H9	119.4
N2—Cu—Cl1	89.27 (8)	C11—C10—C9	121.1 (4)
N1—Cu—Cl1	152.80 (7)	C11—C10—H10	119.5
Cl2—Cu—Cl1	98.24 (4)	C9—C10—H10	119.5
C14—N1—C1	115.5 (2)	C10—C11—C12	118.9 (4)
C14—N1—C7	103.3 (2)	C10—C11—H11	120.5
C1—N1—C7	110.3 (2)	C12—C11—H11	120.5
C14—N1—Cu	115.99 (19)	C13—C12—C11	120.4 (4)
C1—N1—Cu	103.32 (16)	C13—C12—H12	119.8
C7—N1—Cu	108.40 (17)	C11—C12—H12	119.8
C6—N2—C21	117.2 (2)	C12—C13—C8	120.9 (3)
C6—N2—Cu	110.95 (18)	C12—C13—H13	119.6
C21—N2—Cu	108.9 (2)	C8—C13—H13	119.6
C6—N2—H2	103 (2)	N1—C14—C15	118.5 (3)
C21—N2—H2	106 (2)	N1—C14—H14A	107.7
Cu—N2—H2	110 (2)	C15—C14—H14A	107.7
N1—C1—C2	116.4 (2)	N1—C14—H14B	107.7
N1—C1—C6	111.0 (2)	C15—C14—H14B	107.7
C2—C1—C6	111.0 (2)	H14A—C14—H14B	107.1
N1—C1—H1	105.9	C20—C15—C16	118.5 (3)
C2—C1—H1	105.9	C20—C15—C14	119.8 (3)
C6—C1—H1	105.9	C16—C15—C14	121.5 (3)
C3—C2—C1	109.4 (3)	C17—C16—C15	120.0 (4)
C3—C2—H2A	109.8	C17—C16—H16	120.0
C1—C2—H2A	109.8	C15—C16—H16	120.0
C3—C2—H2B	109.8	C18—C17—C16	120.4 (4)
C1—C2—H2B	109.8	C18—C17—H17	119.8
H2A—C2—H2B	108.2	C16—C17—H17	119.8
C4—C3—C2	110.5 (3)	C19—C18—C17	120.1 (5)
C4—C3—H3A	109.6	C19—C18—H18	119.9
C2—C3—H3A	109.6	C17—C18—H18	119.9
C4—C3—H3B	109.6	C18—C19—C20	119.7 (5)
C2—C3—H3B	109.6	C18—C19—H19	120.2
H3A—C3—H3B	108.1	C20—C19—H19	120.2
C3—C4—C5	111.1 (3)	C19—C20—C15	121.2 (4)
C3—C4—H4A	109.4	C19—C20—H20	119.4
C5—C4—H4A	109.4	C15—C20—H20	119.4
C3—C4—H4B	109.4	C22—C21—N2	116.0 (3)
C5—C4—H4B	109.4	C22—C21—H21A	108.3
H4A—C4—H4B	108.0	N2—C21—H21A	108.3
C4—C5—C6	111.9 (3)	C22—C21—H21B	108.3
C4—C5—H5A	109.2	N2—C21—H21B	108.3
C6—C5—H5A	109.2	H21A—C21—H21B	107.4
C4—C5—H5B	109.2	C23—C22—C27	116.9 (3)
C6—C5—H5B	109.2	C23—C22—C21	121.8 (3)
H5A—C5—H5B	107.9	C27—C22—C21	121.3 (3)
N2—C6—C5	112.9 (3)	C22—C23—C24	120.5 (4)
N2—C6—C1	108.0 (2)	C22—C23—H23	119.8
C5—C6—C1	109.3 (2)	C24—C23—H23	119.8
N2—C6—H6	108.8	C25—C24—C23	119.6 (3)
C5—C6—H6	108.8	C25—C24—H24	120.2
C1—C6—H6	108.8	C23—C24—H24	120.2
C8—C7—N1	116.9 (2)	C26—C25—C24	120.6 (4)
C8—C7—H7A	108.1	C26—C25—H25	119.7
N1—C7—H7A	108.1	C24—C25—H25	119.7
C8—C7—H7B	108.1	C27—C26—C25	119.4 (4)
N1—C7—H7B	108.1	C27—C26—H26	120.3
H7A—C7—H7B	107.3	C25—C26—H26	120.3
C9—C8—C13	117.6 (3)	C26—C27—C22	123.0 (3)
C9—C8—C7	121.6 (3)	C26—C27—H27	118.5
C13—C8—C7	120.6 (3)	C22—C27—H27	118.5

N2—Cu—N1—C14	104.1 (2)	C1—N1—C7—C8	−53.7 (3)
Cl2—Cu—N1—C14	−52.04 (19)	Cu—N1—C7—C8	58.8 (3)
Cl1—Cu—N1—C14	−174.54 (15)	N1—C7—C8—C9	−86.8 (3)
N2—Cu—N1—C1	−23.25 (17)	N1—C7—C8—C13	99.2 (3)
Cl2—Cu—N1—C1	−179.41 (15)	C13—C8—C9—C10	−1.4 (5)
Cl1—Cu—N1—C1	58.1 (2)	C7—C8—C9—C10	−175.5 (3)
N2—Cu—N1—C7	−140.32 (18)	C8—C9—C10—C11	2.0 (6)
Cl2—Cu—N1—C7	63.51 (17)	C9—C10—C11—C12	−1.7 (6)
Cl1—Cu—N1—C7	−59.0 (2)	C10—C11—C12—C13	0.8 (6)
N1—Cu—N2—C6	−1.8 (2)	C11—C12—C13—C8	−0.3 (6)
Cl2—Cu—N2—C6	96.1 (3)	C9—C8—C13—C12	0.5 (5)
Cl1—Cu—N2—C6	−154.94 (19)	C7—C8—C13—C12	174.8 (3)
N1—Cu—N2—C21	−132.2 (2)	C1—N1—C14—C15	59.0 (4)
Cl2—Cu—N2—C21	−34.3 (3)	C7—N1—C14—C15	179.6 (3)
Cl1—Cu—N2—C21	74.7 (2)	Cu—N1—C14—C15	−62.0 (3)
C14—N1—C1—C2	45.3 (3)	N1—C14—C15—C20	−114.2 (4)
C7—N1—C1—C2	−71.3 (3)	N1—C14—C15—C16	71.3 (4)
Cu—N1—C1—C2	173.0 (2)	C20—C15—C16—C17	3.5 (5)
C14—N1—C1—C6	−82.8 (3)	C14—C15—C16—C17	178.0 (3)
C7—N1—C1—C6	160.6 (2)	C15—C16—C17—C18	−2.5 (6)
Cu—N1—C1—C6	44.9 (2)	C16—C17—C18—C19	−0.1 (8)
N1—C1—C2—C3	171.8 (3)	C17—C18—C19—C20	1.7 (8)
C6—C1—C2—C3	−60.1 (3)	C18—C19—C20—C15	−0.7 (8)
C1—C2—C3—C4	59.6 (4)	C16—C15—C20—C19	−1.9 (6)
C2—C3—C4—C5	−57.4 (4)	C14—C15—C20—C19	−176.5 (4)
C3—C4—C5—C6	55.2 (4)	C6—N2—C21—C22	57.9 (4)
C21—N2—C6—C5	−86.4 (3)	Cu—N2—C21—C22	−175.2 (3)
Cu—N2—C6—C5	147.6 (2)	N2—C21—C22—C23	78.9 (4)
C21—N2—C6—C1	152.6 (3)	N2—C21—C22—C27	−100.0 (4)
Cu—N2—C6—C1	26.6 (3)	C27—C22—C23—C24	0.3 (5)
C4—C5—C6—N2	−174.6 (3)	C21—C22—C23—C24	−178.6 (3)
C4—C5—C6—C1	−54.3 (4)	C22—C23—C24—C25	0.4 (6)
N1—C1—C6—N2	−48.7 (3)	C23—C24—C25—C26	−1.8 (6)
C2—C1—C6—N2	−179.7 (2)	C24—C25—C26—C27	2.4 (6)
N1—C1—C6—C5	−171.9 (2)	C25—C26—C27—C22	−1.7 (6)
C2—C1—C6—C5	57.1 (3)	C23—C22—C27—C26	0.3 (5)
C14—N1—C7—C8	−177.7 (3)	C21—C22—C27—C26	179.2 (3)

Experimental details

Crystal data
Chemical formula	[CuCl₂(C₂₇H₃₂N₂)]
M_r	519.00
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	10.5806 (7), 15.4409 (8), 16.2579 (12)
V (Å³)	2656.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.40 × 0.40 × 0.40

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	Analytical (ABSCALC; McArdle & Daly, 1999)
T_min, T_max	0.660, 0.666
No. of measured, independent and observed [I > 2σ(I)] reflections	5793, 4931, 3885
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.605

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.06
No. of reflections	4931
No. of parameters	292
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.24
Absolute structure	Flack (1983)
Absolute structure parameter	−0.017 (13)

Computer programs: CAD4 (Enraf–Nonius, 1989), XCAD (McArdle, 1999), SHELXS97 (Sheldrick, 2008), SHELXS97 [SHELXL97?] (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), WinGX (Farrugia, 1999).

Acknowledgements

This research was supported by Kyungpook National University Research Fund, 2008.

References

Alexakis, A., Chauvin, A. S., Stouvenel, R., Vrancken, E., Mutti, S. & Mangeney, P. (2001). Tetrahedron: Asymmetry, 12, 1171–1178. Web of Science CrossRef CAS Google Scholar
Arjan, H., Boyd, E., Coumbarides, G. S., Eames, J., Jones, R. V. H., Stenson, R. A. & Suggate, M. J. (2005). Tetrahedron Lett. 46, 1921–1925. Web of Science CrossRef CAS Google Scholar
Boyd, E., Coumbarides, G. S., Eames, J., Jones, R. V. H., Motevalli, M., Stenson, R. A. & Suggate, M. J. (2006). J. Chem. Crystallogr. 36, 263–269. Web of Science CSD CrossRef CAS Google Scholar
Boyd, E., Coumbarides, G. S., Eames, J., Jones, R. V. H., Stenson, R. A. & Suggate, M. J. (2005). Tetrahedron Lett. 46, 3479–3484. Web of Science CrossRef CAS Google Scholar
Brethon, A., Moreau, J. J. E. & Man, M. W. C. (2004). Tetrahedron: Asymmetry, 15, 495–502. Web of Science CrossRef CAS Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Evans, D. A., Mito, S. & Seidel, D. (2007). J. Am. Chem. Soc. 129, 11583–11592. Web of Science CSD CrossRef PubMed CAS Google Scholar
Evans, D. A. & Seidel, D. (2005). J. Am. Chem. Soc. 127, 9958–9959. Web of Science CSD CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Jones, M. D. & Mahon, M. F. (2008). J. Organomet. Chem. 693, 2377–2382. Web of Science CSD CrossRef CAS Google Scholar
McArdle, P. (1999). XCAD. National University of Ireland, Galway, Ireland. Google Scholar
McArdle, P. & Daly, P. (1999). ABSCALC. National University of Ireland, Galway, Ireland. Google Scholar
Nguyen, Q. T. & Jeong, J. H. (2008a). Bull. Korean Chem. Soc. 29, 483–486. CAS Google Scholar
Nguyen, Q. T. & Jeong, J. H. (2008b). Polyhedron, 27, 3227–3230. Web of Science CSD CrossRef CAS Google Scholar
Roh, S. G., Yoon, J. U. & Jeong, J. H. (2004). Polyhedron, 23, 2063–2067. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tye, H., Eldred, C. & Wills, M. (2002). Tetrahedron Lett. 43, 155–158. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.