supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2471    [ doi:10.1107/S1600536807042675 ]

Dichlorido[N,N,N',N'-tetramethylcyclohexane-1,2-diamine-[kappa]2N,N']zinc(II)

N. Y. Lee, J. U. Yoon and J. H. Jeong

Abstract top

In the title compound, [ZnCl2(C10H22N2)], the ZnII ion coordinates to the N atoms of tetramethylcyclohexane-1,2-diamine and to two chloride ions in an approximately tetrahedral arrangement. The N-Zn-N and Cl-Zn-Cl planes are approximately orthogonal, with a dihedral angle of 89.7 (2)° between them. Four C atoms of the cyclohexane ring, together with their attached H atoms, are disordered equally over two sites.

Comment top

Chiral N,N,N',N'-tetramethylcycloheane-1,2-diamine has been used as enantioselective additive for the asymmetric addition of aryl or alkyl lithium to pro-chiral imines (Cabello et al., 2005; Kizirian et al., 2005). Crystal structures of zinc complexes containing non-macrocyclic cyclohexane- 1,2-diamine as ligand are very rare (Roh et al., 2004). Herein, we report the crystal structure of the ZnII complex bearing N,N,N',N'-tetramethylcycloheane-1,2-diamine and two chloride anions. The geometry around ZnII is a near tetrahedron while the Cu(II) complex bearing the same ligand has a distorted square-planar geometry (Pavlova et al., 2003). The angles between N—Zn—N and Cl—Zn—Cl planes are 89.7 (2)°.

Related literature top

For the use of tetramethylcyclohexane-1,2-diamine in asymmetric addition, see: Cabello et al. (2005); Kizirian et al. (2005). For related structures, see: Roh et al. (2004); Pavlova et al. (2003).

Experimental top

To a solution of ZnCl2 (0.084 g, 0.61 mmol) in THF (10 ml) was added dropwise a solution of trans-(1R,2R)- N,N,N',N'-tetramethylcycloheane-1,2-diamine (0.93 g, 0.61 mmol) in THF (10 ml). The mixture was stirred for 2 days at room temperature. The solvent was removed and the residue was washed with ether to give a white solid. Colorless crystals was obtained from methanol solution. Yield; 1.40 g (75%). Anal. Calcd. for C10H22Cl2N2Zn: C, 39.18; H, 7.23; N, 9.14. Found: C, 39.15; H, 7.24; N, 9.10%. 1H NMR (CDCl3); δ 2.45(m, 4H, CHDA), 2.08(m, 2H, CHDA), 1.86(m, 2H, CHDA), 1.25(m, 1H, CHDA), 1.13(m, 1H, CHDA). 2.27(s, 12H, CH3).

Refinement top

The C3, C5, C6 and C8 carbon atoms of the cyclohexane ring are disordered over two positions. They were refined isotropically at half occupancies. All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.98 Å, Uiso = 1.2Ueq (C) for CH, 0.97 Å, Uiso = 1.2Ueq (C) for CH2 and 0.96 Å, Uiso = 1.5Ueq (C) for CH3 atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD (McArdle, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEXIII (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. A view of Dichloro[trans-(1R,2R)-N,N,N',N'-tetramethylcyclohexane- 1,2-diamine-κ2N·N']zinc(II). Displacement ellipsoids are drawn at the 40% probability level. Hydrogen atoms at methyl groups are omitted for clarity.
Dichlorido[N,N,N',N'-tetramethylcyclohexane-1,2-diamine-κ2N,N']zinc(II) top
Crystal data top
[ZnCl2(C10H22N2)]F000 = 640
Mr = 306.59Dx = 1.406 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 8.2566 (6) Åθ = 9.2–13.3º
b = 14.1915 (13) ŵ = 2.04 mm−1
c = 12.9584 (9) ÅT = 293 (2) K
β = 107.504 (6)ºBlock, colorless
V = 1448.1 (2) Å30.40 × 0.40 × 0.35 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4 four-circle
diffractometer		Rint = 0.011
Radiation source: fine-focus sealed tubeθmax = 25.5º
Monochromator: graphiteθmin = 2.2º
T = 293(2) Kh = −9→9
scintillation counter scansk = −17→0
Absorption correction: ψ scan
(ABSCALC; McArdle & Daly, 1999)		l = 0→15
Tmin = 0.46, Tmax = 0.493 standard reflections
2918 measured reflections every 60 min
2687 independent reflections intensity decay: 0.2%
2388 reflections with I > 2σ(I)
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.067H-atom parameters constrained
wR(F2) = 0.159  w = 1/[σ2(Fo2) + (0.0001P)2 + 8.9534P]
where P = (Fo2 + 2Fc2)/3
S = 1.28(Δ/σ)max < 0.001
2687 reflectionsΔρmax = 0.45 e Å−3
132 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[ZnCl2(C10H22N2)]V = 1448.1 (2) Å3
Mr = 306.59Z = 4
Monoclinic, P21/nMo Kα
a = 8.2566 (6) ŵ = 2.04 mm−1
b = 14.1915 (13) ÅT = 293 (2) K
c = 12.9584 (9) Å0.40 × 0.40 × 0.35 mm
β = 107.504 (6)º
Data collection top
Enraf–Nonius CAD-4 four-circle
diffractometer		2388 reflections with I > 2σ(I)
Absorption correction: ψ scan
(ABSCALC; McArdle & Daly, 1999)		Rint = 0.011
Tmin = 0.46, Tmax = 0.493 standard reflections
2918 measured reflections every 60 min
2687 independent reflections intensity decay: 0.2%
Refinement top
R[F2 > 2σ(F2)] = 0.067132 parameters
wR(F2) = 0.159H-atom parameters constrained
S = 1.28Δρmax = 0.45 e Å−3
2687 reflectionsΔρmin = −0.49 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn0.24797 (10)0.14548 (6)0.43395 (6)0.0467 (3)
Cl10.2396 (3)0.07751 (16)0.58652 (15)0.0690 (6)
Cl20.4590 (3)0.24418 (18)0.4487 (2)0.0833 (8)
N10.0079 (7)0.1968 (4)0.3495 (5)0.0476 (14)
N20.2142 (8)0.0459 (5)0.3122 (5)0.0562 (16)
C1−0.0956 (11)0.2038 (8)0.4228 (8)0.089 (3)
H1A−0.04990.25170.47590.106*
H1B−0.09490.14440.45850.106*
H1C−0.21010.21980.38240.106*
C20.0250 (13)0.2904 (6)0.3069 (10)0.099 (4)
H2A0.10000.28720.26300.119*
H2B0.07080.33320.36590.119*
H2C−0.08450.31240.26390.119*
C3−0.0397 (18)0.1419 (11)0.2458 (12)0.049 (3)*0.50
H30.00880.17440.19520.059*0.50
C3'−0.0814 (17)0.1143 (10)0.2794 (11)0.040 (3)*0.50
H3'−0.10850.06660.32630.048*0.50
C4−0.2412 (9)0.1412 (6)0.1940 (7)0.067 (2)
H4A−0.29540.11210.24280.080*
H4B−0.28460.20470.17790.080*
C5−0.273 (3)0.0825 (16)0.0888 (18)0.087 (6)*0.50
H5A−0.39130.06410.07080.105*0.50
H5B−0.26760.12820.03430.105*0.50
C5'−0.330 (2)0.0612 (12)0.1266 (14)0.060 (4)*0.50
H5C−0.39880.08520.05720.072*0.50
H5D−0.40620.03220.16170.072*0.50
C6−0.211 (3)0.0220 (16)0.0704 (17)0.073 (5)*0.50
H6A−0.19290.03260.00070.088*0.50
H6B−0.2887−0.03070.06170.088*0.50
C6'−0.204 (3)−0.0172 (17)0.1069 (19)0.087 (6)*0.50
H6C−0.2395−0.07700.12950.104*0.50
H6D−0.2240−0.02130.02930.104*0.50
C7−0.0311 (12)−0.0100 (7)0.1544 (7)0.075 (3)
H7A−0.0397−0.07600.17150.090*
H7B0.0549−0.00520.11750.090*
C80.033 (2)0.0454 (12)0.2630 (14)0.053 (4)*0.50
H8−0.01570.01420.31420.064*0.50
C8'0.0396 (18)0.0717 (11)0.2248 (13)0.045 (3)*0.50
H8'0.06420.12070.17830.054*0.50
C90.3344 (12)0.0601 (9)0.2507 (8)0.099 (4)
H9A0.32390.00950.20000.118*
H9B0.44800.06130.29940.118*
H9C0.31040.11890.21240.118*
C100.2425 (18)−0.0485 (7)0.3608 (10)0.117 (5)
H10A0.1814−0.09420.30890.140*
H10B0.2029−0.05020.42330.140*
H10C0.3616−0.06290.38190.140*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn0.0422 (4)0.0500 (5)0.0456 (5)−0.0030 (4)0.0101 (3)0.0028 (4)
Cl10.0779 (14)0.0781 (14)0.0414 (10)−0.0194 (11)0.0034 (9)0.0103 (9)
Cl20.0577 (13)0.0751 (15)0.119 (2)−0.0192 (11)0.0298 (13)0.0030 (14)
N10.044 (3)0.046 (3)0.048 (3)0.006 (3)0.007 (3)0.002 (3)
N20.053 (4)0.065 (4)0.057 (4)0.010 (3)0.026 (3)0.003 (3)
C10.061 (6)0.135 (10)0.076 (6)0.025 (6)0.029 (5)0.009 (6)
C20.090 (7)0.059 (6)0.138 (10)0.012 (5)0.016 (7)0.047 (6)
C40.048 (4)0.069 (5)0.069 (5)0.006 (4)−0.004 (4)0.010 (5)
C70.087 (7)0.075 (6)0.059 (5)−0.015 (5)0.018 (5)−0.022 (5)
C90.074 (6)0.153 (11)0.083 (7)−0.005 (7)0.046 (6)−0.028 (7)
C100.205 (15)0.053 (6)0.103 (9)0.016 (8)0.062 (9)−0.003 (6)
Geometric parameters (Å, °) top
Zn—N22.073 (7)C4—H4A0.9700
Zn—N12.086 (6)C4—H4B0.9700
Zn—Cl22.199 (2)C5—C61.06 (2)
Zn—Cl12.219 (2)C5—H5A0.9700
N1—C11.461 (10)C5—H5B0.9700
N1—C21.462 (10)C5'—C6'1.59 (3)
N1—C31.500 (15)C5'—H5C0.9700
N1—C3'1.528 (14)C5'—H5D0.9700
N2—C81.438 (16)C6—C71.62 (2)
N2—C91.462 (10)C6—H6A0.9700
N2—C101.468 (11)C6—H6B0.9700
N2—C8'1.585 (16)C6'—C71.38 (2)
C1—H1A0.9600C6'—H6C0.9700
C1—H1B0.9600C6'—H6D0.9700
C1—H1C0.9600C7—C8'1.482 (16)
C2—H2A0.9600C7—C81.559 (17)
C2—H2B0.9600C7—H7A0.9700
C2—H2C0.9600C7—H7B0.9700
C3—C81.49 (2)C8—H80.9800
C3—C41.596 (16)C8'—H8'0.9800
C3—H30.9800C9—H9A0.9600
C3'—C41.494 (14)C9—H9B0.9600
C3'—C8'1.513 (19)C9—H9C0.9600
C3'—H3'0.9800C10—H10A0.9600
C4—C5'1.485 (18)C10—H10B0.9600
C4—C51.55 (2)C10—H10C0.9600
N2—Zn—N187.1 (2)H4A—C4—H4B108.9
N2—Zn—Cl2114.97 (19)C6—C5—C4132 (2)
N1—Zn—Cl2115.24 (18)C6—C5—H5A104.3
N2—Zn—Cl1110.38 (19)C4—C5—H5A104.3
N1—Zn—Cl1109.88 (18)C6—C5—H5B104.3
Cl2—Zn—Cl1115.83 (10)C4—C5—H5B104.3
C1—N1—C2109.0 (8)H5A—C5—H5B105.6
C1—N1—C3124.9 (9)C4—C5'—C6'113.4 (14)
C2—N1—C399.4 (9)C4—C5'—H5C108.9
C1—N1—C3'99.6 (8)C6'—C5'—H5C108.9
C2—N1—C3'123.8 (8)C4—C5'—H5D108.9
C3—N1—C3'28.4 (6)C6'—C5'—H5D108.9
C1—N1—Zn109.4 (5)H5C—C5'—H5D107.7
C2—N1—Zn109.3 (5)C5—C6—C7119 (2)
C3—N1—Zn103.9 (6)C5—C6—H6A107.6
C3'—N1—Zn104.9 (6)C7—C6—H6A107.6
C8—N2—C9123.0 (10)C5—C6—H6B107.6
C8—N2—C10101.3 (10)C7—C6—H6B107.6
C9—N2—C10108.2 (8)H6A—C6—H6B107.0
C8—N2—C8'23.6 (7)C7—C6'—C5'120.9 (17)
C9—N2—C8'101.5 (8)C7—C6'—H6C107.1
C10—N2—C8'120.7 (9)C5'—C6'—H6C107.1
C8—N2—Zn103.0 (7)C7—C6'—H6D107.1
C9—N2—Zn111.2 (6)C5'—C6'—H6D107.1
C10—N2—Zn109.2 (6)H6C—C6'—H6D106.8
C8'—N2—Zn105.7 (6)C6'—C7—C8'119.7 (13)
N1—C1—H1A109.5C6'—C7—C8117.7 (13)
N1—C1—H1B109.5C8'—C7—C823.9 (7)
H1A—C1—H1B109.5C6'—C7—C626.3 (11)
N1—C1—H1C109.5C8'—C7—C6107.8 (11)
H1A—C1—H1C109.5C8—C7—C6117.4 (11)
H1B—C1—H1C109.5C6'—C7—H7A83.8
N1—C2—H2A109.5C8'—C7—H7A131.0
N1—C2—H2B109.5C8—C7—H7A108.0
H2A—C2—H2B109.5C6—C7—H7A108.0
N1—C2—H2C109.5C6'—C7—H7B126.8
H2A—C2—H2C109.5C8'—C7—H7B92.1
H2B—C2—H2C109.5C8—C7—H7B108.0
C8—C3—N1111.0 (12)C6—C7—H7B108.0
C8—C3—C4112.4 (12)H7A—C7—H7B107.2
N1—C3—C4109.8 (10)N2—C8—C3112.5 (13)
C8—C3—H3107.8N2—C8—C7115.4 (11)
N1—C3—H3107.8C3—C8—C7108.5 (13)
C4—C3—H3107.8N2—C8—H8106.7
C4—C3'—C8'108.4 (11)C3—C8—H8106.7
C4—C3'—N1113.9 (10)C7—C8—H8106.7
C8'—C3'—N1108.4 (10)C7—C8'—C3'114.1 (12)
C4—C3'—H3'108.7C7—C8'—N2111.3 (11)
C8'—C3'—H3'108.7C3'—C8'—N2110.2 (11)
N1—C3'—H3'108.7C7—C8'—H8'107.0
C5'—C4—C3'114.3 (10)C3'—C8'—H8'107.0
C5'—C4—C531.8 (9)N2—C8'—H8'107.0
C3'—C4—C5113.1 (11)N2—C9—H9A109.5
C5'—C4—C3121.4 (10)N2—C9—H9B109.5
C3'—C4—C327.6 (6)H9A—C9—H9B109.5
C5—C4—C3104.6 (11)N2—C9—H9C109.5
C5'—C4—H4A79.3H9A—C9—H9C109.5
C3'—C4—H4A83.5H9B—C9—H9C109.5
C5—C4—H4A110.8N2—C10—H10A109.5
C3—C4—H4A110.8N2—C10—H10B109.5
C5'—C4—H4B119.9H10A—C10—H10B109.5
C3'—C4—H4B125.7N2—C10—H10C109.5
C5—C4—H4B110.8H10A—C10—H10C109.5
C3—C4—H4B110.8H10B—C10—H10C109.5
N2—Zn—N1—C1128.6 (6)N1—C3—C4—C5−179.8 (12)
Cl2—Zn—N1—C1−115.1 (6)C5'—C4—C5—C6−90 (4)
Cl1—Zn—N1—C117.9 (6)C3'—C4—C5—C69(4)
N2—Zn—N1—C2−112.2 (6)C3—C4—C5—C637 (3)
Cl2—Zn—N1—C24.1 (7)C3'—C4—C5'—C6'−33.8 (19)
Cl1—Zn—N1—C2137.2 (6)C5—C4—C5'—C6'61 (2)
N2—Zn—N1—C3−6.8 (8)C3—C4—C5'—C6'−4(2)
Cl2—Zn—N1—C3109.5 (7)C4—C5—C6—C7−12 (4)
Cl1—Zn—N1—C3−117.4 (7)C4—C5'—C6'—C73(3)
N2—Zn—N1—C3'22.5 (7)C5'—C6'—C7—C8'0(3)
Cl2—Zn—N1—C3'138.8 (6)C5'—C6'—C7—C827 (3)
Cl1—Zn—N1—C3'−88.2 (7)C5'—C6'—C7—C6−69 (3)
N1—Zn—N2—C8−19.6 (9)C5—C6—C7—C6'103 (4)
Cl2—Zn—N2—C8−136.2 (8)C5—C6—C7—C8'−19 (3)
Cl1—Zn—N2—C890.5 (8)C5—C6—C7—C85(3)
N1—Zn—N2—C9113.9 (6)C9—N2—C8—C3−82.1 (16)
Cl2—Zn—N2—C9−2.6 (7)C10—N2—C8—C3157.2 (13)
Cl1—Zn—N2—C9−135.9 (6)C8'—N2—C8—C3−55 (2)
N1—Zn—N2—C10−126.7 (7)Zn—N2—C8—C344.3 (15)
Cl2—Zn—N2—C10116.8 (7)C9—N2—C8—C743.1 (18)
Cl1—Zn—N2—C10−16.5 (7)C10—N2—C8—C7−77.6 (14)
N1—Zn—N2—C8'4.6 (7)C8'—N2—C8—C770 (2)
Cl2—Zn—N2—C8'−112.0 (7)Zn—N2—C8—C7169.4 (10)
Cl1—Zn—N2—C8'114.7 (7)N1—C3—C8—N2−55.0 (18)
C1—N1—C3—C8−93.7 (14)C4—C3—C8—N2−178.4 (10)
C2—N1—C3—C8145.1 (12)N1—C3—C8—C7176.1 (10)
C3'—N1—C3—C8−63.3 (17)C4—C3—C8—C752.7 (17)
Zn—N1—C3—C832.4 (14)C6'—C7—C8—N2176.4 (15)
C1—N1—C3—C431.2 (15)C8'—C7—C8—N2−82 (2)
C2—N1—C3—C4−89.9 (11)C6—C7—C8—N2−153.9 (13)
C3'—N1—C3—C461.7 (16)C6'—C7—C8—C3−56 (2)
Zn—N1—C3—C4157.3 (8)C8'—C7—C8—C345 (2)
C1—N1—C3'—C479.6 (11)C6—C7—C8—C3−26.7 (19)
C2—N1—C3'—C4−41.1 (14)C6'—C7—C8'—C3'27 (2)
C3—N1—C3'—C4−75.5 (18)C8—C7—C8'—C3'−65 (2)
Zn—N1—C3'—C4−167.2 (8)C6—C7—C8'—C3'53.0 (17)
C1—N1—C3'—C8'−159.6 (11)C6'—C7—C8'—N2152.6 (15)
C2—N1—C3'—C8'79.7 (13)C8—C7—C8'—N261 (2)
C3—N1—C3'—C8'45.4 (16)C6—C7—C8'—N2178.4 (11)
Zn—N1—C3'—C8'−46.4 (12)C4—C3'—C8'—C7−56.2 (16)
C8'—C3'—C4—C5'60.1 (15)N1—C3'—C8'—C7179.6 (10)
N1—C3'—C4—C5'−179.1 (11)C4—C3'—C8'—N2177.7 (10)
C8'—C3'—C4—C525.3 (17)N1—C3'—C8'—N253.6 (14)
N1—C3'—C4—C5146.2 (12)C8—N2—C8'—C7−73 (2)
C8'—C3'—C4—C3−51.7 (16)C9—N2—C8'—C784.1 (12)
N1—C3'—C4—C369.2 (17)C10—N2—C8'—C7−35.4 (15)
C8—C3—C4—C5'−26.1 (19)Zn—N2—C8'—C7−159.7 (9)
N1—C3—C4—C5'−150.3 (12)C8—N2—C8'—C3'54 (2)
C8—C3—C4—C3'56.5 (17)C9—N2—C8'—C3'−148.3 (12)
N1—C3—C4—C3'−67.6 (16)C10—N2—C8'—C3'92.2 (13)
C8—C3—C4—C5−55.6 (17)Zn—N2—C8'—C3'−32.2 (13)
Table 1
Selected geometric parameters (Å, °) top
Zn—N22.073 (7)Zn—Cl22.199 (2)
Zn—N12.086 (6)Zn—Cl12.219 (2)
N2—Zn—N187.1 (2)N2—Zn—Cl1110.38 (19)
N2—Zn—Cl2114.97 (19)N1—Zn—Cl1109.88 (18)
N1—Zn—Cl2115.24 (18)Cl2—Zn—Cl1115.83 (10)
references
References top

Cabello, N., Kizirian, J.-C., Gille, S., Alexakis, A., Bernardinelli, G., Pinchard, L. & Caille, J.-C. (2005). Eur. J. Org. Chem. 22, 4835–4842.

Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands.

Kizirian, J.-C., Cabello, N., Pinchard, L., Caille, J.-C. & Alexakis, A. (2005). Tetrahedron, 61, 8939–8946.

McArdle, P. (1995). J. Appl. Cryst. 28, 65–?.

McArdle, P. (1999). XCAD. National University of Ireland, Galway, Ireland.

McArdle, P. & Daly, P. (1999). ABSCALC. National University of Ireland, Galway, Ireland.

Pavlova, S. V., Wen, Y.-S. & Chan, S. I. (2003). Acta Cryst. E59, m792–m793.

Roh, S. G., Yoon, J. U. & Jeong, J. H. (2004). Polyhedron, 23, 2063–2067.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.