supplementary materials


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

Acta Cryst. (2007). E63, m2228    [ doi:10.1107/S1600536807035386 ]

Diaqua(cyclohexane-1,2-diamine-[kappa]2N,N')(N,N,N',N'-tetramethylethylenediamine-[kappa]2N,N')nickel(II) dichloride dihydrate

Y.-Z. Zhang, Z.-L. Chen and S. W. Ng

Abstract top

In the title compound, [Ni(C6H14N2)(C6H16N2)(H2O)2]Cl2·2H2O, the cation lies about a twofold rotation axis. The octahedral complex cation is linked to the Cl- anions by hydrogen bonds to form a layer structure.

Comment top

The crystal structures of few diamine complexes of nickel have been reported; a recent study described the mixed-ligand diaqua complex of substituted ethylenediamines (Liang et al., 2007). The present mixed ligand complex also has coordinated water. The six-coordinate cation and free chloride anions are linked by hydrogen bonds into a layers structure.

Related literature top

For other nickel dichloride complexes of substituted ethylenediamines, see Liang et al. (2007).

Experimental top

To an ethanol solution (5 ml) of nickel chloride hexahydrate (0.238 g, 1 mmol) was added an ethanol solution (10 ml) of 1,2-diaminocyclohexane (0.12 ml, 1 mmol) and N,N,N',N'-tetramethyethylenediamine (0.15 ml, 1 mmol). The solution was filtered. Ether was diffused into the filtrate; blue crystals were isolated in 50% yield after a week.

Refinement top

Carbon-bound hydrogen atoms were placed at calculated positions in the riding model approximation [C—H 0.96 to 0.98 Å, U(H) = 1.2 or 1.5 Ueq(C)]. The water and amino H atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H = N–H = 0.85±0.01 Å.

The C–C bond in the ethylenediamine part of the molecule was restrained to 1.500±0.002 Å; a somewhat tight restraint was necessary.

Computing details top

Data collection: APEX2 (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot. The molecule lies about a twofold rotation axis, and the unlabeled atoms are related to the labeled ones by 1 - x, 1 - y, z.
Diaqua(cyclohexane-1,2-diamine-κ2N,N')(N,N,N',N'- tetramethylethylenediamine-κ2N,N')nickel(II) dichloride dihydrate top
Crystal data top
[Ni(C6H14N2)(C6H16N2)(H2O)2]Cl2·2H2OF(000) = 928
Mr = 432.07Dx = 1.353 Mg m−3
Orthorhombic, Aba2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2acCell parameters from 4527 reflections
a = 14.159 (1) Åθ = 2.7–27.4°
b = 9.843 (1) ŵ = 1.19 mm−1
c = 15.221 (1) ÅT = 295 K
V = 2121.4 (3) Å3Prism, blue
Z = 40.30 × 0.30 × 0.20 mm
Data collection top
Bruker APEX area-detector
diffractometer		2217 independent reflections
Radiation source: fine-focus sealed tube2103 reflections with I > 2σ(I)
graphiteRint = 0.015
φ and ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −18→16
Tmin = 0.702, Tmax = 0.797k = −12→8
6267 measured reflectionsl = −19→19
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)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073 w = 1/[σ2(Fo2) + (0.0479P)2 + 0.4568P]
where P = (Fo2 + 2Fc2)/3
S = 1.12(Δ/σ)max = 0.001
2217 reflectionsΔρmax = 0.50 e Å−3
129 parametersΔρmin = −0.37 e Å−3
11 restraintsAbsolute structure: Flack (1983), with 944 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.01 (1)
Crystal data top
[Ni(C6H14N2)(C6H16N2)(H2O)2]Cl2·2H2OV = 2121.4 (3) Å3
Mr = 432.07Z = 4
Orthorhombic, Aba2Mo Kα radiation
a = 14.159 (1) ŵ = 1.19 mm−1
b = 9.843 (1) ÅT = 295 K
c = 15.221 (1) Å0.30 × 0.30 × 0.20 mm
Data collection top
Bruker APEX area-detector
diffractometer		2217 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2103 reflections with I > 2σ(I)
Tmin = 0.702, Tmax = 0.797Rint = 0.015
6267 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073Δρmax = 0.50 e Å−3
S = 1.12Δρmin = −0.37 e Å−3
2217 reflectionsAbsolute structure: Flack (1983), with 944 Friedel pairs
129 parametersFlack parameter: −0.01 (1)
11 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.50000.49999 (2)0.02217 (10)
Cl10.31836 (4)0.83038 (6)0.61089 (9)0.05226 (16)
O1W0.49376 (9)0.71842 (15)0.5054 (2)0.0329 (3)
O2W0.63652 (17)0.8514 (2)0.5887 (2)0.0839 (10)
N10.4022 (2)0.49706 (13)0.60291 (18)0.0270 (5)
N20.3974 (2)0.49513 (15)0.3947 (2)0.0339 (6)
C10.45361 (14)0.4615 (2)0.68462 (15)0.0283 (4)
H10.46670.36380.68470.034*
C20.3966 (2)0.49752 (19)0.76682 (18)0.0408 (6)
H2A0.38040.59320.76540.049*
H2B0.33830.44570.76710.049*
C30.4519 (2)0.4673 (3)0.85041 (18)0.0520 (6)
H3A0.41640.49980.90070.062*
H3B0.45920.36970.85650.062*
C40.32382 (19)0.5997 (3)0.4023 (2)0.0580 (8)
H4A0.28090.59200.35370.087*
H4B0.35250.68810.40180.087*
H4C0.28990.58740.45630.087*
C50.3493 (2)0.3631 (3)0.3864 (2)0.0549 (7)
H5A0.30510.36680.33870.082*
H5B0.31640.34300.44000.082*
H5C0.39520.29340.37510.082*
C60.45062 (13)0.5269 (4)0.3154 (2)0.0640 (9)
H6A0.45290.62480.30840.077*
H6B0.41730.48990.26520.077*
H1W10.5390 (12)0.760 (3)0.5303 (18)0.062 (10)*
H1W20.4418 (10)0.748 (3)0.5284 (19)0.070 (11)*
H2W10.6916 (15)0.818 (4)0.589 (5)0.17 (3)*
H2W20.638 (3)0.9368 (10)0.587 (3)0.103 (14)*
H1N10.3817 (15)0.5779 (11)0.6136 (18)0.035 (6)*
H1N20.3567 (14)0.4420 (18)0.609 (3)0.068 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01982 (15)0.02320 (15)0.02349 (15)0.00020 (10)0.0000.000
Cl10.0385 (3)0.0394 (3)0.0788 (4)0.0064 (2)0.0048 (3)−0.0112 (3)
O1W0.0306 (6)0.0288 (6)0.0393 (9)0.0005 (5)0.0005 (7)0.0019 (10)
O2W0.0492 (11)0.0482 (11)0.154 (3)−0.0034 (10)−0.0260 (14)−0.0254 (14)
N10.0215 (12)0.0280 (11)0.0313 (13)−0.0018 (5)0.0014 (11)−0.0013 (6)
N20.0307 (14)0.0373 (13)0.0338 (15)−0.0002 (6)−0.0075 (13)−0.0009 (6)
C10.0297 (11)0.0261 (8)0.0290 (10)−0.0011 (9)0.0014 (9)0.0009 (9)
C20.0420 (14)0.0450 (13)0.0354 (13)0.0001 (7)0.0129 (11)−0.0014 (9)
C30.0686 (19)0.0550 (13)0.0325 (12)0.0040 (14)0.0104 (12)0.0025 (11)
C40.0478 (14)0.0505 (14)0.0756 (19)0.0168 (11)−0.0311 (14)−0.0161 (13)
C50.0621 (15)0.0419 (12)0.0608 (15)−0.0105 (11)−0.0321 (14)−0.0009 (11)
C60.060 (2)0.097 (2)0.0350 (16)0.0045 (17)−0.0107 (15)0.0078 (15)
Geometric parameters (Å, °) top
Ni1—N1i2.091 (3)C1—C21.530 (3)
Ni1—N12.091 (3)C1—H10.9800
Ni1—O1Wi2.153 (2)C2—C31.523 (4)
Ni1—N2i2.163 (3)C2—H2A0.9700
Ni1—N22.163 (3)C2—H2B0.9700
Ni1—O1W2.153 (2)C3—C3i1.506 (7)
O1W—H1W10.850 (10)C3—H3A0.9700
O1W—H1W20.865 (10)C3—H3B0.9700
O2W—H2W10.846 (10)C4—H4A0.9600
O2W—H2W20.841 (10)C4—H4B0.9600
N1—C11.483 (4)C4—H4C0.9600
N1—H1N10.862 (9)C5—H5A0.9600
N1—H1N20.847 (10)C5—H5B0.9600
N2—C61.457 (4)C5—H5C0.9600
N2—C41.470 (3)C6—C6i1.496 (2)
N2—C51.473 (3)C6—H6A0.9700
C1—C1i1.516 (4)C6—H6B0.9700
N1i—Ni1—N182.98 (15)N1—C1—H1109.0
N1i—Ni1—O1Wi87.59 (7)C1i—C1—H1109.0
N1—Ni1—O1Wi89.12 (7)C2—C1—H1109.0
N1i—Ni1—O1W89.12 (7)C3—C2—C1111.5 (2)
N1—Ni1—O1W87.59 (7)C3—C2—H2A109.3
O1Wi—Ni1—O1W175.61 (16)C1—C2—H2A109.3
N1i—Ni1—N2i96.31 (6)C3—C2—H2B109.3
N1—Ni1—N2i179.15 (13)C1—C2—H2B109.3
O1Wi—Ni1—N2i91.32 (8)H2A—C2—H2B108.0
O1W—Ni1—N2i91.94 (7)C3i—C3—C2112.41 (18)
N1i—Ni1—N2179.15 (12)C3i—C3—H3A109.1
N1—Ni1—N296.31 (6)C2—C3—H3A109.1
O1Wi—Ni1—N291.94 (7)C3i—C3—H3B109.1
O1W—Ni1—N291.32 (8)C2—C3—H3B109.1
N2i—Ni1—N284.41 (16)H3A—C3—H3B107.9
Ni1—O1W—H1W1118 (2)N2—C4—H4A109.5
Ni1—O1W—H1W2113 (2)N2—C4—H4B109.5
H1W1—O1W—H1W2107.3 (16)H4A—C4—H4B109.5
H2W1—O2W—H2W2111.4 (18)N2—C4—H4C109.5
C1—N1—Ni1107.83 (18)H4A—C4—H4C109.5
C1—N1—H1N1103.0 (19)H4B—C4—H4C109.5
Ni1—N1—H1N1110.5 (16)N2—C5—H5A109.5
C1—N1—H1N297 (3)N2—C5—H5B109.5
Ni1—N1—H1N2127 (2)H5A—C5—H5B109.5
H1N1—N1—H1N2108.3 (15)N2—C5—H5C109.5
C6—N2—C4106.3 (2)H5A—C5—H5C109.5
C6—N2—C5110.9 (3)H5B—C5—H5C109.5
C4—N2—C5107.3 (3)N2—C6—C6i114.0 (2)
C6—N2—Ni1105.19 (19)N2—C6—H6A108.7
C4—N2—Ni1113.75 (19)C6i—C6—H6A108.7
C5—N2—Ni1113.20 (17)N2—C6—H6B108.7
N1—C1—C1i107.93 (16)C6i—C6—H6B108.7
N1—C1—C2111.8 (2)H6A—C6—H6B107.6
C1i—C1—C2109.96 (16)
N1i—Ni1—N1—C1−14.97 (10)N1—Ni1—N2—C5−71.0 (2)
O1Wi—Ni1—N1—C172.71 (13)O1Wi—Ni1—N2—C518.3 (2)
O1W—Ni1—N1—C1−104.38 (13)O1W—Ni1—N2—C5−158.7 (2)
N2—Ni1—N1—C1164.56 (12)N2i—Ni1—N2—C5109.5 (2)
N1—Ni1—N2—C6167.72 (18)Ni1—N1—C1—C1i41.8 (2)
O1Wi—Ni1—N2—C6−102.95 (18)Ni1—N1—C1—C2162.90 (13)
O1W—Ni1—N2—C680.00 (19)N1—C1—C2—C3−177.1 (2)
N2i—Ni1—N2—C6−11.82 (16)C1i—C1—C2—C3−57.3 (3)
N1—Ni1—N2—C451.8 (2)C1—C2—C3—C3i53.0 (3)
O1Wi—Ni1—N2—C4141.1 (2)C4—N2—C6—C6i155.4 (4)
O1W—Ni1—N2—C4−35.9 (2)C5—N2—C6—C6i−88.3 (5)
N2i—Ni1—N2—C4−127.8 (2)Ni1—N2—C6—C6i34.5 (5)
Symmetry codes: (i) −x+1, −y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2W0.85 (1)1.87 (1)2.721 (3)178 (3)
O1W—H1W2···Cl10.87 (1)2.30 (1)3.156 (2)170 (3)
O2W—H2W1···Cl1ii0.85 (1)2.34 (2)3.153 (2)162 (5)
O2W—H2W2···Cl1iii0.84 (1)2.40 (2)3.215 (2)163 (4)
N1—H1N1···Cl10.86 (1)2.64 (1)3.4910 (17)168 (3)
N1—H1N2···Cl1iv0.85 (1)2.71 (1)3.529 (3)163 (3)
Symmetry codes: (ii) x+1/2, −y+3/2, z; (iii) −x+1, −y+2, z; (iv) −x+1/2, y−1/2, z.
Table 1
Selected geometric parameters (Å) top
Ni1—N12.091 (3)Ni1—O1W2.153 (2)
Ni1—N22.163 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O2W0.85 (1)1.87 (1)2.721 (3)178 (3)
O1W—H1W2···Cl10.87 (1)2.30 (1)3.156 (2)170 (3)
O2W—H2W1···Cl1i0.85 (1)2.34 (2)3.153 (2)162 (5)
O2W—H2W2···Cl1ii0.84 (1)2.40 (2)3.215 (2)163 (4)
N1—H1N1···Cl10.86 (1)2.64 (1)3.4910 (17)168 (3)
N1—H1N2···Cl1iii0.85 (1)2.71 (1)3.529 (3)163 (3)
Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) −x+1, −y+2, z; (iii) −x+1/2, y−1/2, z.
Acknowledgements top

The authors thank the Scientific Research Foundation of Guangxi Normal University, the Science Foundation of Guangxi Province, China (grant No. 0542021) and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem., 1, 189–191.

Bruker (2002). APEX2 (Version 1.22A) and SAINT (Version 7.12A). Bruker AXS Inc., Madison, Winconsin, USA. [Please check year - 2002 here, but originally 2004 in computing section]

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Liang, Y.-N., Chen, Z.-L., Zhang, Y.-Z. & Ng, S. W. (2007). Acta Cryst. E63, m2042–?.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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

Westrip, S. P. (2007). publCIF. In preparation.