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Acta Cryst. (2007). E63, m2042    [ doi:10.1107/S1600536807031467 ]

Diaquabis(N-ethyl-N',N'-dimethylethylenediamine-[kappa]2N,N')nickel(II) dichloride

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

Abstract top

In the title compound, [Ni(C6H16N2)2(H2O)2]Cl2, the NiII cation (site symmetry \overline{1}) is coordinated by two N,N-bidentate ligands and two water molecules, resulting in a slightly distorted trans-NiO2N4 octahedron. The complex cations and chloride anions are linked by N-H...Cl and O-H...Cl hydrogen bonds into a chain.

Comment top

A number of nickel dichloride complexes of substituted ethylenediamines have been characterized by X-ray diffraction; these have the nickel atom chelated by two ligands. The octahedral geometry is completed by two water molecules. Such aquanickel salts are exemplified by the N,N-dimethylethylenediamine and N,N-diethylethylenediamine complexes (Ide & Norman, 2007; Ihara et al., 1991). The title compound, (I), shows a similar metal geometry (Fig. 1, Table 1). and the bite angle of the ligand is also similar to those found in such compounds. The components interact by way of N—H···Cl and O—H···Cl hydrogen bonds (Table 2).

Related literature top

For other nickel dichloride complexes of substituted ethylenediamines, see Ide & Norman (2007) and Ihara et al. (1991).

Experimental top

To an ethanol solution (5 ml) of nickel chloride hexahydrate (0.119 g, 0.5 mmol) was added an ethanol solution (5 ml) of N,N-dimethyl-N'-ethyl-ethylenediamine (1.6 ml, 1 mmol). The solution was filtered. Ether was diffused into the filtrate; light blue crystals of (I) were isolated after a week.

Refinement top

The C-bound hydrogen atoms were placed at calculated positions in the riding model approximation [C—H = 0.93–0.98 Å, U(H) = 1.2–1.5 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 and free refinement of their Uiso values.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); 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. View of part of a chain in (I) showing 50% displacement ellipsoids for the non-hydrogen atoms.
Diaquabis[N,N-dimethyl-N'-ethylethylenediamine-κ2N,N']nickel(II) dichloride top
Crystal data top
[Ni(C6H16N2)2(H2O)2]Cl2F(000) = 428
Mr = 398.06Dx = 1.366 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2782 reflections
a = 7.802 (1) Åθ = 2.6–27.5°
b = 12.550 (1) ŵ = 1.29 mm−1
c = 9.935 (1) ÅT = 295 K
β = 95.750 (1)°Block, light blue
V = 967.9 (2) Å30.20 × 0.20 × 0.15 mm
Z = 2
Data collection top
Bruker APEX CCD
diffractometer		2203 independent reflections
Radiation source: fine-focus sealed tube1843 reflections with I > 2σ(I)
graphiteRint = 0.019
φ and ω scansθmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.856, Tmax = 1.000k = −12→16
5912 measured reflectionsl = −12→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0399P)2 + 0.2921P]
where P = (Fo2 + 2Fc2)/3
2203 reflections(Δ/σ)max = 0.001
109 parametersΔρmax = 0.47 e Å−3
3 restraintsΔρmin = −0.35 e Å−3
Crystal data top
[Ni(C6H16N2)2(H2O)2]Cl2V = 967.9 (2) Å3
Mr = 398.06Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.802 (1) ŵ = 1.29 mm−1
b = 12.550 (1) ÅT = 295 K
c = 9.935 (1) Å0.20 × 0.20 × 0.15 mm
β = 95.750 (1)°
Data collection top
Bruker APEX CCD
diffractometer		2203 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1843 reflections with I > 2σ(I)
Tmin = 0.856, Tmax = 1.000Rint = 0.019
5912 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.078Δρmax = 0.47 e Å−3
S = 1.04Δρmin = −0.35 e Å−3
2203 reflectionsAbsolute structure: ?
109 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Ni10.50000.50000.50000.02374 (11)
Cl10.02304 (6)0.31615 (4)0.44701 (7)0.05183 (18)
O1W0.23497 (17)0.52469 (12)0.44802 (15)0.0353 (3)
N10.4525 (2)0.33584 (12)0.46081 (17)0.0303 (3)
N20.5432 (2)0.50319 (12)0.28146 (16)0.0340 (4)
C10.4882 (3)0.14532 (19)0.5352 (3)0.0565 (6)
H1A0.56750.09800.58540.085*
H1B0.46700.12060.44360.085*
H1C0.38180.14700.57600.085*
C20.5644 (3)0.25613 (15)0.5361 (2)0.0415 (5)
H2A0.58790.27960.62910.050*
H2B0.67340.25310.49710.050*
C30.4438 (3)0.32060 (16)0.3122 (2)0.0431 (5)
H3A0.32940.33870.27120.052*
H3B0.46550.24640.29220.052*
C40.5748 (3)0.38971 (18)0.2536 (2)0.0441 (5)
H4A0.68940.37010.29270.053*
H4B0.56890.37850.15670.053*
C50.6964 (3)0.5649 (2)0.2497 (2)0.0560 (6)
H5A0.70560.56220.15410.084*
H5B0.79810.53470.29730.084*
H5C0.68460.63760.27710.084*
C60.3960 (3)0.5413 (2)0.1889 (2)0.0508 (6)
H6A0.42610.53970.09760.076*
H6B0.36810.61300.21250.076*
H6C0.29830.49600.19660.076*
H1W10.170 (3)0.4708 (13)0.448 (3)0.055 (8)*
H1W20.177 (3)0.5738 (14)0.478 (2)0.056 (8)*
H1N0.3539 (16)0.3279 (16)0.486 (2)0.034 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.01999 (17)0.02258 (17)0.02879 (18)0.00071 (11)0.00310 (12)−0.00120 (12)
Cl10.0282 (3)0.0379 (3)0.0903 (5)−0.0015 (2)0.0104 (3)−0.0152 (3)
O1W0.0237 (7)0.0315 (8)0.0510 (9)0.0016 (6)0.0045 (6)−0.0039 (6)
N10.0249 (8)0.0259 (8)0.0403 (9)0.0000 (6)0.0038 (6)−0.0011 (6)
N20.0353 (9)0.0365 (9)0.0304 (8)−0.0016 (7)0.0047 (7)0.0004 (7)
C10.0533 (15)0.0329 (12)0.0823 (18)−0.0003 (10)0.0025 (13)0.0111 (11)
C20.0350 (11)0.0296 (10)0.0581 (14)0.0022 (8)−0.0045 (9)0.0015 (9)
C30.0523 (13)0.0337 (11)0.0427 (12)−0.0035 (9)0.0016 (10)−0.0100 (9)
C40.0495 (13)0.0461 (13)0.0377 (12)0.0050 (10)0.0099 (9)−0.0077 (9)
C50.0536 (14)0.0733 (18)0.0436 (13)−0.0183 (13)0.0171 (11)0.0022 (12)
C60.0577 (15)0.0583 (14)0.0351 (12)0.0045 (12)−0.0010 (10)0.0042 (10)
Geometric parameters (Å, °) top
Ni1—O1W2.103 (1)C1—H1B0.9600
Ni1—O1Wi2.103 (1)C1—H1C0.9600
Ni1—N12.122 (2)C2—H2A0.9700
Ni1—N1i2.122 (2)C2—H2B0.9700
Ni1—N22.231 (2)C3—C41.501 (3)
Ni1—N2i2.231 (2)C3—H3A0.9700
O1W—H1W10.84 (1)C3—H3B0.9700
O1W—H1W20.84 (1)C4—H4A0.9700
N1—C21.480 (2)C4—H4B0.9700
N1—C31.484 (3)C5—H5A0.9600
N1—H1N0.84 (1)C5—H5B0.9600
N2—C41.476 (3)C5—H5C0.9600
N2—C61.477 (3)C6—H6A0.9600
N2—C51.484 (3)C6—H6B0.9600
C1—C21.512 (3)C6—H6C0.9600
C1—H1A0.9600
O1Wi—Ni1—O1W180.0C2—C1—H1C109.5
O1Wi—Ni1—N192.95 (6)H1A—C1—H1C109.5
O1W—Ni1—N187.05 (6)H1B—C1—H1C109.5
O1Wi—Ni1—N1i87.05 (6)N1—C2—C1114.00 (17)
O1W—Ni1—N1i92.95 (6)N1—C2—H2A108.8
N1—Ni1—N1i180.0C1—C2—H2A108.8
O1Wi—Ni1—N290.05 (6)N1—C2—H2B108.8
O1W—Ni1—N289.95 (6)C1—C2—H2B108.8
N1—Ni1—N283.08 (6)H2A—C2—H2B107.6
N1i—Ni1—N296.92 (6)N1—C3—C4110.26 (16)
O1Wi—Ni1—N2i89.95 (6)N1—C3—H3A109.6
O1W—Ni1—N2i90.05 (6)C4—C3—H3A109.6
N1—Ni1—N2i96.92 (6)N1—C3—H3B109.6
N1i—Ni1—N2i83.08 (6)C4—C3—H3B109.6
N2—Ni1—N2i180.0H3A—C3—H3B108.1
Ni1—O1W—H1W1116.9 (18)N2—C4—C3110.61 (17)
Ni1—O1W—H1W2125.3 (17)N2—C4—H4A109.5
H1W1—O1W—H1W2104 (3)C3—C4—H4A109.5
C2—N1—C3112.42 (16)N2—C4—H4B109.5
C2—N1—Ni1118.68 (13)C3—C4—H4B109.5
C3—N1—Ni1107.30 (12)H4A—C4—H4B108.1
C2—N1—H1N106.3 (14)N2—C5—H5A109.5
C3—N1—H1N109.3 (15)N2—C5—H5B109.5
Ni1—N1—H1N102.1 (14)H5A—C5—H5B109.5
C4—N2—C6109.24 (17)N2—C5—H5C109.5
C4—N2—C5108.09 (17)H5A—C5—H5C109.5
C6—N2—C5106.93 (18)H5B—C5—H5C109.5
C4—N2—Ni1102.09 (12)N2—C6—H6A109.5
C6—N2—Ni1115.32 (13)N2—C6—H6B109.5
C5—N2—Ni1114.83 (13)H6A—C6—H6B109.5
C2—C1—H1A109.5N2—C6—H6C109.5
C2—C1—H1B109.5H6A—C6—H6C109.5
H1A—C1—H1B109.5H6B—C6—H6C109.5
O1Wi—Ni1—N1—C229.32 (15)N1i—Ni1—N2—C6−80.96 (15)
O1W—Ni1—N1—C2−150.68 (15)O1Wi—Ni1—N2—C5−42.98 (16)
N2—Ni1—N1—C2119.01 (15)O1W—Ni1—N2—C5137.02 (16)
N2i—Ni1—N1—C2−60.99 (15)N1—Ni1—N2—C5−135.94 (16)
O1Wi—Ni1—N1—C3−99.41 (13)N1i—Ni1—N2—C544.06 (16)
O1W—Ni1—N1—C380.59 (13)N2i—Ni1—N2—C5114 (100)
N2—Ni1—N1—C3−9.72 (13)C3—N1—C2—C1−72.2 (2)
N2i—Ni1—N1—C3170.28 (13)Ni1—N1—C2—C1161.47 (17)
O1Wi—Ni1—N2—C473.70 (13)C2—N1—C3—C4−94.2 (2)
O1W—Ni1—N2—C4−106.30 (13)Ni1—N1—C3—C438.0 (2)
N1—Ni1—N2—C4−19.27 (12)C6—N2—C4—C3−76.6 (2)
N1i—Ni1—N2—C4160.74 (12)C5—N2—C4—C3167.39 (18)
O1Wi—Ni1—N2—C6−168.00 (15)Ni1—N2—C4—C345.94 (19)
O1W—Ni1—N2—C612.00 (15)N1—C3—C4—N2−59.9 (2)
N1—Ni1—N2—C699.04 (15)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···Cl10.84 (1)2.26 (1)3.095 (2)174 (2)
O1W—H1W2···Cl1ii0.84 (1)2.26 (1)3.090 (2)169 (2)
N1—H1N···Cl10.84 (1)2.58 (1)3.349 (2)154 (2)
Symmetry codes: (ii) −x, −y+1, −z+1.
Table 1
Selected geometric parameters (Å) top
Ni1—O1W2.103 (1)Ni1—N22.231 (2)
Ni1—N12.122 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···Cl10.84 (1)2.26 (1)3.095 (2)174 (2)
O1W—H1W2···Cl1i0.84 (1)2.26 (1)3.090 (2)169 (2)
N1—H1N···Cl10.84 (1)2.58 (1)3.349 (2)154 (2)
Symmetry codes: (i) −x, −y+1, −z+1.
Acknowledgements top

The authors thank the Scientifc Research Foundation of Guangxi Normal University, the Science Foundation of Guangxi (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 (2004). or (2002). APEX2 (Version 1.22A) and SAINT (Version 7.12A). Bruker AXS Inc., Madison, Wisconsin, USA. Please check date; 2004 above.

Ide, D. M. M. & Norman, R. E. (2007). Acta Cryst. E63, m558–m560.

Ihara, Y., Satake, Y., Fujimoto, Y., Senda, H., Suzuki, M. & Uehara, A. (1991). Bull. Chem. Soc. Jpn, 61, 2349–2352.

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.