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Acta Cryst. (2007). E63, m2148    [ doi:10.1107/S1600536807033788 ]

catena-Poly[N-methylmorpholinium [nickelate(II)-tri-[mu]-chlorido]]

M. M. Turnbull

Abstract top

The structure of the title complex, {(C5H12NO)[NiCl3]}n, shows pseudo-octahedral geometry about the NiII ions with discrete N-methylmorpholinium cations. The cation has mirror symmetry; Ni and one Cl atom also lie on a mirror plane. The Ni atoms are linked via bridging Cl ions into a linear chain parallel to the a axis. The bridging Cl ions create a pseudo-octahedral geometry about each Ni atom with a Jahn-Teller compression. Bifurcated N-H...Cl hydrogen bonding occurs between the cations and anions.

Comment top

The Ni(II) ions in (I), Fig. 1, exhibit a Jahn-Teller compression with two pairs of longer (2.448 (2) Å and 2.437 (2) Å) and one pair of shorter Ni—Cl bonds (2.346 (2) Å) in their octahedral Cl6 environments. The Cl ions bridge Ni(II) ions to form tri-bridged chains parallel to the a-axis (Fig. 2). This type of trichloride-bridged chain has been previously reported for the tetramethylammonium (Stucky, 1968) and methylphenylethylammonium (Harlow and Simonsen, 1977) salts, although neither complex exhibits the Jahn-Teller distortion seen here. The methylammonium salt is also a tri-bridged chain, but which shows a typical Jahn-Teller elongation (Willett, 1966).

The N-methylmorpholinium ions pack in stacks parallel to the c-axis surrounding the chains and isolating them from each other. Bifurcated hydrogen bonds between the morpholinium N—H proton and Cl2 help stabilize the crystal structure (Fig. 2).

Related literature top

For related literature see: Harlow & Simonsen (1977); Stucky (1968); Willett (1966).

Experimental top

The complex was prepared from a solution of one equivalent of NiCl2 and two equivalents of N-methylmorpholine in 1 M HCl(aq). The solution was allowed to evaporate in air until a viscous syrup resulted whereupon it was transferred to a desiccator. After one week, green crystals of (N-methylmorpholinium)3ClNiCl4 grew along with yellow crystals of (I). The crystals are highly hygroscopic. Crystals were transferred in a drop of the mother liquor and then moved directly into an adjacent drop of fluorocarbon oil without exposure to the air. No attempt was made to maximize the yield.

Refinement top

N—H atom was freely refined (N—H = 0.85 (6) Å. The C-bound H atoms were included in the riding model approximation with C—H = 0.96 Å, and with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: XSCANS (Siemens, 1992); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1990); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of the N-methylmorpholinium cation (the cation has mirror symmetry) and the coordination sphere for the Ni cation (the Ni and Cl1 atoms lie on a mirror plane). Symmetry operations A: x - 1/2, y, 0.5 - z; B: x, 0.5 - y, z and C: x - 1/2, 0.5 - y, 0.5 - z.
[Figure 2] Fig. 2. Packing diagram of (I) viewed down the b-axis. Dotted lines represent hydrogen bonds.
catena-Poly[N-methylmorpholinium [nickelate(II)-tri-µ-chlorido]] top
Crystal data top
(C5H12NO)[NiCl3]F(000) = 544
Mr = 267.22Dx = 1.971 Mg m−3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 21 reflections
a = 6.119 (3) Åθ = 2.5–13.7°
b = 10.220 (6) ŵ = 2.99 mm−1
c = 14.401 (8) ÅT = 160 K
V = 900.6 (9) Å3Rod, yellow
Z = 40.40 × 0.10 × 0.10 mm
Data collection top
Siemens P4
diffractometer		888 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
graphiteθmax = 30.0°, θmin = 2.4°
ω scansh = −8→3
Absorption correction: ψ scan
(SHELXTL; Siemens, 1990)		k = −1→14
Tmin = 0.654, Tmax = 0.742l = −1→20
2281 measured reflections3 standard reflections every 97 reflections
1384 independent reflections intensity decay: 3.7%
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)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0431P)2]
where P = (Fo2 + 2Fc2)/3
1384 reflections(Δ/σ)max < 0.001
60 parametersΔρmax = 0.61 e Å−3
0 restraintsΔρmin = −0.98 e Å−3
Crystal data top
(C5H12NO)[NiCl3]V = 900.6 (9) Å3
Mr = 267.22Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 6.119 (3) ŵ = 2.99 mm−1
b = 10.220 (6) ÅT = 160 K
c = 14.401 (8) Å0.40 × 0.10 × 0.10 mm
Data collection top
Siemens P4
diffractometer		888 reflections with I > 2σ(I)
Absorption correction: ψ scan
(SHELXTL; Siemens, 1990)		Rint = 0.050
Tmin = 0.654, Tmax = 0.742θmax = 30.0°
2281 measured reflections3 standard reflections every 97 reflections
1384 independent reflections intensity decay: 3.7%
Refinement top
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.106Δρmax = 0.61 e Å−3
S = 1.02Δρmin = −0.98 e Å−3
1384 reflectionsAbsolute structure: ?
60 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni0.11686 (14)0.25000.25034 (5)0.01101 (17)
Cl1−0.1351 (2)0.25000.37571 (8)0.0147 (3)
Cl20.36888 (16)0.09476 (9)0.32313 (6)0.0131 (2)
N1−0.6499 (9)0.25000.5313 (3)0.0153 (10)
H1−0.641 (10)0.25000.473 (4)0.018*
C2−0.7788 (7)0.1295 (4)0.5539 (3)0.0161 (8)
H2A−0.68650.05290.54730.019*
H2B−0.89980.12110.51080.019*
C3−0.8655 (7)0.1365 (4)0.6519 (3)0.0189 (8)
H3A−0.95300.05940.66450.023*
H3B−0.74380.13700.69510.023*
O4−0.9946 (7)0.25000.6661 (3)0.0222 (10)
C7−0.4300 (10)0.25000.5764 (4)0.0199 (13)
H7A−0.44720.25000.64260.024*
H7B−0.35070.32670.55780.024*0.50
H7C−0.35070.17330.55780.024*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0094 (3)0.0142 (3)0.0095 (3)0.0000.0004 (3)0.000
Cl10.0113 (6)0.0233 (7)0.0096 (5)0.000−0.0013 (6)0.000
Cl20.0127 (4)0.0135 (4)0.0132 (4)0.0000 (4)0.0001 (4)0.0009 (3)
N10.015 (2)0.023 (2)0.0074 (19)0.0000.002 (2)0.000
C20.0182 (19)0.0114 (19)0.0186 (19)−0.0012 (17)−0.0048 (17)0.0011 (17)
C30.019 (2)0.0194 (19)0.0179 (18)−0.004 (2)0.0011 (19)0.0057 (15)
O40.016 (2)0.029 (3)0.022 (2)0.0000.0073 (19)0.000
C70.017 (3)0.025 (3)0.017 (3)0.0000.001 (2)0.000
Geometric parameters (Å, °) top
Ni—Cl1i2.3664 (18)C2—H2A0.9700
Ni—Cl12.3739 (19)C2—H2B0.9700
Ni—Cl2ii2.4371 (14)C3—O41.418 (5)
Ni—Cl22.4483 (14)C3—H3A0.9700
N1—C71.494 (8)C3—H3B0.9700
N1—C21.499 (5)C7—H7A0.9600
N1—H10.85 (6)C7—H7B0.9600
C2—C31.510 (6)C7—H7C0.9600
Cl1i—Ni—Cl1179.41 (7)C3—C2—H2A109.6
Cl1i—Ni—Cl2iii93.80 (5)N1—C2—H2B109.6
Cl1—Ni—Cl2ii85.75 (5)C3—C2—H2B109.6
Cl2iii—Ni—Cl2ii81.24 (6)H2A—C2—H2B108.1
Cl1i—Ni—Cl285.66 (5)O4—C3—C2111.7 (4)
Cl1—Ni—Cl294.78 (5)O4—C3—H3A109.3
Cl2iii—Ni—Cl298.99 (5)C2—C3—H3A109.3
Cl2ii—Ni—Cl2179.43 (5)O4—C3—H3B109.3
Cl2iv—Ni—Cl280.79 (6)C2—C3—H3B109.3
Niiii—Cl1—Ni80.39 (6)H3A—C3—H3B107.9
Nii—Cl2—Ni77.55 (5)C3iv—O4—C3109.8 (4)
C7—N1—C2112.3 (3)N1—C7—H7A109.5
C2—N1—C2iv110.5 (5)N1—C7—H7B109.5
C7—N1—H1112 (5)H7A—C7—H7B109.5
C2—N1—H1105 (2)N1—C7—H7C109.5
N1—C2—C3110.4 (4)H7A—C7—H7C109.5
N1—C2—H2A109.6H7B—C7—H7C109.5
Cl2iii—Ni—Cl1—Niiii−40.75 (3)Cl2iii—Ni—Cl2—Nii132.91 (5)
Cl2ii—Ni—Cl1—Niiii40.75 (3)Cl2iv—Ni—Cl2—Nii−46.57 (4)
Cl2iv—Ni—Cl1—Niiii139.44 (3)C7—N1—C2—C375.1 (5)
Cl2—Ni—Cl1—Niiii−139.44 (3)C2iv—N1—C2—C3−51.2 (6)
Cl1i—Ni—Cl2—Nii39.73 (3)N1—C2—C3—O456.8 (5)
Cl1—Ni—Cl2—Nii−140.65 (4)C2—C3—O4—C3iv−61.6 (5)
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x−1/2, −y+1/2, −z+1/2; (iii) x−1/2, y, −z+1/2; (iv) x, −y+1/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl2v0.85 (6)2.67 (5)3.393 (4)144 (1)
Symmetry codes: (v) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···Cl2i0.85 (6)2.67 (5)3.393 (4)144 (1)
Symmetry codes: (i) x−1, y, z.
Acknowledgements top

The author is grateful to the staff at the University of Canterbury for their hospitality during his sabbatical visit.

references
References top

Harlow, R. L. & Simonsen, S. H. (1977). Acta Cryst. B33, 3234–3237.

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

Siemens (1990). SHELXTL/PC. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Siemens (1992). XSCANS. Version 2.0. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Stucky, G. D. (1968). Acta Cryst. B24, 330–337.

Willett, R. D. (1966). J. Chem. Phys. 45, 3737–3740.