Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033788/tk2175sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033788/tk2175Isup2.hkl |
CCDC reference: 657583
Key indicators
- Single-crystal X-ray study
- T = 160 K
- Mean (C-C) = 0.006 Å
- R factor = 0.050
- wR factor = 0.106
- Data-to-parameter ratio = 23.1
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni (2) 2.05
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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.
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).
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).
For related literature see: Harlow & Simonsen (1977); Stucky (1968); Willett (1966).
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.
(C5H12NO)[NiCl3] | F(000) = 544 |
Mr = 267.22 | Dx = 1.971 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 21 reflections |
a = 6.119 (3) Å | θ = 2.5–13.7° |
b = 10.220 (6) Å | µ = 2.99 mm−1 |
c = 14.401 (8) Å | T = 160 K |
V = 900.6 (9) Å3 | Rod, yellow |
Z = 4 | 0.40 × 0.10 × 0.10 mm |
Siemens P4 diffractometer | 888 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 30.0°, θmin = 2.4° |
ω scans | h = −8→3 |
Absorption correction: ψ scan (SHELXTL; Siemens, 1990) | k = −1→14 |
Tmin = 0.654, Tmax = 0.742 | l = −1→20 |
2281 measured reflections | 3 standard reflections every 97 reflections |
1384 independent reflections | intensity decay: 3.7% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | H 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 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.98 e Å−3 |
(C5H12NO)[NiCl3] | V = 900.6 (9) Å3 |
Mr = 267.22 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 6.119 (3) Å | µ = 2.99 mm−1 |
b = 10.220 (6) Å | T = 160 K |
c = 14.401 (8) Å | 0.40 × 0.10 × 0.10 mm |
Siemens P4 diffractometer | 888 reflections with I > 2σ(I) |
Absorption correction: ψ scan (SHELXTL; Siemens, 1990) | Rint = 0.050 |
Tmin = 0.654, Tmax = 0.742 | 3 standard reflections every 97 reflections |
2281 measured reflections | intensity decay: 3.7% |
1384 independent reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.106 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.61 e Å−3 |
1384 reflections | Δρmin = −0.98 e Å−3 |
60 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni | 0.11686 (14) | 0.2500 | 0.25034 (5) | 0.01101 (17) | |
Cl1 | −0.1351 (2) | 0.2500 | 0.37571 (8) | 0.0147 (3) | |
Cl2 | 0.36888 (16) | 0.09476 (9) | 0.32313 (6) | 0.0131 (2) | |
N1 | −0.6499 (9) | 0.2500 | 0.5313 (3) | 0.0153 (10) | |
H1 | −0.641 (10) | 0.2500 | 0.473 (4) | 0.018* | |
C2 | −0.7788 (7) | 0.1295 (4) | 0.5539 (3) | 0.0161 (8) | |
H2A | −0.6865 | 0.0529 | 0.5473 | 0.019* | |
H2B | −0.8998 | 0.1211 | 0.5108 | 0.019* | |
C3 | −0.8655 (7) | 0.1365 (4) | 0.6519 (3) | 0.0189 (8) | |
H3A | −0.9530 | 0.0594 | 0.6645 | 0.023* | |
H3B | −0.7438 | 0.1370 | 0.6951 | 0.023* | |
O4 | −0.9946 (7) | 0.2500 | 0.6661 (3) | 0.0222 (10) | |
C7 | −0.4300 (10) | 0.2500 | 0.5764 (4) | 0.0199 (13) | |
H7A | −0.4472 | 0.2500 | 0.6426 | 0.024* | |
H7B | −0.3507 | 0.3267 | 0.5578 | 0.024* | 0.50 |
H7C | −0.3507 | 0.1733 | 0.5578 | 0.024* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0094 (3) | 0.0142 (3) | 0.0095 (3) | 0.000 | 0.0004 (3) | 0.000 |
Cl1 | 0.0113 (6) | 0.0233 (7) | 0.0096 (5) | 0.000 | −0.0013 (6) | 0.000 |
Cl2 | 0.0127 (4) | 0.0135 (4) | 0.0132 (4) | 0.0000 (4) | 0.0001 (4) | 0.0009 (3) |
N1 | 0.015 (2) | 0.023 (2) | 0.0074 (19) | 0.000 | 0.002 (2) | 0.000 |
C2 | 0.0182 (19) | 0.0114 (19) | 0.0186 (19) | −0.0012 (17) | −0.0048 (17) | 0.0011 (17) |
C3 | 0.019 (2) | 0.0194 (19) | 0.0179 (18) | −0.004 (2) | 0.0011 (19) | 0.0057 (15) |
O4 | 0.016 (2) | 0.029 (3) | 0.022 (2) | 0.000 | 0.0073 (19) | 0.000 |
C7 | 0.017 (3) | 0.025 (3) | 0.017 (3) | 0.000 | 0.001 (2) | 0.000 |
Ni—Cl1i | 2.3664 (18) | C2—H2A | 0.9700 |
Ni—Cl1 | 2.3739 (19) | C2—H2B | 0.9700 |
Ni—Cl2ii | 2.4371 (14) | C3—O4 | 1.418 (5) |
Ni—Cl2 | 2.4483 (14) | C3—H3A | 0.9700 |
N1—C7 | 1.494 (8) | C3—H3B | 0.9700 |
N1—C2 | 1.499 (5) | C7—H7A | 0.9600 |
N1—H1 | 0.85 (6) | C7—H7B | 0.9600 |
C2—C3 | 1.510 (6) | C7—H7C | 0.9600 |
Cl1i—Ni—Cl1 | 179.41 (7) | C3—C2—H2A | 109.6 |
Cl1i—Ni—Cl2iii | 93.80 (5) | N1—C2—H2B | 109.6 |
Cl1—Ni—Cl2ii | 85.75 (5) | C3—C2—H2B | 109.6 |
Cl2iii—Ni—Cl2ii | 81.24 (6) | H2A—C2—H2B | 108.1 |
Cl1i—Ni—Cl2 | 85.66 (5) | O4—C3—C2 | 111.7 (4) |
Cl1—Ni—Cl2 | 94.78 (5) | O4—C3—H3A | 109.3 |
Cl2iii—Ni—Cl2 | 98.99 (5) | C2—C3—H3A | 109.3 |
Cl2ii—Ni—Cl2 | 179.43 (5) | O4—C3—H3B | 109.3 |
Cl2iv—Ni—Cl2 | 80.79 (6) | C2—C3—H3B | 109.3 |
Niiii—Cl1—Ni | 80.39 (6) | H3A—C3—H3B | 107.9 |
Nii—Cl2—Ni | 77.55 (5) | C3iv—O4—C3 | 109.8 (4) |
C7—N1—C2 | 112.3 (3) | N1—C7—H7A | 109.5 |
C2—N1—C2iv | 110.5 (5) | N1—C7—H7B | 109.5 |
C7—N1—H1 | 112 (5) | H7A—C7—H7B | 109.5 |
C2—N1—H1 | 105 (2) | N1—C7—H7C | 109.5 |
N1—C2—C3 | 110.4 (4) | H7A—C7—H7C | 109.5 |
N1—C2—H2A | 109.6 | H7B—C7—H7C | 109.5 |
Cl2iii—Ni—Cl1—Niiii | −40.75 (3) | Cl2iii—Ni—Cl2—Nii | 132.91 (5) |
Cl2ii—Ni—Cl1—Niiii | 40.75 (3) | Cl2iv—Ni—Cl2—Nii | −46.57 (4) |
Cl2iv—Ni—Cl1—Niiii | 139.44 (3) | C7—N1—C2—C3 | 75.1 (5) |
Cl2—Ni—Cl1—Niiii | −139.44 (3) | C2iv—N1—C2—C3 | −51.2 (6) |
Cl1i—Ni—Cl2—Nii | 39.73 (3) | N1—C2—C3—O4 | 56.8 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl2v | 0.85 (6) | 2.67 (5) | 3.393 (4) | 144 (1) |
Symmetry code: (v) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | (C5H12NO)[NiCl3] |
Mr | 267.22 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 160 |
a, b, c (Å) | 6.119 (3), 10.220 (6), 14.401 (8) |
V (Å3) | 900.6 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.99 |
Crystal size (mm) | 0.40 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Siemens P4 |
Absorption correction | ψ scan (SHELXTL; Siemens, 1990) |
Tmin, Tmax | 0.654, 0.742 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2281, 1384, 888 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.106, 1.02 |
No. of reflections | 1384 |
No. of parameters | 60 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.61, −0.98 |
Computer programs: XSCANS (Siemens, 1992), XSCANS, SHELXTL (Siemens, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl2i | 0.85 (6) | 2.67 (5) | 3.393 (4) | 143.5 (9) |
Symmetry code: (i) x−1, y, z. |
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).