Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111050116/fg3235sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111050116/fg3235I_100Ksup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111050116/fg3235I_240Ksup3.hkl |
CCDC references: 862224; 862225
(n-C3H7NH3)Cl (5.0 g) was dissolved with NiCl2.6H2O at a 2:1 molar ratio in 6M HCl (40 ml) and the solution maintained at 333 K until a dark-red solid formed upon evaporation. Crystals of (I) cut from the solid mass are orange in color. Thermal analysis was performed using a TA Instruments Q200 DSC cooled by an RCS refrigeration system with a crystalline sample mass of 4.8 mg ramped between 183 and 313 K at a rate of 5.00 K min-1.
A series of structures from ambient temperature to 80 K were determined. Since the details of the 80, 100 and 120 K structures agree with only minor differences, the structure at 100 K alone is reported here. Likewise, the details of the 210 K, 240 K and ambient-temperature structures agree, including disorder of the n-propyl chains, so the 240 K structure alone is reported here.
H-atom positions were calculated using a riding model, with methyl C—H = 0.96, methylene C—H = 0.97 and ammonium N—H = 0.89 Å, with twofold disorder of –NH3 and –CH3 groups, and with Uiso(H) = 1.5Ueq(C, N). Bond lengths and angles within the organic cations conform to expected values (Ladd & Palmer, 1994). Low-angle reflections obscured by the beamstop (as indicated by F2o << F2c) were omitted from the refinement. Exceptions and details for the 100 and 240 K structures follow.
At 100 K, atom Cl1 and some of the C atoms exhibit elongated displacement ellipsoids parallel to a, suggesting disorder about the mirror plane. However, SHELXL97 (Sheldrick, 2008) did not recommend splitting the atom sites, and refinement of a disordered model only gave a modest improvement in R factors (wR = 0.051 against 104 parameters). Solution and refinement in the noncentrosymmetric space group C2ce yielded similar elongation of displacement ellipsoids. Hence, the ordered centrosymmetric model was retained. H atoms bound to N11 were calculated without disorder.
At 240 K, difference-map peaks near the central atoms, CX2 and CX3, of the propylammonium cations indicate a minor disordered component in which the orientation of these atoms is flipped. A common site-occupation factor [0.232 (8) for cation 1 and 0.128 (9) for cation 2] and a common isotropic displacement parameter were refined for the minor-conformation CX2 and CX3 atoms in each propylammonium chain. C—N and C—C bond lengths within the minor components were set at 1.50 Å with loose restraints.
For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
(C3H10N)4[Ni3Cl10] | Dx = 1.778 Mg m−3 |
Mr = 771.09 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmce | Cell parameters from 4076 reflections |
a = 6.9132 (1) Å | θ = 1.0–37.0° |
b = 23.9825 (2) Å | µ = 2.88 mm−1 |
c = 17.3695 (2) Å | T = 100 K |
V = 2879.79 (6) Å3 | Prism, orange |
Z = 4 | 0.25 × 0.19 × 0.16 mm |
F(000) = 1576 |
Nonius KappaCCD area-detector diffractometer | 3904 independent reflections |
Graphite monochromator | 3435 reflections with I > 2σ(I) |
Detector resolution: 9 pixels mm-1 | Rint = 0.043 |
CCD scans | θmax = 37.0°, θmin = 3.4° |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | h = 0→11 |
Tmin = 0.527, Tmax = 0.638 | k = 0→40 |
3904 measured reflections | l = 0→29 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.019P)2 + 4.7563P] where P = (Fo2 + 2Fc2)/3 |
3904 reflections | (Δ/σ)max = 0.001 |
85 parameters | Δρmax = 0.70 e Å−3 |
0 restraints | Δρmin = −1.10 e Å−3 |
(C3H10N)4[Ni3Cl10] | V = 2879.79 (6) Å3 |
Mr = 771.09 | Z = 4 |
Orthorhombic, Cmce | Mo Kα radiation |
a = 6.9132 (1) Å | µ = 2.88 mm−1 |
b = 23.9825 (2) Å | T = 100 K |
c = 17.3695 (2) Å | 0.25 × 0.19 × 0.16 mm |
Nonius KappaCCD area-detector diffractometer | 3904 independent reflections |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 3435 reflections with I > 2σ(I) |
Tmin = 0.527, Tmax = 0.638 | Rint = 0.043 |
3904 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.70 e Å−3 |
3904 reflections | Δρmin = −1.10 e Å−3 |
85 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) | |
Ni1 | 0.0000 | 0.437029 (7) | 0.150913 (10) | 0.01063 (4) | |
Ni2 | 0.0000 | 0.5000 | 0.0000 | 0.00910 (5) | |
Cl1 | 0.0000 | 0.340258 (14) | 0.16434 (2) | 0.01974 (7) | |
Cl2 | 0.2500 | 0.450502 (14) | 0.2500 | 0.01337 (6) | |
Cl3 | 0.0000 | 0.536300 (13) | 0.127854 (18) | 0.01294 (6) | |
Cl4 | 0.23670 (3) | 0.434124 (9) | 0.046224 (13) | 0.01319 (4) | |
N11 | 0.0000 | 0.34717 (5) | 0.34565 (7) | 0.0158 (2) | |
H11A | 0.0000 | 0.3555 | 0.2957 | 0.024* | |
H11B | 0.1051 | 0.3614 | 0.3677 | 0.024* | 0.50 |
H11C | −0.1051 | 0.3614 | 0.3677 | 0.024* | 0.50 |
C12 | 0.0000 | 0.28585 (7) | 0.35532 (10) | 0.0303 (4) | |
H12A | 0.1134 | 0.2705 | 0.3301 | 0.045* | 0.50 |
H12B | −0.1134 | 0.2705 | 0.3301 | 0.045* | 0.50 |
C13 | 0.0000 | 0.26829 (9) | 0.43810 (11) | 0.0302 (4) | |
H13A | −0.1135 | 0.2835 | 0.4634 | 0.045* | 0.50 |
H13B | 0.1135 | 0.2835 | 0.4634 | 0.045* | 0.50 |
C14 | 0.0000 | 0.20519 (10) | 0.44665 (16) | 0.0471 (7) | |
H14A | 0.0000 | 0.1956 | 0.5003 | 0.071* | 0.50 |
H14B | 0.1134 | 0.1901 | 0.4225 | 0.071* | 0.25 |
H14C | −0.1134 | 0.1901 | 0.4225 | 0.071* | 0.25 |
H14D | 0.0000 | 0.1882 | 0.3966 | 0.071* | 0.50 |
H14E | −0.1134 | 0.1938 | 0.4744 | 0.071* | 0.25 |
H14F | 0.1134 | 0.1938 | 0.4744 | 0.071* | 0.25 |
N21 | 0.5000 | 0.53121 (5) | 0.12649 (8) | 0.0192 (2) | |
H21A | 0.5000 | 0.5019 | 0.1579 | 0.029* | 0.50 |
H21B | 0.6051 | 0.5303 | 0.0969 | 0.029* | 0.25 |
H21C | 0.3949 | 0.5303 | 0.0969 | 0.029* | 0.25 |
H21D | 0.5000 | 0.5397 | 0.0766 | 0.029* | 0.50 |
H21E | 0.3949 | 0.5113 | 0.1376 | 0.029* | 0.25 |
H21F | 0.6051 | 0.5113 | 0.1376 | 0.029* | 0.25 |
C22 | 0.5000 | 0.58316 (8) | 0.17255 (10) | 0.0272 (4) | |
H22A | 0.3866 | 0.5837 | 0.2054 | 0.041* | 0.50 |
H22B | 0.6134 | 0.5837 | 0.2054 | 0.041* | 0.50 |
C23 | 0.5000 | 0.63269 (9) | 0.12407 (15) | 0.0597 (10) | |
H23A | 0.3865 | 0.6322 | 0.0912 | 0.090* | 0.50 |
H23B | 0.6135 | 0.6322 | 0.0912 | 0.090* | 0.50 |
C24 | 0.5000 | 0.68647 (10) | 0.1726 (2) | 0.0647 (10) | |
H24A | 0.5000 | 0.7183 | 0.1391 | 0.097* | 0.50 |
H24B | 0.6134 | 0.6873 | 0.2045 | 0.097* | 0.25 |
H24C | 0.3866 | 0.6873 | 0.2045 | 0.097* | 0.25 |
H24D | 0.5000 | 0.6770 | 0.2263 | 0.097* | 0.50 |
H24E | 0.3866 | 0.7080 | 0.1609 | 0.097* | 0.25 |
H24F | 0.6134 | 0.7080 | 0.1609 | 0.097* | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01414 (8) | 0.01036 (7) | 0.00738 (7) | 0.000 | 0.000 | 0.00029 (5) |
Ni2 | 0.00843 (9) | 0.01193 (10) | 0.00695 (9) | 0.000 | 0.000 | 0.00068 (7) |
Cl1 | 0.0368 (2) | 0.00980 (12) | 0.01261 (13) | 0.000 | 0.000 | −0.00047 (10) |
Cl2 | 0.01577 (13) | 0.01483 (12) | 0.00952 (11) | 0.000 | −0.00253 (10) | 0.000 |
Cl3 | 0.01896 (14) | 0.01166 (12) | 0.00820 (11) | 0.000 | 0.000 | −0.00013 (9) |
Cl4 | 0.01282 (9) | 0.01534 (9) | 0.01141 (8) | 0.00329 (7) | −0.00187 (7) | −0.00033 (7) |
N11 | 0.0194 (6) | 0.0140 (5) | 0.0141 (5) | 0.000 | 0.000 | 0.0002 (4) |
C12 | 0.0595 (14) | 0.0144 (6) | 0.0170 (7) | 0.000 | 0.000 | 0.0016 (5) |
C13 | 0.0415 (11) | 0.0301 (9) | 0.0190 (7) | 0.000 | 0.000 | 0.0089 (6) |
C14 | 0.0729 (19) | 0.0298 (10) | 0.0386 (12) | 0.000 | 0.000 | 0.0196 (9) |
N21 | 0.0260 (6) | 0.0135 (5) | 0.0181 (6) | 0.000 | 0.000 | −0.0010 (4) |
C22 | 0.0464 (11) | 0.0197 (7) | 0.0155 (6) | 0.000 | 0.000 | −0.0039 (5) |
C23 | 0.132 (3) | 0.0158 (8) | 0.0317 (11) | 0.000 | 0.000 | −0.0006 (8) |
C24 | 0.115 (3) | 0.0171 (9) | 0.0617 (18) | 0.000 | 0.000 | −0.0122 (10) |
Ni1—Cl1 | 2.3325 (4) | C14—H14F | 0.9600 |
Ni1—Cl2 | 2.4604 (1) | N21—C22 | 1.481 (2) |
Ni1—Cl3 | 2.4142 (4) | N21—H21A | 0.8900 |
Ni1—Cl4 | 2.4473 (3) | N21—H21B | 0.8900 |
Ni2—Cl3 | 2.3853 (3) | N21—H21C | 0.8900 |
Ni2—Cl4 | 2.4121 (2) | N21—H21D | 0.8900 |
N11—C12 | 1.480 (2) | N21—H21E | 0.8900 |
N11—H11A | 0.8900 | N21—H21F | 0.8900 |
N11—H11B | 0.8900 | C22—C23 | 1.456 (3) |
N11—H11C | 0.8900 | C22—H22A | 0.9700 |
C12—C13 | 1.498 (2) | C22—H22B | 0.9700 |
C12—H12A | 0.9700 | C23—C24 | 1.541 (3) |
C12—H12B | 0.9700 | C23—H23A | 0.9700 |
C13—C14 | 1.520 (3) | C23—H23B | 0.9700 |
C13—H13A | 0.9700 | C24—H24A | 0.9600 |
C13—H13B | 0.9700 | C24—H24B | 0.9600 |
C14—H14A | 0.9600 | C24—H24C | 0.9600 |
C14—H14B | 0.9600 | C24—H24D | 0.9600 |
C14—H14C | 0.9600 | C24—H24E | 0.9600 |
C14—H14D | 0.9600 | C24—H24F | 0.9600 |
C14—H14E | 0.9600 | ||
Cl1—Ni1—Cl2 | 93.482 (11) | H14D—C14—H14E | 109.5 |
Cl1—Ni1—Cl3 | 176.187 (14) | C13—C14—H14F | 109.5 |
Cl1—Ni1—Cl4 | 92.633 (10) | H14D—C14—H14F | 109.5 |
Cl2—Ni1—Cl2i | 89.247 (6) | H14E—C14—H14F | 109.5 |
Cl2—Ni1—Cl3 | 89.230 (10) | C22—N21—H21A | 109.5 |
Cl2—Ni1—Cl4 | 93.084 (6) | C22—N21—H21B | 109.5 |
Cl2—Ni1—Cl4i | 173.311 (11) | H21A—N21—H21B | 109.5 |
Cl3—Ni1—Cl4 | 84.537 (9) | C22—N21—H21C | 109.5 |
Cl4—Ni1—Cl4i | 83.927 (12) | H21A—N21—H21C | 109.5 |
Cl3—Ni2—Cl4 | 85.937 (8) | H21B—N21—H21C | 109.5 |
Cl4—Ni2—Cl4ii | 94.563 (12) | C22—N21—H21D | 109.5 |
Ni1—Cl2—Ni1iii | 164.908 (17) | C22—N21—H21E | 109.5 |
Ni2—Cl3—Ni1 | 78.144 (10) | H21D—N21—H21E | 109.5 |
Ni2—Cl4—Ni1 | 77.001 (8) | C22—N21—H21F | 109.5 |
C12—N11—H11A | 109.5 | H21D—N21—H21F | 109.5 |
C12—N11—H11B | 109.5 | H21E—N21—H21F | 109.5 |
H11A—N11—H11B | 109.5 | C23—C22—N21 | 111.96 (16) |
C12—N11—H11C | 109.5 | C23—C22—H22A | 109.2 |
H11A—N11—H11C | 109.5 | N21—C22—H22A | 109.2 |
H11B—N11—H11C | 109.5 | C23—C22—H22B | 109.2 |
N11—C12—C13 | 112.85 (15) | N21—C22—H22B | 109.2 |
N11—C12—H12A | 109.0 | H22A—C22—H22B | 107.9 |
C13—C12—H12A | 109.0 | C22—C23—C24 | 111.5 (2) |
N11—C12—H12B | 109.0 | C22—C23—H23A | 109.3 |
C13—C12—H12B | 109.0 | C24—C23—H23A | 109.3 |
H12A—C12—H12B | 107.8 | C22—C23—H23B | 109.3 |
C12—C13—C14 | 111.94 (18) | C24—C23—H23B | 109.3 |
C12—C13—H13A | 109.2 | H23A—C23—H23B | 108.0 |
C14—C13—H13A | 109.2 | C23—C24—H24A | 109.5 |
C12—C13—H13B | 109.2 | C23—C24—H24B | 109.5 |
C14—C13—H13B | 109.2 | H24A—C24—H24B | 109.5 |
H13A—C13—H13B | 107.9 | C23—C24—H24C | 109.5 |
C13—C14—H14A | 109.5 | H24A—C24—H24C | 109.5 |
C13—C14—H14B | 109.5 | H24B—C24—H24C | 109.5 |
H14A—C14—H14B | 109.5 | C23—C24—H24D | 109.5 |
C13—C14—H14C | 109.5 | C23—C24—H24E | 109.5 |
H14A—C14—H14C | 109.5 | H24D—C24—H24E | 109.5 |
H14B—C14—H14C | 109.5 | C23—C24—H24F | 109.5 |
C13—C14—H14D | 109.5 | H24D—C24—H24F | 109.5 |
C13—C14—H14E | 109.5 | H24E—C24—H24F | 109.5 |
Symmetry codes: (i) −x, y, z; (ii) x, −y+1, −z; (iii) x+1/2, y, −z+1/2. |
100 K |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···Cl1 | 0.89 | 2.31 | 3.1536 (13) | 158 |
N11—H11B···Cl4iv | 0.89 | 2.54 | 3.3451 (10) | 150 |
Symmetry code: (iv) −x+1/2, y, −z+1/2. |
(C3H10N)4[Ni3Cl10] | Dx = 1.744 Mg m−3 |
Mr = 771.09 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmce | Cell parameters from 4129 reflections |
a = 6.9786 (1) Å | θ = 1.0–37.0° |
b = 24.0608 (5) Å | µ = 2.84 mm−1 |
c = 17.4131 (3) Å | T = 240 K |
V = 2923.85 (9) Å3 | Prism, colourless |
Z = 4 | 0.25 × 0.19 × 0.16 mm |
F(000) = 1576 |
Nonius KappaCCD area-detector diffractometer | 3960 independent reflections |
Graphite monochromator | 2216 reflections with I > 2σ(I) |
Detector resolution: 9 pixels mm-1 | Rint = 0.094 |
CCD scans | θmax = 37.0°, θmin = 3.3° |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | h = 0→11 |
Tmin = 0.540, Tmax = 0.646 | k = 0→40 |
3960 measured reflections | l = 0→29 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0357P)2] where P = (Fo2 + 2Fc2)/3 |
3960 reflections | (Δ/σ)max < 0.001 |
97 parameters | Δρmax = 0.72 e Å−3 |
6 restraints | Δρmin = −1.30 e Å−3 |
(C3H10N)4[Ni3Cl10] | V = 2923.85 (9) Å3 |
Mr = 771.09 | Z = 4 |
Orthorhombic, Cmce | Mo Kα radiation |
a = 6.9786 (1) Å | µ = 2.84 mm−1 |
b = 24.0608 (5) Å | T = 240 K |
c = 17.4131 (3) Å | 0.25 × 0.19 × 0.16 mm |
Nonius KappaCCD area-detector diffractometer | 3960 independent reflections |
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | 2216 reflections with I > 2σ(I) |
Tmin = 0.540, Tmax = 0.646 | Rint = 0.094 |
3960 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 6 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.72 e Å−3 |
3960 reflections | Δρmin = −1.30 e Å−3 |
97 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) | |
Ni1 | 0.0000 | 0.436485 (14) | 0.151274 (18) | 0.01973 (9) | |
Ni2 | 0.0000 | 0.5000 | 0.0000 | 0.01977 (11) | |
Cl1 | 0.0000 | 0.34022 (3) | 0.16579 (4) | 0.02974 (16) | |
Cl2 | 0.2500 | 0.45049 (3) | 0.2500 | 0.02529 (14) | |
Cl3 | 0.0000 | 0.53563 (3) | 0.12793 (3) | 0.02425 (14) | |
Cl4 | 0.23513 (7) | 0.434117 (19) | 0.04622 (2) | 0.02446 (11) | |
N11 | 0.0000 | 0.34802 (11) | 0.34736 (13) | 0.0350 (6) | 0.768 (8) |
H11A | 0.0000 | 0.3557 | 0.2974 | 0.053* | 0.384 (4) |
H11B | 0.1041 | 0.3625 | 0.3690 | 0.053* | 0.192 (2) |
H11C | −0.1041 | 0.3625 | 0.3690 | 0.053* | 0.192 (2) |
H11D | 0.0000 | 0.3648 | 0.3929 | 0.053* | 0.384 (4) |
H11E | −0.1041 | 0.3580 | 0.3213 | 0.053* | 0.192 (2) |
H11F | 0.1041 | 0.3580 | 0.3213 | 0.053* | 0.192 (2) |
C12 | 0.0000 | 0.28705 (16) | 0.3584 (3) | 0.0410 (13) | 0.768 (8) |
H12A | −0.1122 | 0.2716 | 0.3333 | 0.049* | 0.384 (4) |
H12B | 0.1122 | 0.2716 | 0.3333 | 0.049* | 0.384 (4) |
C13 | 0.0000 | 0.2698 (2) | 0.4382 (3) | 0.0644 (19) | 0.768 (8) |
H13A | −0.1124 | 0.2848 | 0.4635 | 0.077* | 0.384 (4) |
H13B | 0.1124 | 0.2848 | 0.4635 | 0.077* | 0.384 (4) |
C14 | 0.0000 | 0.20715 (18) | 0.4462 (3) | 0.0827 (16) | 0.768 (8) |
H14A | 0.0000 | 0.1974 | 0.4997 | 0.124* | 0.384 (4) |
H14B | 0.1123 | 0.1922 | 0.4221 | 0.124* | 0.192 (2) |
H14C | −0.1123 | 0.1922 | 0.4221 | 0.124* | 0.192 (2) |
H14D | 0.0000 | 0.1904 | 0.3962 | 0.124* | 0.384 (4) |
H14E | −0.1123 | 0.1957 | 0.4738 | 0.124* | 0.192 (2) |
H14F | 0.1123 | 0.1957 | 0.4738 | 0.124* | 0.192 (2) |
N21 | 0.5000 | 0.53174 (10) | 0.12543 (15) | 0.0354 (6) | 0.872 (9) |
H21A | 0.5000 | 0.5028 | 0.1572 | 0.053* | 0.436 (4) |
H21B | 0.6041 | 0.5305 | 0.0960 | 0.053* | 0.218 (2) |
H21C | 0.3959 | 0.5305 | 0.0960 | 0.053* | 0.218 (2) |
H21D | 0.5000 | 0.5398 | 0.0755 | 0.053* | 0.436 (4) |
H21E | 0.3959 | 0.5120 | 0.1368 | 0.053* | 0.218 (2) |
H21F | 0.6041 | 0.5120 | 0.1368 | 0.053* | 0.218 (2) |
C22 | 0.5000 | 0.58305 (18) | 0.1698 (2) | 0.0577 (15) | 0.872 (9) |
H22A | 0.3882 | 0.5826 | 0.2029 | 0.087* | 0.436 (4) |
H22B | 0.6118 | 0.5826 | 0.2029 | 0.087* | 0.436 (4) |
C23 | 0.5000 | 0.6324 (2) | 0.1305 (3) | 0.098 (2) | 0.872 (9) |
H23A | 0.3880 | 0.6332 | 0.0976 | 0.147* | 0.436 (4) |
H23B | 0.6120 | 0.6332 | 0.0976 | 0.147* | 0.436 (4) |
C24 | 0.5000 | 0.68499 (18) | 0.1795 (3) | 0.0893 (17) | 0.872 (9) |
H24A | 0.5000 | 0.7170 | 0.1466 | 0.134* | 0.436 (4) |
H24B | 0.6123 | 0.6855 | 0.2113 | 0.134* | 0.218 (2) |
H24C | 0.3877 | 0.6855 | 0.2113 | 0.134* | 0.218 (2) |
H24D | 0.5000 | 0.6750 | 0.2328 | 0.134* | 0.436 (4) |
H24E | 0.3877 | 0.7065 | 0.1682 | 0.134* | 0.218 (2) |
H24F | 0.6123 | 0.7065 | 0.1682 | 0.134* | 0.218 (2) |
N11A | 0.0000 | 0.34802 (11) | 0.34736 (13) | 0.0350 (6) | 0.232 (8) |
H11G | 0.0000 | 0.3302 | 0.3026 | 0.053* | 0.116 (4) |
H11H | 0.1041 | 0.3692 | 0.3507 | 0.053* | 0.058 (2) |
H11I | −0.1041 | 0.3692 | 0.3507 | 0.053* | 0.058 (2) |
H11J | 0.0000 | 0.3823 | 0.3667 | 0.053* | 0.116 (4) |
H11K | −0.1041 | 0.3432 | 0.3186 | 0.053* | 0.058 (2) |
H11L | 0.1041 | 0.3432 | 0.3186 | 0.053* | 0.058 (2) |
C12A | 0.0000 | 0.3067 (5) | 0.4114 (7) | 0.062 (5)* | 0.232 (8) |
H12C | 0.1124 | 0.3124 | 0.4432 | 0.075* | 0.116 (4) |
H12D | −0.1124 | 0.3124 | 0.4432 | 0.075* | 0.116 (4) |
C13A | 0.0000 | 0.2488 (5) | 0.3818 (8) | 0.062 (5)* | 0.232 (8) |
H13C | 0.1124 | 0.2431 | 0.3500 | 0.075* | 0.116 (4) |
H13D | −0.1124 | 0.2431 | 0.3500 | 0.075* | 0.116 (4) |
C14A | 0.0000 | 0.20715 (18) | 0.4462 (3) | 0.0827 (16) | 0.232 (8) |
H14G | 0.0000 | 0.2263 | 0.4946 | 0.124* | 0.116 (4) |
H14H | 0.1123 | 0.1843 | 0.4426 | 0.124* | 0.058 (2) |
H14I | −0.1123 | 0.1843 | 0.4426 | 0.124* | 0.058 (2) |
H14J | 0.0000 | 0.1702 | 0.4253 | 0.124* | 0.116 (4) |
H14K | −0.1123 | 0.2123 | 0.4772 | 0.124* | 0.058 (2) |
H14L | 0.1123 | 0.2123 | 0.4772 | 0.124* | 0.058 (2) |
N21A | 0.5000 | 0.53174 (10) | 0.12543 (15) | 0.0354 (6) | 0.128 (9) |
H21G | 0.5000 | 0.5224 | 0.1749 | 0.053* | 0.064 (4) |
H21H | 0.6041 | 0.5180 | 0.1028 | 0.053* | 0.032 (2) |
H21I | 0.3959 | 0.5180 | 0.1028 | 0.053* | 0.032 (2) |
H21J | 0.5000 | 0.5165 | 0.0788 | 0.053* | 0.064 (4) |
H21K | 0.3959 | 0.5209 | 0.1509 | 0.053* | 0.032 (2) |
H21L | 0.6041 | 0.5209 | 0.1509 | 0.053* | 0.032 (2) |
C22A | 0.5000 | 0.5938 (4) | 0.1182 (16) | 0.066 (9)* | 0.128 (9) |
H22C | 0.6122 | 0.6050 | 0.0892 | 0.079* | 0.064 (4) |
H22D | 0.3878 | 0.6050 | 0.0892 | 0.079* | 0.064 (4) |
C23A | 0.5000 | 0.6239 (5) | 0.1930 (15) | 0.066 (9)* | 0.128 (9) |
H23C | 0.6126 | 0.6135 | 0.2224 | 0.079* | 0.064 (4) |
H23D | 0.3874 | 0.6135 | 0.2224 | 0.079* | 0.064 (4) |
C24A | 0.5000 | 0.68499 (18) | 0.1795 (3) | 0.0893 (17) | 0.128 (9) |
H24G | 0.5000 | 0.6922 | 0.1252 | 0.134* | 0.064 (4) |
H24H | 0.6123 | 0.7011 | 0.2022 | 0.134* | 0.032 (2) |
H24I | 0.3877 | 0.7011 | 0.2022 | 0.134* | 0.032 (2) |
H24J | 0.5000 | 0.7041 | 0.2279 | 0.134* | 0.064 (4) |
H24K | 0.3877 | 0.6951 | 0.1509 | 0.134* | 0.032 (2) |
H24L | 0.6123 | 0.6951 | 0.1509 | 0.134* | 0.032 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01847 (17) | 0.02395 (18) | 0.01676 (15) | 0.000 | 0.000 | 0.00053 (13) |
Ni2 | 0.0175 (2) | 0.0264 (3) | 0.0154 (2) | 0.000 | 0.000 | 0.00148 (18) |
Cl1 | 0.0370 (4) | 0.0229 (3) | 0.0293 (3) | 0.000 | 0.000 | −0.0012 (3) |
Cl2 | 0.0209 (3) | 0.0343 (3) | 0.0207 (3) | 0.000 | −0.0049 (2) | 0.000 |
Cl3 | 0.0291 (3) | 0.0259 (3) | 0.0178 (3) | 0.000 | 0.000 | −0.0008 (2) |
Cl4 | 0.0198 (2) | 0.0326 (2) | 0.0210 (2) | 0.00412 (19) | 0.00082 (16) | 0.00104 (18) |
N11 | 0.0406 (16) | 0.0352 (14) | 0.0293 (13) | 0.000 | 0.000 | 0.0040 (11) |
C12 | 0.053 (3) | 0.024 (2) | 0.047 (3) | 0.000 | 0.000 | 0.0064 (18) |
C13 | 0.087 (4) | 0.060 (4) | 0.046 (3) | 0.000 | 0.000 | 0.018 (3) |
C14 | 0.077 (3) | 0.067 (3) | 0.104 (4) | 0.000 | 0.000 | 0.047 (3) |
N21 | 0.0358 (15) | 0.0286 (13) | 0.0419 (14) | 0.000 | 0.000 | −0.0018 (11) |
C22 | 0.087 (4) | 0.040 (3) | 0.046 (3) | 0.000 | 0.000 | −0.016 (2) |
C23 | 0.173 (7) | 0.036 (3) | 0.086 (4) | 0.000 | 0.000 | −0.007 (3) |
C24 | 0.098 (4) | 0.042 (3) | 0.128 (5) | 0.000 | 0.000 | −0.029 (3) |
N11A | 0.0406 (16) | 0.0352 (14) | 0.0293 (13) | 0.000 | 0.000 | 0.0040 (11) |
C14A | 0.077 (3) | 0.067 (3) | 0.104 (4) | 0.000 | 0.000 | 0.047 (3) |
N21A | 0.0358 (15) | 0.0286 (13) | 0.0419 (14) | 0.000 | 0.000 | −0.0018 (11) |
C24A | 0.098 (4) | 0.042 (3) | 0.128 (5) | 0.000 | 0.000 | −0.029 (3) |
Ni1—Cl1 | 2.3299 (8) | C24—H24D | 0.9600 |
Ni1—Cl2 | 2.4724 (2) | C24—H24E | 0.9600 |
Ni1—Cl3 | 2.4200 (7) | C24—H24F | 0.9600 |
Ni1—Cl4 | 2.4580 (5) | N11A—C12A | 1.494 (13) |
Ni2—Cl3 | 2.3869 (6) | N11A—H11G | 0.8900 |
Ni2—Cl4 | 2.4193 (4) | N11A—H11H | 0.8900 |
N11—C12 | 1.480 (5) | N11A—H11I | 0.8900 |
N11—H11A | 0.8900 | N11A—H11J | 0.8900 |
N11—H11B | 0.8900 | N11A—H11K | 0.8900 |
N11—H11C | 0.8900 | N11A—H11L | 0.8900 |
N11—H11D | 0.8900 | C12A—C13A | 1.485 (10) |
N11—H11E | 0.8900 | C12A—H12C | 0.9700 |
N11—H11F | 0.8900 | C12A—H12D | 0.9700 |
C12—C13 | 1.450 (6) | C13A—H13C | 0.9700 |
C12—H12A | 0.9700 | C13A—H13D | 0.9700 |
C12—H12B | 0.9700 | C13A—C14A | 1.504 (14) |
C13—C14 | 1.514 (6) | C14A—H14G | 0.9600 |
C13—H13A | 0.9700 | C14A—H14H | 0.9600 |
C13—H13B | 0.9700 | C14A—H14I | 0.9600 |
C14—H14A | 0.9600 | C14A—H14J | 0.9600 |
C14—H14B | 0.9600 | C14A—H14K | 0.9600 |
C14—H14C | 0.9600 | C14A—H14L | 0.9600 |
C14—H14D | 0.9600 | N21A—C22A | 1.498 (11) |
C14—H14E | 0.9600 | N21A—H21G | 0.8900 |
C14—H14F | 0.9600 | N21A—H21H | 0.8900 |
N21—C22 | 1.456 (5) | N21A—H21I | 0.8900 |
N21—H21A | 0.8900 | N21A—H21J | 0.8900 |
N21—H21B | 0.8900 | N21A—H21K | 0.8900 |
N21—H21C | 0.8900 | N21A—H21L | 0.8900 |
N21—H21D | 0.8900 | C22A—C23A | 1.490 (10) |
N21—H21E | 0.8900 | C22A—H22C | 0.9700 |
N21—H21F | 0.8900 | C22A—H22D | 0.9700 |
C22—C23 | 1.370 (7) | C23A—H23C | 0.9700 |
C22—H22A | 0.9700 | C23A—H23D | 0.9700 |
C22—H22B | 0.9700 | C23A—C24A | 1.490 (13) |
C23—C24 | 1.525 (6) | C24A—H24G | 0.9600 |
C23—H23A | 0.9700 | C24A—H24H | 0.9600 |
C23—H23B | 0.9700 | C24A—H24I | 0.9600 |
C24—H24A | 0.9600 | C24A—H24J | 0.9600 |
C24—H24B | 0.9600 | C24A—H24K | 0.9600 |
C24—H24C | 0.9600 | C24A—H24L | 0.9600 |
Cl1—Ni1—Cl2 | 93.44 (2) | C23—C24—H24C | 109.5 |
Cl1—Ni1—Cl3 | 176.56 (3) | H24A—C24—H24C | 109.5 |
Cl1—Ni1—Cl4 | 93.308 (18) | H24B—C24—H24C | 109.5 |
Cl2—Ni1—Cl2i | 89.765 (11) | C23—C24—H24D | 109.5 |
Cl2—Ni1—Cl3 | 89.00 (2) | C23—C24—H24E | 109.5 |
Cl2—Ni1—Cl4 | 92.840 (11) | H24D—C24—H24E | 109.5 |
Cl2—Ni1—Cl4i | 172.61 (2) | C23—C24—H24F | 109.5 |
Cl3—Ni1—Cl4 | 84.136 (17) | H24D—C24—H24F | 109.5 |
Cl4—Ni1—Cl4i | 83.76 (2) | H24E—C24—H24F | 109.5 |
Cl3—Ni2—Cl4 | 85.691 (16) | H11G—N11A—H11H | 109.5 |
Cl4—Ni2—Cl4ii | 94.59 (2) | H11G—N11A—H11I | 109.5 |
Ni1—Cl2—Ni1iii | 164.34 (4) | C12A—N11A—H11G | 109.5 |
Ni1—Cl3—Ni2 | 78.62 (2) | H11H—N11A—H11I | 109.5 |
Ni1—Cl4—Ni2 | 77.270 (15) | H11J—N11A—H11K | 109.5 |
C12—N11—H11A | 109.5 | H11J—N11A—H11L | 109.5 |
C12—N11—H11B | 109.5 | C12A—N11A—H11H | 109.5 |
H11A—N11—H11B | 109.5 | C12A—N11A—H11I | 109.5 |
C12—N11—H11C | 109.5 | C12A—N11A—H11J | 109.5 |
H11A—N11—H11C | 109.5 | C12A—N11A—H11K | 109.5 |
H11B—N11—H11C | 109.5 | H11K—N11A—H11L | 109.5 |
C12—N11—H11D | 109.5 | C12A—N11A—H11L | 109.5 |
C12—N11—H11E | 109.5 | N11A—C12A—C13A | 111.4 (9) |
H11D—N11—H11E | 109.5 | N11A—C12A—H12C | 109.3 |
C12—N11—H11F | 109.5 | N11A—C12A—H12D | 109.3 |
H11D—N11—H11F | 109.5 | C13A—C12A—H12C | 109.3 |
H11E—N11—H11F | 109.5 | C13A—C12A—H12D | 109.3 |
N11—C12—C13 | 114.1 (4) | H12C—C12A—H12D | 108.0 |
C13—C12—H12A | 108.7 | C12A—C13A—H13C | 109.3 |
N11—C12—H12A | 108.7 | C12A—C13A—H13D | 109.3 |
C13—C12—H12B | 108.7 | H13C—C13A—H13D | 108.0 |
N11—C12—H12B | 108.7 | C12A—C13A—H13C | 109.3 |
H12A—C12—H12B | 107.6 | C12A—C13A—H13D | 109.3 |
C12—C13—C14 | 111.9 (4) | C12A—C13A—C14A | 111.5 (9) |
C12—C13—H13A | 109.2 | C13A—C14A—H14G | 109.5 |
C14—C13—H13A | 109.2 | C13A—C14A—H14H | 109.5 |
C12—C13—H13B | 109.2 | C13A—C14A—H14I | 109.5 |
C14—C13—H13B | 109.2 | C13A—C14A—H14J | 109.5 |
H13A—C13—H13B | 107.9 | C13A—C14A—H14K | 109.5 |
C13—C14—H14A | 109.5 | C13A—C14A—H14L | 109.5 |
C13—C14—H14B | 109.5 | H14G—C14A—H14H | 109.5 |
H14A—C14—H14B | 109.5 | H14G—C14A—H14I | 109.5 |
C13—C14—H14C | 109.5 | H14H—C14A—H14I | 109.5 |
H14A—C14—H14C | 109.5 | H14J—C14A—H14K | 109.5 |
H14B—C14—H14C | 109.5 | H14J—C14A—H14L | 109.5 |
C13—C14—H14D | 109.5 | H14K—C14A—H14L | 109.5 |
C13—C14—H14E | 109.5 | H21G—N21A—H21H | 109.5 |
H14D—C14—H14E | 109.5 | H21G—N21A—H21I | 109.5 |
C13—C14—H14F | 109.5 | C22A—N21A—H21G | 109.5 |
H14D—C14—H14F | 109.5 | H21H—N21A—H21I | 109.5 |
H14E—C14—H14F | 109.5 | H21J—N21A—H21K | 109.5 |
C22—N21—H21A | 109.5 | H21J—N21A—H21L | 109.5 |
C22—N21—H21B | 109.5 | C22A—N21A—H21J | 109.5 |
H21A—N21—H21B | 109.5 | H21K—N21A—H21L | 109.5 |
C22—N21—H21C | 109.5 | C22A—N21A—H21K | 109.5 |
H21A—N21—H21C | 109.5 | C22A—N21A—H21L | 109.5 |
H21B—N21—H21C | 109.5 | N21A—C22A—H22C | 108.7 |
C22—N21—H21D | 109.5 | N21A—C22A—H22D | 108.7 |
C22—N21—H21E | 109.5 | N21A—C22A—C23A | 114.3 (9) |
H21D—N21—H21E | 109.5 | C23A—C22A—H22C | 108.7 |
C22—N21—H21F | 109.5 | C23A—C22A—H22D | 108.7 |
H21D—N21—H21F | 109.5 | H22C—C22A—H22D | 107.6 |
H21E—N21—H21F | 109.5 | C22A—C23A—H23C | 109.7 |
N21—C22—C23 | 118.0 (4) | C22A—C23A—H23D | 109.7 |
C23—C22—H22A | 107.8 | H23C—C23A—H23D | 108.2 |
N21—C22—H22A | 107.8 | C23A—C24A—H24G | 109.5 |
C23—C22—H22B | 107.8 | C23A—C24A—H24H | 109.5 |
N21—C22—H22B | 107.8 | C23A—C24A—H24I | 109.5 |
H22A—C22—H22B | 107.1 | C23A—C24A—H24J | 109.5 |
C22—C23—C24 | 116.1 (5) | C23A—C24A—H24K | 109.5 |
C22—C23—H23A | 108.3 | C23A—C24A—H24L | 109.5 |
C24—C23—H23A | 108.3 | H24G—C24A—H24H | 109.5 |
C22—C23—H23B | 108.3 | H24G—C24A—H24I | 109.5 |
C24—C23—H23B | 108.3 | H24H—C24A—H24I | 109.5 |
H23A—C23—H23B | 107.4 | H24J—C24A—H24K | 109.5 |
C23—C24—H24A | 109.5 | H24J—C24A—H24L | 109.5 |
C23—C24—H24B | 109.5 | H24K—C24A—H24L | 109.5 |
H24A—C24—H24B | 109.5 |
Symmetry codes: (i) −x, y, z; (ii) x, −y+1, −z; (iii) x+1/2, y, −z+1/2. |
Experimental details
(I_100K) | (I_240K) | |
Crystal data | ||
Chemical formula | (C3H10N)4[Ni3Cl10] | (C3H10N)4[Ni3Cl10] |
Mr | 771.09 | 771.09 |
Crystal system, space group | Orthorhombic, Cmce | Orthorhombic, Cmce |
Temperature (K) | 100 | 240 |
a, b, c (Å) | 6.9132 (1), 23.9825 (2), 17.3695 (2) | 6.9786 (1), 24.0608 (5), 17.4131 (3) |
V (Å3) | 2879.79 (6) | 2923.85 (9) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.88 | 2.84 |
Crystal size (mm) | 0.25 × 0.19 × 0.16 | 0.25 × 0.19 × 0.16 |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) | Multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.527, 0.638 | 0.540, 0.646 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3904, 3904, 3435 | 3960, 3960, 2216 |
Rint | 0.043 | 0.094 |
(sin θ/λ)max (Å−1) | 0.846 | 0.848 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.056, 1.03 | 0.038, 0.088, 1.00 |
No. of reflections | 3904 | 3960 |
No. of parameters | 85 | 97 |
No. of restraints | 0 | 6 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.70, −1.10 | 0.72, −1.30 |
Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Ni1—Cl1 | 2.3325 (4) | Ni1—Cl4 | 2.4473 (3) |
Ni1—Cl2 | 2.4604 (1) | Ni2—Cl3 | 2.3853 (3) |
Ni1—Cl3 | 2.4142 (4) | Ni2—Cl4 | 2.4121 (2) |
Cl1—Ni1—Cl2 | 93.482 (11) | Cl3—Ni1—Cl4 | 84.537 (9) |
Cl1—Ni1—Cl3 | 176.187 (14) | Cl4—Ni1—Cl4i | 83.927 (12) |
Cl1—Ni1—Cl4 | 92.633 (10) | Cl3—Ni2—Cl4 | 85.937 (8) |
Cl2—Ni1—Cl2i | 89.247 (6) | Cl4—Ni2—Cl4ii | 94.563 (12) |
Cl2—Ni1—Cl3 | 89.230 (10) | Ni1—Cl2—Ni1iii | 164.908 (17) |
Cl2—Ni1—Cl4 | 93.084 (6) | Ni2—Cl3—Ni1 | 78.144 (10) |
Cl2—Ni1—Cl4i | 173.311 (11) | Ni2—Cl4—Ni1 | 77.001 (8) |
Symmetry codes: (i) −x, y, z; (ii) x, −y+1, −z; (iii) x+1/2, y, −z+1/2. |
100 K |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11A···Cl1 | 0.890 | 2.311 | 3.1536 (13) | 157.96 |
N11—H11B···Cl4iv | 0.890 | 2.543 | 3.3451 (10) | 150.19 |
Symmetry code: (iv) −x+1/2, y, −z+1/2. |
Ni1—Cl1 | 2.3299 (8) | Ni1—Cl4 | 2.4580 (5) |
Ni1—Cl2 | 2.4724 (2) | Ni2—Cl3 | 2.3869 (6) |
Ni1—Cl3 | 2.4200 (7) | Ni2—Cl4 | 2.4193 (4) |
Cl1—Ni1—Cl2 | 93.44 (2) | Cl3—Ni1—Cl4 | 84.136 (17) |
Cl1—Ni1—Cl3 | 176.56 (3) | Cl4—Ni1—Cl4i | 83.76 (2) |
Cl1—Ni1—Cl4 | 93.308 (18) | Cl3—Ni2—Cl4 | 85.691 (16) |
Cl2—Ni1—Cl2i | 89.765 (11) | Cl4—Ni2—Cl4ii | 94.59 (2) |
Cl2—Ni1—Cl3 | 89.00 (2) | Ni1—Cl2—Ni1iii | 164.34 (4) |
Cl2—Ni1—Cl4 | 92.840 (11) | Ni1—Cl3—Ni2 | 78.62 (2) |
Cl2—Ni1—Cl4i | 172.61 (2) | Ni1—Cl4—Ni2 | 77.270 (15) |
Symmetry codes: (i) −x, y, z; (ii) x, −y+1, −z; (iii) x+1/2, y, −z+1/2. |
Layered organic–inorganic hybrid materials are of interest for electrical and optical device applications (Mitzi et al., 2001; Mitzi, 2004). Among these are A2MX4 layer perovskites (A = organic cation, M = metal cation and X = monatomic anion), descended from the parent K2NiF4 structure, in which layers of corner-sharing MX6 octahedra are interleaved with bilayers of organic cations (Maxcy & Willett, 2004). The organic bilayers are typically composed of n-alkylammonium or anilinium cations in which the –NH3 head group fits into the inorganic layer, so as to form hydrogen bonds with the anions, while the nonpolar tails of the cations project into the center of the bilayer. Layer perovskites are also a source for the study of structural phase transitions, often involving progressive disorder of the organic cation, of which a prominent example is the sequence of six different phases in (n-C3H7NH3)2[MnCl4] [Depmeier, 2009, and references therein; Cambridge Structural Database (CSD, Version ???; Allen, 2002) refcodes: PAMMNC01–17, 26, and 36].
Dussarrat et al. (1995) have examined structures derived from K2NiF4 through crystallographic shears. Among these is the Ba4(Ti,Pt)3O10 structure (Blattner et al., 1948) consisting of trimetal segments of face-sharing MO6 octahedra bridged through corner-sharing to two other segments at each end to establish a zigzag layer in the ac plane of the orthorhombic Cmce unit cell. The zigzag layer is derived from the parent K2NiF4 structure by dividing the (NiF42-)n network layer into slabs two NiF6 complexes wide. Alternate slabs are displaced perpendicular to the layer plane to a point approximately midway between the layers, with F- ions added to maintain full Ni2+ coordination, and with small lateral displacements of the slabs to give regular octahedral holes between slabs from neighboring layers. Additional Ni2+ cations are then positioned in these octahedral holes to generate the trimetal segments of face-sharing NiF6 octahedra. Inorganic A4M3X10 compounds with this structure type are well known and typically occur when A is a large group IA or IIA metal cation and X is a small anion, e.g. F-, O2- or H-. Cs4Mg3F10 (Steinfink & Brunton, 1969) is also used to identify the aristotype structure with further examples, such as Ba4Ir3O10 (Wilkens & Müller-Buschbaum, 1991), Ba4(Ir,Al)3O10 (Müller-Buschbaum & Neubacher, 1990; Neubacher & Müller-Buschbaum, 1991), Cs4M'3F10 (M' = Co, Ni or Zn; Schmidt et al., 1992), Ba4Ru3O10 (Dussarrat et al., 1996; Carim et al., 2000), Sr4Mn3O10 (Floros et al., 2000) and Cs4Mg3H10 (Bertheville et al., 2002), illustrating the range of this structure type. A related structure is exemplified by Cs4Cu3F10, in which linear tricopper segments of face-sharing CuF6 octahedra are likewise bridged through corner-sharing to two other segments at each end, but in a stepwise fashion so that the terminal ligands on neighboring corner-shared CuF6 octahedra are trans, rather than cis as in the Cs4Mg3F10-type structures (Kissel & Hoppe, 1988; Dussarrat et al., 1995).
Over the past two decades several examples of hybrid organic–inorganic compounds in the Cs4Mg3F10 structure type have been identified. First reported was the structure of (C6H5NH3)4[Cd3Br10] (Ishihara et al., 1994; CSD refcode POPHAD); the isomorphous chloride structure is more recent (Costin-Hogan et al., 2008; CSD refcode EGUFUI). The structures of two [Pb3I10]4- salts, viz. C6H5CH2SC(NH2)2+ (Raptopoulou et al., 2002; CSD refcode IGECIG) and C6H5(CH2)3NH3+ (Billing & Lemmerer, 2006a; CSD refcode WEHSAE), followed. (i-C3H7NH3)4[Cd3Cl10] (Gagor et al., 2011), which exhibits a sequence of three phases upon cooling (CSD refcodes IPEMAS, IPEMAS01 and IPEMAS02 for phases I–III, respectively) and possesses the smallest A cation of these hybrid Cs4Mg3F10-type compounds, is the most recent. Of note also are the [(C6H5)N(CH3)3]4[Pb3Br10] (Wiest et al., 1999; CSD refcode CAQVIZ) and [(C6H5)N(CH3)3]4[Sn3I10] (Lode & Krautscheid, 2001; CSD refcode RAJMUK) structures, which belong to the Cs4Cu3F10 structure type. We present here the 100 and 240 K structures of the title compound, (n-C3H7NH3)4[Ni3Cl10], (I), which is the first example of a hybrid Cs4Mg3F10-type structure containing an open-shell transition metal ion.
Compound (I) remains in the Cs4Mg3F10 aristotype space group from ambient temperature to 80 K with an undistorted {[Ni3Cl10]4-}n zigzag layer network, unlike other hybrid structures (at ambient temperature or below) in which neighboring trimetal segments are displaced to give non-rectangular voids between them and lower space-group symmetry. The Ni2+ ions of the 2/m-symmetric trinickel segment exhibit compressed square–bipyramidal coordination environments. Atoms Cl1 and Cl3 are axial for the terminal atom Ni1, with an average bond length of 2.3734 Å (2.3750 Å at 240 K) versus an average equatorial bond length of 2.4539 Å (2.4652 Å at 240 K). While both axial lengths are less than the equatorial lengths, Ni1—Cl1 is substantially shorter than Ni1—Cl3, since the former is terminal while the latter is bridging. The central Ni2 environment is less compressed, with the difference between equatorial Ni2—Cl4 and axial Ni2—Cl3 bond lengths equal to 0.0268 Å (0.0324 Å at 240 K). Atom Cl2 monobridges to a neighboring trinickel segment to generate the zigzag layer, with the Ni1—Cl2—Ni1iv bridge [symmetry code: (iv) x + 1/2, y, -z + 1/2] almost linear (164–165°); indeed, this is the most linear of the hybrid compounds, where values of 142.51 (3) (CSD refcode WEHSAE), 142.79 (POPHAD), 144.56 (EGUFUI), 153.83 and 154.38 (IPEMAS02), 155.32 (IPEMAS01), 158.42 (IPEMAS) and 159.01 (5)° (IGECIG) are observed. A plot of the trinickel segment with the two non-equivalent n-propylammonium cations in (I) is presented in Fig. 1 for the 100 and 240 K structures. Coordinate bond lengths and angles are presented in Tables 1 (100 K) and 3 (240 K).
As the first hybrid metal–organic Cs4Mg3F10-type structure with an open-shell metal cation (d8, S = 1), the magnetic properties of (I) are of interest. Exchange coupling between electron spin on neighboring metal cations in bridged systems depends on, among other factors, the M—X—M bridging angle (Kahn, 1985), with the ferromagnetic (FM) coupling expected at 90° becoming antiferromagnetic (AFM) as the bridge angle deviates from this. Thus, the quasi-linear monobridge between trinickel segments favors AFM coupling. Magnetic susceptibility measurements of linear chain tri-µ-chlorido-bridged ANiCl3 compounds indicate the crossover point from FM to AFM coupling likely occurs close to the bridging angle values (77–79°) within the trinickel segment of (I). In [(CH3)4N][NiCl3], for example, the bridging Cl—Ni—Cl angle is 78.74° (Stucky, 1968) with weak FM coupling (J/k = 1.7 K; Hijmans et al., 1984). The Cs+, NH4+, Rb+ and Tl+ salts confirm the trend by showing, respectively, greater AFM coupling correlated with shorter neighboring Ni···Ni distances within the chain and, hence, smaller Ni—Cl—Ni angles (Witteveen & van Veen, 1974). Thus, the coupling within the trinickel segment should be weak (whether AFM or FM), with AFM coupling along the rows of Ni1 atoms at the folds of the zigzag layer (corresponding to the crystallographically sheared slabs derived from the parent K2NiF4 structure type) dominant. In contrast, Cs4Ni3F10 shows spontaneous magnetization in the range 9.5 to 21 K, attributed to strong FM coupling within the trinickel segment similar to that within the (NiF3-)n linear chains of CsNiF3, but AFM ordering below 9.5 K, attributed to weaker coupling between trinuclear segments across the quasi-linear Ni—F—Ni bridges (Schmidt et al., 1992).
The mirror-symmetric propylammonium cations of (I) exhibit staggered conformations but with differences in disorder (although no thermal anomaly is observed between 183 and 313 K). Displacement ellipsoids elongated perpendicular to the mirror plane for C atoms and Cl1 at 100 K suggest dynamic disorder across the plane, although no disorder is present in the model. Such anisotropy is absent at 240 K, but minor disorder components are observed in which the central C-atom conformation is reversed. Given the large area available to the propylammonium cation, it is not surprising that disorder is present. Four cation head groups in (I) occupy a given side of the inorganic layer demarcated by a and c, to give an area of 30.0197 (2) Å2 [30.3798 (3) Å2 at 240 K] per cation. In comparison, the area occupied per cation on a given side of the inorganic layer in (n-C3H7NH3)2[MnCl4] is only 27–28 Å2, and this in a system for which cation disorder is a key feature. Ammonium head groups for both cations fit into cages formed by chloride ions of neighboring trinickel segments of the layer: the N11 head group is surrounded by seven close N···Cl contacts [3.1536 (13) (Cl1), 3.3451 (11) (Cl4 × 2), 3.4480 (11) (Cl2 × 2) and 3.4649 (1) (Cl1 × 2) Å at 100 K], and the N21 head group by eight close N···Cl contacts [3.2677 (11) (Cl4 × 2), 3.3669 (11) (Cl2 × 2), 3.4588 (1) (Cl3 × 2) and 3.6061 (12) (Cl4 × 2) Å at 100 K]. The N atoms are almost on a line between two equivalent Cl ligands of parallel neighboring trinickel segments but are set slightly further into the layer, as shown by Cl1v···N11···Cl1vi [172.06 (4)°; symmetry codes: (v) -x + 1/2, y, -z + 1/2; (vi) -x - 1/2, y, -z + 1/2] and Cl3···N21···Cl3vii [175.88 (5)°; symmetry code: (vii) x + 1, y, z] angles at 100 K slightly less than 180°, so as to position the head group to take advantage of these abundant hydrogen-bonding opportunities. The only ordered head group is that of atom N11 at 100 K, where the H atoms link to the Cl atoms with the closest N···Cl contacts (Cl1 and Cl4), and for which hydrogen-bond parameters are listed in Table 2.
The n-propylammonium cations of (I) form an interdigitated bilayer, interleaved between the inorganic layers, in which methyl groups from both sides are packed together in the middle to provide more efficient use of space than a bilayer in which the terminal groups of the organic cations abut one another. Such a packing arrangement in the center of the bilayer is found for (n-C3H7NH3)2[MnCl4], where it is seen as an important factor in the phase behavior of the system (Depmeier, 2009). However, the zigzag inorganic layer induces a more complicated bilayer structure than that found in a layer perovskite. Cation 1 (N11) is located about the convex folds of the inorganic layer so that the tail groups from cations on one side of the bilayer penetrate further into the opposite side to position terminal atom C14 of one cation slightly past atom C13viii [symmetry code: (viii) x + 1/2, -y + 1/2, -z + 1] of the cation on the opposite side. Cations on different sides of the convex fold are related by an a-glide operation that positions atoms C13 and C14 as the walls of a groove parallel to a. Cations 2 (N21) are located about the concave folds of the inorganic layers with their alkyl tails pointing toward each other, so that terminal atoms C24 act as a tongue that fits in the groove formed by cations 1 on the opposite side. While this description of the bilayer structure is most apparent when viewed along a, note that trinickel segments across the fold (and in layers above and below) are staggered relative to each other. As a result, the cations on the opposite walls of the groove are staggered, as are those in the tongue. Since the repeat distance between equivalent cations along a is almost 7 Å, the image of a tight-fitting tongue-and-groove is oversimplified. Indeed, a calculation of voids (probe radius = 0.8 Å, grid spacing = 0.1 Å; MercuryCSD, Version 2.4; Macrae et al., 2008) finds the only voids (5.588 Å3 × 4 = 1.6% of unit-cell volume) between neighboring cations 2 in the bilayer. The disposition of the phenylalkyl groups in IGECIG and WEHSAE is similar, although in these cases the voids in the organic bilayer (calculated under the same conditions) occupy a far larger fraction of the unit-cell volume (10–11%) because of the larger spacing required by the larger atoms in the {[Pb3I10]4-}n layer. The phenylammonium cation disposition in POPHAD and EGUFUI can also be described in this manner with bilayer voids occupying the same unit-cell volume fraction as in (I), although the tongue-and-groove arrangement of these more rigid cations is less defined. The three phases of IPEMAS show void fractions in an intermediate range of 4.2, 3.4 and 3.9% for phases I–III, respectively. Hence the structure of (I), in which the slender propylammonium cation is paired with the smallest metal cation/halide pair of these hybrid structures, has one of the most efficient organic cation packings of the hybrid Cs4Mg3F10-type compounds. A packing diagram of (I) at 100 K viewed parallel to a to show the interleaved inorganic layers and organic bilayers is presented in Fig. 2.
Compound (I) is similar in many respects to the isomorphous high-temperature phase I of (i-C3H7NH3)4[Cd3Cl10] (CSD refcode IPEMAS). The zigzag inorganic layer here is also undistorted and the two independent organic cations are located at the convex or concave folds of the inorganic layer. However, the isopropyl group is bulky enough that the alkyl tails are not interdigitated. (n-C3H7NH3)8[Pb5I18] (Billing & Lemmerer, 2006b; GEHPEP) provides an interesting comparison structure in which the same organic cation as in (I) is found with a more complicated inorganic layer. Here, squares of corner-sharing PbI6 octahedra, similar to the corner-sharing arrangement in the layer perovskites, form parallel stacks, while Pb3I12 segments of face-sharing PbI6 octahedra, similar to those found in the Cs4Mg3F10-type structures, link adjacent stacks. Three of the eight unique n-C3H7NH3+ cations in GEHPEP do exhibit disorder similar to that reported for the 240 K structure of (I), although with a lower occupancy for the major component (54–60%).