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[(CH3)3PH]3[Sb2Cl9] experiences four phase transitions which were found by means of calorimetry, thermogravimetry and X-ray diffraction. The crystal structure was solved in the space group P63/mmc at 382 K (phase I), Pnam at 295 K (phase II) and Pna21 at 175 K (phase V). We observed an unusual increase in symmetry from the monoclinic to the ortho­rhombic form at the IV\rightarrowV transition. The parent hexagonal high-temperature phase I consists of highly disordered [(CH3)3PH]+ cations and [Sb2Cl9]3− anions with an octahedral environment of SbIII. The transition from phases I to II is associated with the ordering of [(CH3)3PH]+ cations. Moreover, the successive transformations from phases I to V are related to the change in the arrangement of Cl atoms in [Sb2Cl9]3− anions from the discrete `face-sharing bioctahedra' (phase I) to two corner-sharing square pyramids. A mechanism for the phase transitions is proposed. It is observed that weak C—H...Cl interactions are responsible for the structure arrangement in low-temperature phases.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768108027353/bm5058sup1.cif
Contains datablocks 175K, 295K, 382K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768108027353/bm5058175Ksup2.hkl
Contains datablock 175K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768108027353/bm5058295Ksup3.hkl
Contains datablock 295K

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108768108027353/bm5058382Ksup4.hkl
Contains datablock 382K

CCDC references: 705577; 705578; 705579

Computing details top

For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
[Figure 7]
[Figure 8]
[Figure 9]
[Figure 10]
[Figure 11]
[Figure 12]
[Figure 13]
(175K) top
Crystal data top
3(C3H10P)·Cl5Sb·Cl4SbDx = 1.757 Mg m3
Mr = 793.79Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 54675 reflections
a = 14.842 (3) Åθ = 3.9–43.9°
b = 9.3475 (19) ŵ = 2.76 mm1
c = 21.624 (4) ÅT = 175 K
V = 3000.1 (10) Å3Prism, colourles
Z = 40.25 × 0.17 × 0.17 mm
F(000) = 1536
Data collection top
Radiation source: fine-focus sealed tube10215 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
Absorption correction: multi-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
θmax = 43.9°, θmin = 3.9°
Tmin = 0.56, Tmax = 0.63h = 1728
54675 measured reflectionsk = 1717
16806 independent reflectionsl = 3630
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)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.061 w = 1/[σ2(Fo2) + (0.028P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max = 0.027
16806 reflectionsΔρmax = 1.32 e Å3
275 parametersΔρmin = 1.31 e Å3
40 restraintsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 6577 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.48 (1)
Crystal data top
3(C3H10P)·Cl5Sb·Cl4SbV = 3000.1 (10) Å3
Mr = 793.79Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 14.842 (3) ŵ = 2.76 mm1
b = 9.3475 (19) ÅT = 175 K
c = 21.624 (4) Å0.25 × 0.17 × 0.17 mm
Data collection top
Absorption correction: multi-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
16806 independent reflections
Tmin = 0.56, Tmax = 0.6310215 reflections with I > 2σ(I)
54675 measured reflectionsRint = 0.041
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.061Δρmax = 1.32 e Å3
S = 0.94Δρmin = 1.31 e Å3
16806 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881, 6577 Friedel pairs
275 parametersAbsolute structure parameter: 0.48 (1)
40 restraints
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*/Ueq
Sb10.868146 (9)0.502076 (12)0.771895 (7)0.02757 (3)
Sb20.851422 (9)0.492172 (11)0.953298 (6)0.02600 (3)
Cl10.83779 (3)0.71555 (5)0.86443 (3)0.03507 (10)
Cl30.99641 (4)0.39562 (6)0.89204 (3)0.04123 (12)
Cl20.75835 (4)0.32016 (6)0.83404 (4)0.05077 (15)
Cl120.96900 (4)0.68021 (6)0.71659 (3)0.03810 (11)
Cl110.73589 (4)0.59855 (5)0.72251 (3)0.03766 (11)
Cl130.88782 (4)0.33077 (6)0.68513 (3)0.04269 (13)
Cl220.94898 (3)0.65232 (5)1.00883 (3)0.03596 (10)
Cl210.71255 (3)0.59416 (6)1.00994 (3)0.03866 (11)
Cl230.86955 (4)0.31075 (6)1.03697 (3)0.03991 (12)
P11.03722 (4)0.00601 (6)0.87499 (3)0.03608 (13)
C111.08503 (16)0.1668 (3)0.86552 (15)0.0464 (5)
H11A1.1259 (19)0.168 (3)0.8331 (12)0.070*
H11B1.1247 (19)0.190 (3)0.9041 (11)0.070*
H11C1.0437 (15)0.241 (3)0.8640 (14)0.070*
C120.9754 (2)0.0124 (2)0.94499 (15)0.0530 (7)
H12A0.93060.06160.94490.080*
H12B0.94660.10390.94870.080*
H12C1.01560.00150.97920.080*
C130.9677 (3)0.0468 (4)0.81157 (17)0.0751 (11)
H13A0.93660.13500.81930.113*
H13B0.92470.02870.80580.113*
H13C1.00400.05620.77500.113*
P20.68769 (4)0.98294 (6)1.02823 (3)0.03452 (12)
C230.78894 (16)0.9489 (2)1.06940 (11)0.0365 (5)
H23B0.7804 (19)0.942 (3)1.1114 (11)0.055*
H23A0.8211 (18)0.869 (2)1.0530 (11)0.055*
H23C0.829 (2)1.034 (2)1.0622 (13)0.055*
C220.63161 (16)1.1378 (3)1.05551 (13)0.0439 (6)
H22A0.67051.21921.05120.066*
H22B0.61621.12531.09830.066*
H22C0.57771.15281.03180.066*
C210.7117 (2)0.9999 (3)0.94782 (14)0.0589 (9)
H21A0.753 (2)1.079 (3)0.9424 (18)0.088*
H21B0.744 (2)0.915 (2)0.9316 (17)0.088*
H21C0.659 (2)1.013 (3)0.929 (2)0.088*
P30.69312 (4)0.97587 (6)0.69695 (3)0.03122 (11)
C310.68749 (19)0.9687 (2)0.77891 (12)0.0396 (5)
H31C0.6293 (15)0.970 (3)0.7875 (17)0.059*
H31B0.7186 (18)0.887 (2)0.7955 (14)0.059*
H31A0.7196 (19)1.054 (2)0.7956 (14)0.059*
C320.64301 (19)1.1368 (4)0.66985 (16)0.0528 (7)
H32A0.6726 (19)1.213 (3)0.6847 (14)0.079*
H32B0.643 (2)1.135 (4)0.6240 (12)0.079*
H32C0.5803 (19)1.135 (3)0.6815 (13)0.079*
C330.80679 (18)0.9653 (3)0.67134 (13)0.0450 (6)
H33C0.843 (2)1.049 (3)0.6852 (13)0.067*
H33A0.830 (2)0.883 (3)0.6861 (13)0.067*
H33B0.805 (2)0.971 (3)0.6268 (11)0.067*
H3P0.644 (2)0.863 (3)0.6713 (15)0.067*
H2P0.639 (2)0.874 (3)1.0360 (14)0.067*
H1P1.106 (2)0.093 (3)0.8848 (13)0.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.02843 (5)0.02350 (6)0.03079 (7)0.00097 (4)0.00381 (5)0.00124 (5)
Sb20.02703 (5)0.02250 (6)0.02846 (7)0.00034 (4)0.00023 (5)0.00070 (5)
Cl10.0389 (3)0.0298 (2)0.0366 (2)0.00180 (17)0.0044 (2)0.0010 (2)
Cl30.0327 (2)0.0355 (2)0.0554 (3)0.00407 (19)0.0017 (2)0.0053 (2)
Cl20.0393 (3)0.0317 (3)0.0812 (4)0.0079 (2)0.0080 (3)0.0043 (3)
Cl120.0354 (2)0.0367 (3)0.0422 (3)0.00196 (19)0.0012 (2)0.0030 (2)
Cl110.0377 (3)0.0343 (2)0.0410 (3)0.00774 (19)0.0101 (2)0.0065 (2)
Cl130.0475 (3)0.0335 (3)0.0471 (3)0.0054 (2)0.0023 (2)0.0140 (2)
Cl220.0352 (2)0.0303 (2)0.0423 (3)0.00344 (18)0.0049 (2)0.0030 (2)
Cl210.0337 (2)0.0415 (3)0.0407 (3)0.00604 (19)0.0043 (2)0.0006 (2)
Cl230.0501 (3)0.0287 (2)0.0409 (3)0.0020 (2)0.0034 (2)0.0081 (2)
P10.0326 (3)0.0340 (3)0.0417 (4)0.0055 (2)0.0048 (2)0.0045 (2)
C110.0353 (12)0.0482 (12)0.0558 (14)0.0106 (9)0.0027 (11)0.0111 (13)
C120.0638 (18)0.0355 (12)0.0599 (18)0.0005 (10)0.0257 (15)0.0088 (11)
C130.114 (3)0.0471 (16)0.065 (2)0.0119 (18)0.027 (2)0.0006 (15)
P20.0293 (3)0.0334 (3)0.0408 (3)0.00089 (19)0.0014 (2)0.0095 (2)
C230.0423 (12)0.0329 (11)0.0344 (12)0.0039 (9)0.0013 (9)0.0027 (9)
C220.0410 (12)0.0442 (13)0.0464 (15)0.0125 (10)0.0037 (10)0.0097 (11)
C210.0619 (17)0.084 (2)0.0309 (14)0.0357 (14)0.0109 (14)0.0150 (13)
P30.0339 (3)0.0304 (2)0.0294 (3)0.00254 (19)0.0029 (2)0.0041 (2)
C310.0578 (15)0.0313 (10)0.0298 (12)0.0008 (9)0.0050 (11)0.0005 (9)
C320.0451 (14)0.0565 (16)0.0568 (18)0.0107 (11)0.0018 (12)0.0244 (14)
C330.0419 (13)0.0393 (12)0.0537 (17)0.0016 (10)0.0066 (11)0.0115 (11)
Geometric parameters (Å, º) top
Sb1—Cl112.4097 (6)P2—C211.782 (3)
Sb1—Cl132.4839 (7)P2—H2P1.26 (3)
Sb1—Cl122.5385 (6)C23—H23B0.92 (2)
Sb1—Cl22.7117 (7)C23—H23A0.96 (2)
Sb1—Cl12.8616 (7)C23—H23C1.01 (2)
Sb2—Cl222.4041 (6)C22—H22A0.9600
Sb2—Cl232.4944 (7)C22—H22B0.9600
Sb2—Cl212.5802 (6)C22—H22C0.9600
Sb2—Cl32.6833 (7)C21—H21A0.97 (3)
Sb2—Cl12.8448 (7)C21—H21B0.99 (3)
P1—C131.758 (3)C21—H21C0.88 (3)
P1—C121.771 (3)P3—C311.775 (3)
P1—C111.776 (2)P3—C331.778 (3)
P1—H1P1.32 (3)P3—C321.777 (3)
C11—H11A0.93 (2)P3—H3P1.40 (3)
C11—H11B1.04 (2)C31—H31C0.88 (2)
C11—H11C0.93 (2)C31—H31B0.96 (2)
C12—H12A0.9600C31—H31A1.00 (2)
C12—H12B0.9600C32—H32A0.89 (2)
C12—H12C0.9600C32—H32B0.99 (3)
C13—H13A0.9600C32—H32C0.96 (3)
C13—H13B0.9600C33—H33C0.99 (2)
C13—H13C0.9600C33—H33A0.90 (2)
P2—C221.771 (2)C33—H33B0.96 (2)
P2—C231.775 (2)
Cl11—Sb1—Cl1390.13 (2)C23—P2—C21109.63 (14)
Cl11—Sb1—Cl1291.50 (2)C22—P2—H2P110.6 (15)
Cl13—Sb1—Cl1289.87 (2)C23—P2—H2P105.7 (14)
Cl11—Sb1—Cl287.98 (2)C21—P2—H2P108.4 (14)
Cl13—Sb1—Cl292.33 (2)P2—C23—H23B113.0 (19)
Cl12—Sb1—Cl2177.74 (2)P2—C23—H23A112.1 (16)
Cl11—Sb1—Cl185.448 (19)H23B—C23—H23A112 (2)
Cl13—Sb1—Cl1175.03 (2)P2—C23—H23C106.3 (18)
Cl12—Sb1—Cl187.99 (2)H23B—C23—H23C107 (2)
Cl2—Sb1—Cl189.78 (2)H23A—C23—H23C105.5 (19)
Cl22—Sb2—Cl2389.77 (3)P2—C22—H22A109.5
Cl22—Sb2—Cl2190.80 (2)P2—C22—H22B109.5
Cl23—Sb2—Cl2189.60 (2)H22A—C22—H22B109.5
Cl22—Sb2—Cl388.45 (2)P2—C22—H22C109.5
Cl23—Sb2—Cl392.46 (2)H22A—C22—H22C109.5
Cl21—Sb2—Cl3177.807 (19)H22B—C22—H22C109.5
Cl22—Sb2—Cl185.60 (2)P2—C21—H21A108 (2)
Cl23—Sb2—Cl1175.28 (2)P2—C21—H21B112 (2)
Cl21—Sb2—Cl189.58 (2)H21A—C21—H21B105 (3)
Cl3—Sb2—Cl188.31 (2)P2—C21—H21C106 (3)
Sb2—Cl1—Sb187.10 (2)H21A—C21—H21C113 (3)
C13—P1—C12110.84 (19)H21B—C21—H21C112 (3)
C13—P1—C11109.98 (16)C31—P3—C32109.97 (14)
C12—P1—C11109.65 (13)C31—P3—C33110.69 (14)
C13—P1—H1P116.4 (13)C32—P3—C33109.95 (13)
C12—P1—H1P104.0 (13)C31—P3—H3P110.1 (14)
C11—P1—H1P105.6 (13)C32—P3—H3P107.0 (14)
P1—C11—H11A110.8 (19)C33—P3—H3P109.1 (13)
P1—C11—H11B108.7 (17)P3—C31—H31C105 (2)
H11A—C11—H11B103.5 (19)P3—C31—H31B112.2 (18)
P1—C11—H11C114.9 (18)H31C—C31—H31B114 (2)
H11A—C11—H11C114 (2)P3—C31—H31A108.0 (17)
H11B—C11—H11C104 (2)H31C—C31—H31A112 (2)
P1—C12—H12A109.5H31B—C31—H31A106 (2)
P1—C12—H12B109.5P3—C32—H32A110 (2)
H12A—C12—H12B109.5P3—C32—H32B108 (2)
P1—C12—H12C109.5H32A—C32—H32B112 (3)
H12A—C12—H12C109.5P3—C32—H32C108 (2)
H12B—C12—H12C109.5H32A—C32—H32C113 (2)
P1—C13—H13A109.5H32B—C32—H32C105 (2)
P1—C13—H13B109.5P3—C33—H33C112 (2)
H13A—C13—H13B109.5P3—C33—H33A107 (2)
P1—C13—H13C109.5H33C—C33—H33A111 (2)
H13A—C13—H13C109.5P3—C33—H33B107 (2)
H13B—C13—H13C109.5H33C—C33—H33B105 (2)
C22—P2—C23112.17 (12)H33A—C33—H33B114 (2)
C22—P2—C21110.27 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C31—H31B···Cl10.96 (2)2.81 (2)3.741 (3)162 (2)
C21—H21B···Cl10.99 (3)2.74 (3)3.717 (3)168 (3)
C31—H31A···Cl2i1.00 (2)2.69 (2)3.650 (3)163 (2)
C33—H33C···Cl13i0.99 (2)2.72 (3)3.634 (3)154 (2)
C33—H33B···Cl21ii0.96 (2)2.79 (3)3.703 (3)159 (2)
C23—H23B···Cl11iii0.92 (2)2.82 (2)3.613 (3)145 (2)
C23—H23C···Cl23i1.01 (2)2.71 (2)3.656 (2)157 (3)
C21—H21C···Cl3iv0.88 (3)2.69 (3)3.552 (3)167 (3)
C11—H11B···Cl21v1.04 (2)2.78 (2)3.714 (3)149 (2)
P3—H3P···Cl12iv1.40 (3)2.81 (3)3.6571 (10)117 (2)
P1—H1P···Cl2v1.32 (3)2.64 (3)3.7679 (11)142 (2)
Symmetry codes: (i) x, y+1, z; (ii) x+3/2, y+1/2, z1/2; (iii) x+3/2, y+1/2, z+1/2; (iv) x1/2, y+3/2, z; (v) x+1/2, y+1/2, z.
(295K) top
Crystal data top
3(C3H10P)·Cl9Sb2Dx = 1.709 Mg m3
Mr = 793.81Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnamCell parameters from 4162 reflections
a = 15.070 (3) Åθ = 3.2–29.4°
b = 9.3026 (19) ŵ = 2.68 mm1
c = 22.008 (4) ÅT = 295 K
V = 3085.3 (11) Å3Prism, colourles
Z = 40.25 × 0.17 × 0.17 mm
F(000) = 1536
Data collection top
Radiation source: fine-focus sealed tube2130 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.037
Absorption correction: multi-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
θmax = 29.4°, θmin = 3.2°
Tmin = 0.58, Tmax = 0.64h = 2020
36684 measured reflectionsk = 1212
4156 independent reflectionsl = 2929
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)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107 w = 1/[σ2(Fo2) + (0.0347P)2 + 1.255P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.002
4156 reflectionsΔρmax = 0.56 e Å3
129 parametersΔρmin = 0.54 e Å3
6 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0023 (2)
Crystal data top
3(C3H10P)·Cl9Sb2V = 3085.3 (11) Å3
Mr = 793.81Z = 4
Orthorhombic, PnamMo Kα radiation
a = 15.070 (3) ŵ = 2.68 mm1
b = 9.3026 (19) ÅT = 295 K
c = 22.008 (4) Å0.25 × 0.17 × 0.17 mm
Data collection top
Absorption correction: multi-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
4156 independent reflections
Tmin = 0.58, Tmax = 0.642130 reflections with I > 2σ(I)
36684 measured reflectionsRint = 0.037
Refinement top
R[F2 > 2σ(F2)] = 0.0316 restraints
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.56 e Å3
4156 reflectionsΔρmin = 0.54 e Å3
129 parameters
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)
Sb10.651921 (19)0.49571 (2)0.838482 (12)0.05549 (13)
Cl10.68062 (12)0.27704 (17)0.75000.0771 (5)
Cl20.74978 (16)0.6770 (3)0.77004 (14)0.1003 (14)0.50
Cl30.51205 (14)0.5815 (2)0.76919 (11)0.0854 (11)0.50
Cl110.78634 (8)0.41039 (14)0.89209 (6)0.0856 (4)
Cl120.55617 (9)0.32562 (14)0.89428 (6)0.0888 (4)
Cl130.62685 (9)0.67931 (14)0.91890 (6)0.0930 (4)
P10.97405 (14)0.50818 (19)0.75000.0855 (6)
C11A1.0553 (10)0.5380 (14)0.8054 (6)0.109 (4)*0.50
C11B1.0059 (12)0.5542 (17)0.8230 (7)0.126 (5)*0.50
C120.9297 (5)0.3298 (7)0.75000.086 (2)
P20.32392 (9)0.48936 (13)0.91547 (6)0.0760 (4)
C210.3137 (7)0.4896 (5)0.8368 (2)0.120 (3)
H21A0.27440.56550.82470.179*
H21B0.29020.39890.82360.179*
H21C0.37100.50450.81880.179*
C220.3732 (4)0.6475 (7)0.9411 (3)0.123 (2)
H22A0.34050.72860.92610.185*
H22B0.43320.65230.92650.185*
H22C0.37320.64870.98470.185*
C230.2206 (4)0.4606 (6)0.9500 (3)0.1004 (17)
H23A0.191 (3)0.377 (3)0.936 (2)0.151*
H23B0.224 (4)0.459 (4)0.9931 (8)0.151*
H23C0.188 (3)0.544 (3)0.938 (2)0.151*
H1P0.90250.60680.75000.151*
H2P0.37920.38430.94120.151*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.0581 (2)0.04964 (18)0.0588 (2)0.00152 (13)0.00503 (12)0.00207 (12)
Cl10.0812 (11)0.0598 (9)0.0902 (11)0.0069 (8)0.0000.000
Cl20.0757 (14)0.0690 (13)0.156 (4)0.0162 (11)0.0032 (15)0.0022 (15)
Cl30.0621 (12)0.0728 (13)0.121 (3)0.0037 (10)0.0105 (12)0.0055 (13)
Cl110.0811 (8)0.0878 (9)0.0880 (8)0.0163 (7)0.0159 (7)0.0115 (7)
Cl120.0861 (9)0.0861 (8)0.0941 (8)0.0042 (7)0.0042 (7)0.0085 (7)
Cl130.1001 (9)0.0771 (8)0.1018 (9)0.0168 (7)0.0099 (8)0.0312 (7)
P10.0755 (13)0.0688 (11)0.1122 (16)0.0030 (9)0.0000.000
C120.087 (5)0.071 (4)0.101 (5)0.020 (4)0.0000.000
P20.0730 (8)0.0811 (9)0.0738 (8)0.0073 (6)0.0019 (6)0.0121 (6)
C210.180 (7)0.121 (6)0.058 (3)0.037 (4)0.013 (4)0.011 (3)
C220.098 (4)0.145 (5)0.127 (5)0.029 (4)0.007 (4)0.049 (4)
C230.109 (4)0.099 (4)0.093 (4)0.007 (3)0.007 (4)0.007 (3)
Geometric parameters (Å, º) top
Sb1—Cl122.4686 (13)C11A—C11B0.853 (18)
Sb1—Cl112.4749 (13)P2—C211.737 (5)
Sb1—Cl132.4884 (13)P2—C221.742 (6)
Sb1—Cl22.699 (3)P2—C231.753 (6)
Sb1—Cl32.721 (2)P2—H2P1.4028
Sb1—Cl12.8491 (12)C21—H21A0.9600
Cl1—Sb1i2.8491 (12)C21—H21B0.9600
Cl2—Cl2i0.882 (6)C21—H21C0.9600
Cl3—Cl3i0.845 (5)C22—H22A0.9600
P1—C11Bi1.730 (16)C22—H22B0.9600
P1—C11B1.730 (16)C22—H22C0.9600
P1—C11Ai1.749 (14)C23—H23A0.95 (3)
P1—C11A1.749 (14)C23—H23B0.96 (3)
P1—C121.789 (7)C23—H23C0.96 (3)
P1—H1P1.4164
Cl12—Sb1—Cl1192.05 (5)C11A—P1—H1P115.5
Cl12—Sb1—Cl1389.85 (5)C12—P1—H1P108.4
Cl11—Sb1—Cl1390.31 (4)C11B—C11A—P174.6 (16)
Cl12—Sb1—Cl2175.79 (7)C11A—C11B—P177.0 (16)
Cl11—Sb1—Cl291.10 (7)C21—P2—C22111.0 (3)
Cl13—Sb1—Cl292.93 (7)C21—P2—C23110.7 (4)
Cl12—Sb1—Cl390.80 (6)C22—P2—C23111.6 (3)
Cl11—Sb1—Cl3174.36 (6)C21—P2—H2P117.1
Cl13—Sb1—Cl394.57 (6)C22—P2—H2P101.8
Cl2—Sb1—Cl385.83 (8)C23—P2—H2P104.3
Cl12—Sb1—Cl188.34 (5)P2—C21—H21A109.5
Cl11—Sb1—Cl188.43 (4)P2—C21—H21B109.5
Cl13—Sb1—Cl1177.76 (4)H21A—C21—H21B109.5
Cl2—Sb1—Cl188.95 (7)P2—C21—H21C109.5
Cl3—Sb1—Cl186.79 (6)H21A—C21—H21C109.5
Sb1—Cl1—Sb1i86.23 (5)H21B—C21—H21C109.5
Cl2i—Cl2—Sb1123.92 (6)P2—C22—H22A109.5
Cl3i—Cl3—Sb1124.08 (5)P2—C22—H22B109.5
C11Bi—P1—C11B136.4 (12)H22A—C22—H22B109.5
C11B—P1—C11Ai114.4 (9)P2—C22—H22C109.5
C11Bi—P1—C11A114.4 (9)H22A—C22—H22C109.5
C11Bi—P1—C12109.5 (6)H22B—C22—H22C109.5
C11B—P1—C12109.5 (6)P2—C23—H23A114 (3)
C11Ai—P1—C12114.1 (5)P2—C23—H23B112 (4)
C11A—P1—C12114.1 (5)H23A—C23—H23B110 (3)
C11Bi—P1—H1P92.9P2—C23—H23C102 (3)
C11B—P1—H1P92.9H23A—C23—H23C110 (4)
C11Ai—P1—H1P115.5H23B—C23—H23C108 (4)
Symmetry code: (i) x, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C21—H21C···Cl30.962.493.447 (9)171
C21—H21B···Cl1ii0.962.833.719 (7)154
C21—H21A···Cl2iii0.962.713.566 (7)149
C23—H23C···Cl13iii0.96 (3)2.76 (2)3.699 (6)165 (4)
C23—H23B···Cl11iv0.95 (1)2.81 (3)3.679 (6)153 (3)
P1—H1P···Cl21.422.433.753 (3)153
P1—H1P···Cl2i1.422.433.753 (3)153
Symmetry codes: (i) x, y, z+3/2; (ii) x1/2, y+1/2, z; (iii) x1/2, y+3/2, z; (iv) x+1, y+1, z+2.
(382K) top
Crystal data top
C18H60Cl18P6Sb4Dx = 1.637 Mg m3
Mr = 1587.67Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/mmcCell parameters from 6828 reflections
a = 9.1910 (13) Åθ = 2.6–26.7°
c = 22.011 (4) ŵ = 2.57 mm1
V = 1610.3 (4) Å3T = 382 K
Z = 1Prism, colourles
F(000) = 7680.25 × 0.17 × 0.17 mm
Data collection top
Radiation source: fine-focus sealed tube312 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Absorption correction: multi-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
θmax = 26.7°, θmin = 2.6°
Tmin = 0.57, Tmax = 0.64h = 1111
6828 measured reflectionsk = 118
680 independent reflectionsl = 1227
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullPrimary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.053Secondary atom site location: difference Fourier map
wR(F2) = 0.169 w = 1/[σ2(Fo2) + (0.070P)2 + 2.750P]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.015
680 reflectionsΔρmax = 0.31 e Å3
34 parametersΔρmin = 0.43 e Å3
Crystal data top
C18H60Cl18P6Sb4Z = 1
Mr = 1587.67Mo Kα radiation
Hexagonal, P63/mmcµ = 2.57 mm1
a = 9.1910 (13) ÅT = 382 K
c = 22.011 (4) Å0.25 × 0.17 × 0.17 mm
V = 1610.3 (4) Å3
Data collection top
Absorption correction: multi-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
680 independent reflections
Tmin = 0.57, Tmax = 0.64312 reflections with I > 2σ(I)
6828 measured reflectionsRint = 0.031
Refinement top
R[F2 > 2σ(F2)] = 0.05334 parameters
wR(F2) = 0.1690 restraints
S = 0.99Δρmax = 0.31 e Å3
680 reflectionsΔρmin = 0.43 e Å3
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)
Sb10.66670.33330.16271 (4)0.1208 (4)
Cl110.4174 (5)0.2087 (3)0.0997 (2)0.305 (2)
Cl10.5294 (2)0.0588 (5)0.25000.279 (3)
P10.00000.00000.25000.196 (3)
C110.103 (3)0.206 (5)0.2740 (19)0.255 (18)*0.33
C120.00000.00000.166 (2)0.30 (3)0.50
P20.66670.33330.0872 (3)0.178 (2)
C210.7727 (12)0.545 (2)0.0614 (11)0.264 (10)0.67
C220.66670.33330.1635 (9)0.271 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.1203 (4)0.1203 (4)0.1219 (7)0.0601 (2)0.0000.000
Cl110.222 (3)0.400 (5)0.235 (3)0.1110 (15)0.108 (3)0.0542 (13)
Cl10.335 (6)0.103 (3)0.321 (7)0.0514 (13)0.0000.000
P10.168 (4)0.168 (4)0.251 (9)0.0841 (18)0.0000.000
C120.34 (5)0.34 (5)0.20 (5)0.17 (2)0.0000.000
P20.183 (3)0.183 (3)0.168 (4)0.0913 (14)0.0000.000
C210.280 (17)0.181 (16)0.30 (2)0.090 (8)0.038 (9)0.077 (18)
C220.34 (3)0.34 (3)0.140 (17)0.168 (13)0.0000.000
Geometric parameters (Å, º) top
Sb1—Cl11i2.421 (4)P1—C11vii1.72 (4)
Sb1—Cl112.421 (4)P1—C12v1.86 (5)
Sb1—Cl11ii2.421 (4)P1—C121.86 (5)
P1—C111.72 (4)C11—C11v1.05 (8)
P1—C11iii1.72 (4)P2—C221.68 (2)
P1—C11iv1.72 (4)P2—C21ii1.780 (19)
P1—C11v1.72 (4)P2—C211.780 (19)
P1—C11vi1.72 (4)P2—C21i1.780 (19)
Cl11i—Sb1—Cl1190.44 (16)C11v—P1—C12v107.8 (14)
Cl11i—Sb1—Cl11ii90.44 (16)C11vi—P1—C12v72.2 (14)
Cl11—Sb1—Cl11ii90.44 (16)C11vii—P1—C12v107.8 (14)
C11—P1—C11iii123.2 (5)C11—P1—C12107.8 (14)
C11—P1—C11iv111.1 (13)C11iii—P1—C1272.2 (14)
C11iii—P1—C11v111.1 (13)C11iv—P1—C12107.8 (14)
C11iv—P1—C11v123.2 (5)C11v—P1—C1272.2 (14)
C11—P1—C11vi111.1 (13)C11vi—P1—C12107.8 (14)
C11iii—P1—C11vi123.2 (5)C11vii—P1—C1272.2 (14)
C11iv—P1—C11vi111.1 (13)C12v—P1—C12180.000 (2)
C11v—P1—C11vi123.2 (5)C11v—C11—P172.2 (14)
C11—P1—C11vii123.2 (5)C22—P2—C21ii108.6 (8)
C11iii—P1—C11vii111.1 (13)C22—P2—C21108.6 (8)
C11iv—P1—C11vii123.2 (5)C21ii—P2—C21110.4 (8)
C11v—P1—C11vii111.1 (13)C22—P2—C21i108.6 (8)
C11—P1—C12v72.2 (14)C21ii—P2—C21i110.4 (8)
C11iii—P1—C12v107.8 (14)C21—P2—C21i110.4 (8)
C11iv—P1—C12v72.2 (14)
Symmetry codes: (i) y+1, xy, z; (ii) x+y+1, x+1, z; (iii) y, xy, z+1/2; (iv) y, xy, z; (v) x, y, z+1/2; (vi) x+y, x, z; (vii) x+y, x, z+1/2.

Experimental details

(175K)(295K)(382K)
Crystal data
Chemical formula3(C3H10P)·Cl5Sb·Cl4Sb3(C3H10P)·Cl9Sb2C18H60Cl18P6Sb4
Mr793.79793.811587.67
Crystal system, space groupOrthorhombic, Pna21Orthorhombic, PnamHexagonal, P63/mmc
Temperature (K)175295382
a, b, c (Å)14.842 (3), 9.3475 (19), 21.624 (4)15.070 (3), 9.3026 (19), 22.008 (4)9.1910 (13), 9.1910 (13), 22.011 (4)
α, β, γ (°)90, 90, 9090, 90, 9090, 90, 120
V3)3000.1 (10)3085.3 (11)1610.3 (4)
Z441
Radiation typeMo KαMo KαMo Kα
µ (mm1)2.762.682.57
Crystal size (mm)0.25 × 0.17 × 0.170.25 × 0.17 × 0.170.25 × 0.17 × 0.17
Data collection
Diffractometer???
Absorption correctionMulti-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
Multi-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
Multi-scan
CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.6 (release 21-05-2007 CrysAlis171 .NET) (compiled May 21 2007,16:32:00) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
Tmin, Tmax0.56, 0.630.58, 0.640.57, 0.64
No. of measured, independent and
observed [I > 2σ(I)] reflections
54675, 16806, 10215 36684, 4156, 2130 6828, 680, 312
Rint0.0410.0370.031
(sin θ/λ)max1)0.9750.6920.633
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.061, 0.94 0.031, 0.107, 1.04 0.053, 0.169, 0.99
No. of reflections168064156680
No. of parameters27512934
No. of restraints4060
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement?
Δρmax, Δρmin (e Å3)1.32, 1.310.56, 0.540.31, 0.43
Absolute structureFlack H D (1983), Acta Cryst. A39, 876-881, 6577 Friedel pairs??
Absolute structure parameter0.48 (1)??

Computer programs: SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).

Hydrogen-bond geometry (Å, º) for (175K) top
D—H···AD—HH···AD···AD—H···A
C31—H31B···Cl10.96 (2)2.81 (2)3.741 (3)162 (2)
C21—H21B···Cl10.99 (3)2.74 (3)3.717 (3)168 (3)
C31—H31A···Cl2i1.00 (2)2.69 (2)3.650 (3)163 (2)
C33—H33C···Cl13i0.99 (2)2.72 (3)3.634 (3)154 (2)
C33—H33B···Cl21ii0.96 (2)2.79 (3)3.703 (3)159 (2)
C23—H23B···Cl11iii0.92 (2)2.82 (2)3.613 (3)145 (2)
C23—H23C···Cl23i1.01 (2)2.71 (2)3.656 (2)157 (3)
C21—H21C···Cl3iv0.88 (3)2.69 (3)3.552 (3)167 (3)
C11—H11B···Cl21v1.04 (2)2.78 (2)3.714 (3)149 (2)
P3—H3P···Cl12iv1.40 (3)2.81 (3)3.6571 (10)116.8 (17)
P1—H1P···Cl2v1.32 (3)2.64 (3)3.7679 (11)141.6 (18)
Symmetry codes: (i) x, y+1, z; (ii) x+3/2, y+1/2, z1/2; (iii) x+3/2, y+1/2, z+1/2; (iv) x1/2, y+3/2, z; (v) x+1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) for (295K) top
D—H···AD—HH···AD···AD—H···A
C21—H21C···Cl30.962.493.447 (9)171.3
C21—H21B···Cl1i0.962.833.719 (7)153.6
C21—H21A···Cl2ii0.962.713.566 (7)149.3
C23—H23C···Cl13ii0.96 (3)2.761 (16)3.699 (6)165 (4)
C23—H23B···Cl11iii0.952 (14)2.81 (3)3.679 (6)153 (3)
P1—H1P···Cl21.422.433.753 (3)153.4
P1—H1P···Cl2iv1.422.433.753 (3)153.4
Symmetry codes: (i) x1/2, y+1/2, z; (ii) x1/2, y+3/2, z; (iii) x+1, y+1, z+2; (iv) x, y, z+3/2.
 

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