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The crystal structures of the two isomers bis(1-phenylethylammonium) hexachloridostannate(IV) and bis(2-phenylethylammonium) hexachloridostannate(IV), both (C
8H
12N)
2[SnCl
6], exhibit alternating organic and inorganic layers, which interact
via N—H
Cl hydrogen bonding. The inorganic layer contains an extended two-dimensional hydrogen-bonded sheet. The Sn atom in the 1-phenylethylammonium salt lies on an inversion centre.
Supporting information
CCDC references: 641786; 641787
For the preparation of (I), 1-phenylethylamine (0.068 g, 0.561 mmol) was
combined with tin(II) chloride (0.054 g, 0.259 mmol) and dissolved in
concentrated HCl (5 ml, 0.057 mol, 33%, Aldrich). The resulting solution was
left open to the atmosphere and crystals grew by slow evaporation. A
colourless, plate-like crystal was selected for the X-ray diffraction study.
2-Phenylethylammonium chloride was prepared by the dropwise addition of excess
concentrated HCl (4.82 ml, 0.059 mol, 37%, Aldrich) to a solution of
2-phenylethylamine (2.4 ml, 0.020 mol, 99%, Aldrich) in chloroform (10 ml,
99%, Saarchem). The resulting precipitate was filtered off and left to dry.
Crystals of (II) were grown by slow evaporation from an aqueous solution of
stoichiometric amounts (1:2) of tin(II) chloride (0.065 g, 0.340 mmol) and
2-phenylethylammonium chloride (0.107 g, 0.679 mmol) to total dryness. A
colourless crystal was selected for the X-ray diffraction study.
H atoms were placed geometrically and refined in idealized positions in the
riding-model approximation, with C—H = 0.93 (ArH), 0.98 (CH), 0.97 (CH2)
and 0.96 Å (CH3) and N—H = 0.89 Å; Uiso(H) =
1.5Ueq(N), 1.5Ueq(C) for methyl H atoms and
1.2Ueq(C) for other H atoms. The highest residual peaks in the final
ΔF syntheses lie 1.07 Å from Cl2 in (I) and 1.67 Å from Cl5 in
(II). Location of deepest hole for (II)?
Data collection: SMART-NT (Bruker, 1998) for (I); CrysAlis CCD (Oxford Diffraction 2003) for (II). Cell refinement: SAINT-Plus (Bruker, 1999) for (I); CrysAlis CCD for (II). Data reduction: SAINT-Plus for (I); CrysAlis RED (Oxford Diffraction, 2003) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Diamond (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
(I) Bis(1-phenylethylammonium) hexachloridostannate(IV)
top
Crystal data top
(C8H12N)2[SnCl6] | F(000) = 572 |
Mr = 575.76 | Dx = 1.597 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 937 reflections |
a = 12.243 (2) Å | θ = 3.2–28.2° |
b = 7.1124 (13) Å | µ = 1.74 mm−1 |
c = 13.777 (3) Å | T = 293 K |
β = 93.697 (3)° | Plate, colourless |
V = 1197.2 (4) Å3 | 0.48 × 0.28 × 0.13 mm |
Z = 2 | |
Data collection top
Bruker APEX II CCD area-detector diffractometer | 1736 reflections with I > 2σ(I) |
ω scans | Rint = 0.067 |
Absorption correction: integration (XPREP; Bruker, 1999) | θmax = 25.5°, θmin = 1.7° |
Tmin = 0.443, Tmax = 0.821 | h = −14→14 |
6461 measured reflections | k = −5→8 |
2228 independent reflections | l = −16→16 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + 2.608P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.097 | (Δ/σ)max = 0.001 |
S = 1.30 | Δρmax = 0.96 e Å−3 |
2228 reflections | Δρmin = −0.50 e Å−3 |
103 parameters | |
Crystal data top
(C8H12N)2[SnCl6] | V = 1197.2 (4) Å3 |
Mr = 575.76 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.243 (2) Å | µ = 1.74 mm−1 |
b = 7.1124 (13) Å | T = 293 K |
c = 13.777 (3) Å | 0.48 × 0.28 × 0.13 mm |
β = 93.697 (3)° | |
Data collection top
Bruker APEX II CCD area-detector diffractometer | 2228 independent reflections |
Absorption correction: integration (XPREP; Bruker, 1999) | 1736 reflections with I > 2σ(I) |
Tmin = 0.443, Tmax = 0.821 | Rint = 0.067 |
6461 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.30 | Δρmax = 0.96 e Å−3 |
2228 reflections | Δρmin = −0.50 e Å−3 |
103 parameters | |
Special details top
Experimental. Numerical integration absorption corrections based on indexed crystal faces were
applied using the XPREP routine (Bruker, 1999) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.7645 (5) | 0.2771 (7) | 0.2768 (5) | 0.0612 (14) | |
H1F | 0.7052 | 0.1975 | 0.2533 | 0.092* | |
H1E | 0.7924 | 0.2341 | 0.3397 | 0.092* | |
H1D | 0.8217 | 0.2727 | 0.2324 | 0.092* | |
C2 | 0.7239 (4) | 0.4772 (6) | 0.2847 (4) | 0.0430 (10) | |
H2 | 0.6963 | 0.5181 | 0.2197 | 0.052* | |
C3 | 0.8111 (2) | 0.6143 (4) | 0.3215 (2) | 0.0432 (10) | |
C4 | 0.8496 (3) | 0.7438 (5) | 0.2563 (2) | 0.0631 (15) | |
H4 | 0.8184 | 0.7497 | 0.193 | 0.076* | |
C5 | 0.9347 (3) | 0.8645 (5) | 0.2857 (4) | 0.082 (2) | |
H5 | 0.9604 | 0.9512 | 0.2421 | 0.098* | |
C6 | 0.9812 (3) | 0.8557 (6) | 0.3803 (4) | 0.096 (3) | |
H6 | 1.0381 | 0.9365 | 0.4 | 0.115* | |
C7 | 0.9427 (3) | 0.7262 (7) | 0.4455 (3) | 0.099 (3) | |
H7 | 0.9738 | 0.7203 | 0.5088 | 0.119* | |
C8 | 0.8576 (3) | 0.6055 (6) | 0.4161 (2) | 0.0738 (18) | |
H8 | 0.8318 | 0.5188 | 0.4597 | 0.089* | |
N1 | 0.6295 (3) | 0.4797 (6) | 0.3499 (3) | 0.0455 (9) | |
H1A | 0.5785 | 0.3988 | 0.3275 | 0.068* | |
H1B | 0.6012 | 0.5948 | 0.3508 | 0.068* | |
H1C | 0.6533 | 0.4469 | 0.4099 | 0.068* | |
Sn1 | 0.5 | 0 | 0.5 | 0.03701 (15) | |
Cl1 | 0.40919 (10) | 0.28166 (16) | 0.43644 (9) | 0.0468 (3) | |
Cl2 | 0.44804 (10) | 0.07795 (18) | 0.66444 (8) | 0.0474 (3) | |
Cl3 | 0.67011 (10) | 0.17346 (18) | 0.52875 (9) | 0.0530 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.068 (4) | 0.045 (3) | 0.072 (4) | −0.005 (3) | 0.025 (3) | −0.006 (3) |
C2 | 0.048 (3) | 0.047 (3) | 0.034 (2) | −0.004 (2) | −0.0015 (19) | 0.0019 (19) |
C3 | 0.034 (2) | 0.038 (2) | 0.058 (3) | 0.0021 (19) | 0.007 (2) | 0.000 (2) |
C4 | 0.048 (3) | 0.050 (3) | 0.094 (5) | 0.003 (2) | 0.016 (3) | 0.008 (3) |
C5 | 0.058 (4) | 0.046 (3) | 0.146 (7) | −0.009 (3) | 0.034 (4) | −0.004 (4) |
C6 | 0.062 (4) | 0.069 (4) | 0.159 (9) | −0.021 (3) | 0.024 (5) | −0.048 (5) |
C7 | 0.080 (5) | 0.114 (6) | 0.102 (6) | −0.022 (5) | −0.007 (4) | −0.034 (5) |
C8 | 0.069 (4) | 0.086 (5) | 0.065 (4) | −0.021 (3) | −0.005 (3) | −0.003 (3) |
N1 | 0.039 (2) | 0.047 (2) | 0.051 (2) | −0.0008 (17) | 0.0062 (18) | −0.0026 (18) |
Sn1 | 0.0422 (3) | 0.0345 (2) | 0.0344 (2) | −0.00069 (18) | 0.00287 (17) | 0.00158 (17) |
Cl1 | 0.0517 (6) | 0.0403 (6) | 0.0485 (6) | 0.0066 (5) | 0.0042 (5) | 0.0064 (5) |
Cl2 | 0.0544 (7) | 0.0528 (7) | 0.0352 (6) | 0.0057 (5) | 0.0053 (5) | −0.0008 (5) |
Cl3 | 0.0525 (7) | 0.0564 (7) | 0.0491 (7) | −0.0153 (6) | −0.0049 (5) | 0.0103 (6) |
Geometric parameters (Å, º) top
C1—C2 | 1.514 (7) | C5—H5 | 0.93 |
C1—H1F | 0.96 | C6—C7 | 1.39 |
C1—H1E | 0.96 | C6—H6 | 0.93 |
C1—H1D | 0.96 | C7—C8 | 1.39 |
C2—N1 | 1.508 (6) | C7—H7 | 0.93 |
C2—C3 | 1.509 (5) | C8—H8 | 0.93 |
C2—H2 | 0.98 | N1—H1A | 0.89 |
C3—C4 | 1.39 | N1—H1B | 0.89 |
C3—C8 | 1.39 | N1—H1C | 0.89 |
C4—C5 | 1.39 | Sn1—Cl1 | 2.4270 (11) |
C4—H4 | 0.93 | Sn1—Cl3 | 2.4310 (12) |
C5—C6 | 1.39 | Sn1—Cl2 | 2.4557 (12) |
| | | |
C2—C1—H1F | 109.5 | C4—C5—H5 | 120 |
C2—C1—H1E | 109.5 | C5—C6—C7 | 120 |
H1F—C1—H1E | 109.5 | C5—C6—H6 | 120 |
C2—C1—H1D | 109.5 | C7—C6—H6 | 120 |
H1F—C1—H1D | 109.5 | C8—C7—C6 | 120 |
H1E—C1—H1D | 109.5 | C8—C7—H7 | 120 |
N1—C2—C3 | 110.2 (4) | C6—C7—H7 | 120 |
N1—C2—C1 | 108.8 (4) | C7—C8—C3 | 120 |
C3—C2—C1 | 113.8 (4) | C7—C8—H8 | 120 |
N1—C2—H2 | 108 | C3—C8—H8 | 120 |
C3—C2—H2 | 108 | C2—N1—H1A | 109.5 |
C1—C2—H2 | 108 | C2—N1—H1B | 109.5 |
C4—C3—C8 | 120 | H1A—N1—H1B | 109.5 |
C4—C3—C2 | 118.3 (3) | C2—N1—H1C | 109.5 |
C8—C3—C2 | 121.6 (3) | H1A—N1—H1C | 109.5 |
C5—C4—C3 | 120 | H1B—N1—H1C | 109.5 |
C5—C4—H4 | 120 | Cl1—Sn1—Cl2 | 90.38 (4) |
C3—C4—H4 | 120 | Cl1—Sn1—Cl3 | 90.44 (4) |
C6—C5—C4 | 120 | Cl2—Sn1—Cl3 | 90.30 (4) |
C6—C5—H5 | 120 | | |
| | | |
N1—C2—C3—C4 | −128.8 (3) | C3—C4—C5—C6 | 0 |
C1—C2—C3—C4 | 108.7 (4) | C4—C5—C6—C7 | 0 |
N1—C2—C3—C8 | 55.3 (4) | C5—C6—C7—C8 | 0 |
C1—C2—C3—C8 | −67.1 (5) | C6—C7—C8—C3 | 0 |
C8—C3—C4—C5 | 0 | C4—C3—C8—C7 | 0 |
C2—C3—C4—C5 | −175.9 (3) | C2—C3—C8—C7 | 175.8 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl2i | 0.89 | 2.68 | 3.302 (4) | 128 |
N1—H1A···Cl1 | 0.89 | 2.76 | 3.331 (4) | 123 |
N1—H1B···Cl2ii | 0.89 | 2.41 | 3.289 (4) | 170 |
N1—H1C···Cl3 | 0.89 | 2.54 | 3.302 (5) | 144 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1. |
(II) Bis(2-phenylethylammonium) hexachloridostannate(IV)
top
Crystal data top
(C8H12N)2[SnCl6] | F(000) = 1144 |
Mr = 575.76 | Dx = 1.695 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 763 reflections |
a = 7.335 (3) Å | θ = 2.4–31.3° |
b = 25.695 (4) Å | µ = 1.85 mm−1 |
c = 11.974 (2) Å | T = 293 K |
β = 90.03 (2)° | Plate, colourless |
V = 2256.8 (11) Å3 | 0.2 × 0.2 × 0.15 mm |
Z = 4 | |
Data collection top
Oxford Excalibur2 CCD area detector diffractometer | 3144 reflections with I > 2σ(I) |
ω–2θ scans ##AUTHOR: Please check diffractometer and scan type. | Rint = 0.038 |
Absorption correction: multi-scan (WinGX; Farrugia, 1999) | θmax = 25.5°, θmin = 4.2° |
Tmin = 0.709, Tmax = 0.753 | h = −5→8 |
14565 measured reflections | k = −31→31 |
4159 independent reflections | l = −14→14 |
Refinement top
Refinement on F2 | 150 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.050 | w = 1/[σ2(Fo2) + (0.049P)2 + 6.342P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.122 | (Δ/σ)max = 0.008 |
S = 1.05 | Δρmax = 1.01 e Å−3 |
4159 reflections | Δρmin = −1.00 e Å−3 |
202 parameters | |
Crystal data top
(C8H12N)2[SnCl6] | V = 2256.8 (11) Å3 |
Mr = 575.76 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.335 (3) Å | µ = 1.85 mm−1 |
b = 25.695 (4) Å | T = 293 K |
c = 11.974 (2) Å | 0.2 × 0.2 × 0.15 mm |
β = 90.03 (2)° | |
Data collection top
Oxford Excalibur2 CCD area detector diffractometer | 4159 independent reflections |
Absorption correction: multi-scan (WinGX; Farrugia, 1999) | 3144 reflections with I > 2σ(I) |
Tmin = 0.709, Tmax = 0.753 | Rint = 0.038 |
14565 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 150 restraints |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.01 e Å−3 |
4159 reflections | Δρmin = −1.00 e Å−3 |
202 parameters | |
Special details top
Experimental. absorption corrections were made in the WinGX suite of programs
(Blessing, 1995). |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.2106 (10) | 0.6086 (3) | 0.3904 (6) | 0.0605 (18) | |
H1A1 | 0.2166 | 0.6256 | 0.4626 | 0.073* | |
H1A2 | 0.0859 | 0.611 | 0.3639 | 0.073* | |
C2A | 0.3343 (11) | 0.6371 (3) | 0.3094 (7) | 0.075 (2) | |
H2A1 | 0.4572 | 0.6377 | 0.3394 | 0.09* | |
H2A2 | 0.3375 | 0.6182 | 0.2392 | 0.09* | |
C3A | 0.2734 (6) | 0.69113 (14) | 0.2883 (4) | 0.0560 (15) | |
C4A | 0.3153 (6) | 0.73071 (19) | 0.3631 (3) | 0.0579 (16) | |
H4A | 0.3712 | 0.7228 | 0.4308 | 0.069* | |
C5A | 0.2737 (7) | 0.78205 (17) | 0.3369 (5) | 0.0690 (18) | |
H5A | 0.3018 | 0.8085 | 0.387 | 0.083* | |
C6A | 0.1901 (7) | 0.79381 (17) | 0.2358 (5) | 0.080 (2) | |
H6A | 0.1623 | 0.8282 | 0.2182 | 0.095* | |
C7A | 0.1482 (7) | 0.7542 (2) | 0.1609 (4) | 0.077 (2) | |
H7A | 0.0923 | 0.7621 | 0.0933 | 0.093* | |
C8A | 0.1898 (7) | 0.7029 (2) | 0.1872 (4) | 0.0720 (18) | |
H8A | 0.1617 | 0.6764 | 0.1371 | 0.086* | |
N1 | 0.2597 (8) | 0.5529 (2) | 0.4041 (5) | 0.0558 (15) | |
H1A | 0.1835 | 0.538 | 0.4523 | 0.084* | |
H1B | 0.3732 | 0.5505 | 0.4298 | 0.084* | |
H1C | 0.2518 | 0.5369 | 0.3384 | 0.084* | |
C1B | 0.7207 (17) | 0.6267 (3) | 0.9090 (8) | 0.103 (3) | |
H1B1 | 0.5928 | 0.6328 | 0.8932 | 0.124* | |
H1B2 | 0.7902 | 0.6405 | 0.8467 | 0.124* | |
C2B | 0.7709 (19) | 0.6569 (4) | 1.0121 (9) | 0.121 (3) | |
H2B1 | 0.6989 | 0.6445 | 1.0745 | 0.146* | |
H2B2 | 0.8984 | 0.6509 | 1.0294 | 0.146* | |
C3B | 0.7403 (8) | 0.71276 (15) | 0.9977 (5) | 0.081 (2) | |
C4B | 0.6669 (8) | 0.7335 (2) | 1.0950 (4) | 0.079 (2) | |
H4B | 0.6245 | 0.7115 | 1.1509 | 0.095* | |
C5B | 0.6570 (7) | 0.7871 (2) | 1.1088 (4) | 0.0745 (19) | |
H5B | 0.6079 | 0.801 | 1.174 | 0.089* | |
C6B | 0.7204 (7) | 0.82003 (15) | 1.0253 (5) | 0.0720 (19) | |
H6B | 0.7138 | 0.8559 | 1.0346 | 0.086* | |
C7B | 0.7938 (7) | 0.7993 (2) | 0.9280 (4) | 0.0676 (18) | |
H7B | 0.8362 | 0.8213 | 0.8721 | 0.081* | |
C8B | 0.8037 (7) | 0.7457 (2) | 0.9142 (4) | 0.0695 (18) | |
H8B | 0.8528 | 0.7318 | 0.849 | 0.083* | |
N2 | 0.7513 (8) | 0.5700 (2) | 0.9146 (5) | 0.0540 (15) | |
H2A | 0.7143 | 0.5553 | 0.8512 | 0.081* | |
H2B | 0.6886 | 0.5567 | 0.9715 | 0.081* | |
H2C | 0.8696 | 0.5637 | 0.9245 | 0.081* | |
Sn1 | 0.24446 (5) | 0.516656 (16) | 0.75527 (3) | 0.03282 (15) | |
Cl1 | 0.4767 (2) | 0.56867 (7) | 0.66429 (14) | 0.0504 (4) | |
Cl2 | 0.0129 (2) | 0.46313 (7) | 0.84425 (14) | 0.0481 (4) | |
Cl3 | 0.4835 (2) | 0.46809 (6) | 0.85029 (13) | 0.0448 (4) | |
Cl4 | 0.0030 (2) | 0.56365 (7) | 0.66037 (14) | 0.0489 (4) | |
Cl5 | 0.2577 (2) | 0.45597 (7) | 0.59993 (13) | 0.0481 (4) | |
Cl6 | 0.2341 (2) | 0.57647 (7) | 0.91037 (13) | 0.0468 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.065 (4) | 0.052 (3) | 0.064 (4) | 0.008 (3) | 0.011 (4) | 0.010 (3) |
C2A | 0.068 (4) | 0.054 (3) | 0.105 (5) | 0.002 (3) | 0.027 (4) | 0.010 (3) |
C3A | 0.045 (3) | 0.049 (3) | 0.074 (4) | 0.003 (3) | 0.015 (3) | 0.003 (3) |
C4A | 0.046 (4) | 0.056 (3) | 0.071 (4) | 0.004 (3) | 0.004 (3) | 0.002 (3) |
C5A | 0.057 (4) | 0.050 (3) | 0.100 (5) | 0.000 (3) | 0.008 (4) | −0.005 (4) |
C6A | 0.063 (4) | 0.070 (4) | 0.105 (5) | 0.007 (4) | 0.017 (4) | 0.029 (3) |
C7A | 0.054 (4) | 0.104 (5) | 0.075 (4) | 0.005 (4) | 0.004 (4) | 0.027 (3) |
C8A | 0.059 (4) | 0.086 (4) | 0.070 (4) | −0.004 (4) | 0.005 (3) | −0.005 (3) |
N1 | 0.067 (4) | 0.044 (3) | 0.056 (4) | −0.005 (3) | −0.003 (3) | 0.001 (3) |
C1B | 0.136 (7) | 0.050 (4) | 0.124 (7) | 0.004 (5) | −0.015 (6) | −0.011 (4) |
C2B | 0.169 (7) | 0.064 (4) | 0.132 (6) | −0.001 (5) | −0.024 (6) | −0.010 (4) |
C3B | 0.098 (5) | 0.052 (3) | 0.093 (5) | −0.001 (4) | −0.002 (4) | −0.008 (3) |
C4B | 0.075 (5) | 0.085 (4) | 0.077 (4) | −0.014 (4) | 0.003 (4) | 0.005 (4) |
C5B | 0.062 (4) | 0.091 (4) | 0.071 (4) | 0.010 (4) | −0.002 (4) | −0.025 (4) |
C6B | 0.061 (4) | 0.060 (4) | 0.095 (5) | 0.005 (4) | −0.016 (4) | −0.020 (3) |
C7B | 0.051 (4) | 0.067 (4) | 0.085 (4) | −0.007 (4) | −0.001 (3) | 0.009 (3) |
C8B | 0.061 (4) | 0.071 (4) | 0.077 (4) | 0.007 (4) | 0.010 (4) | −0.017 (3) |
N2 | 0.054 (3) | 0.050 (3) | 0.058 (4) | −0.002 (3) | 0.001 (3) | −0.002 (3) |
Sn1 | 0.0291 (2) | 0.0391 (2) | 0.0303 (2) | −0.00212 (19) | −0.00026 (15) | 0.00088 (18) |
Cl1 | 0.0431 (9) | 0.0618 (11) | 0.0462 (9) | −0.0168 (8) | 0.0086 (7) | 0.0063 (8) |
Cl2 | 0.0411 (9) | 0.0526 (10) | 0.0506 (10) | −0.0120 (8) | 0.0075 (7) | 0.0093 (8) |
Cl3 | 0.0401 (8) | 0.0473 (10) | 0.0469 (9) | 0.0081 (7) | −0.0103 (7) | 0.0022 (7) |
Cl4 | 0.0403 (9) | 0.0571 (11) | 0.0493 (10) | 0.0072 (8) | −0.0114 (7) | 0.0090 (8) |
Cl5 | 0.0563 (10) | 0.0502 (10) | 0.0379 (8) | −0.0030 (8) | 0.0003 (7) | −0.0128 (7) |
Cl6 | 0.0546 (10) | 0.0503 (10) | 0.0356 (8) | −0.0001 (8) | 0.0014 (7) | −0.0087 (7) |
Geometric parameters (Å, º) top
C1A—N1 | 1.485 (8) | C1B—H1B2 | 0.97 |
C1A—C2A | 1.517 (11) | C2B—C3B | 1.462 (11) |
C1A—H1A1 | 0.97 | C2B—H2B1 | 0.97 |
C1A—H1A2 | 0.97 | C2B—H2B2 | 0.97 |
C2A—C3A | 1.481 (8) | C3B—C4B | 1.39 |
C2A—H2A1 | 0.97 | C3B—C8B | 1.39 |
C2A—H2A2 | 0.97 | C4B—C5B | 1.39 |
C3A—C4A | 1.39 | C4B—H4B | 0.93 |
C3A—C8A | 1.39 | C5B—C6B | 1.39 |
C4A—C5A | 1.39 | C5B—H5B | 0.93 |
C4A—H4A | 0.93 | C6B—C7B | 1.39 |
C5A—C6A | 1.39 | C6B—H6B | 0.93 |
C5A—H5A | 0.93 | C7B—C8B | 1.39 |
C6A—C7A | 1.39 | C7B—H7B | 0.93 |
C6A—H6A | 0.93 | C8B—H8B | 0.93 |
C7A—C8A | 1.39 | N2—H2A | 0.89 |
C7A—H7A | 0.93 | N2—H2B | 0.89 |
C8A—H8A | 0.93 | N2—H2C | 0.89 |
N1—H1A | 0.89 | Sn1—Cl1 | 2.4244 (17) |
N1—H1B | 0.89 | Sn1—Cl2 | 2.4316 (16) |
N1—H1C | 0.89 | Sn1—Cl3 | 2.4342 (17) |
C1B—N2 | 1.477 (9) | Sn1—Cl4 | 2.4257 (17) |
C1B—C2B | 1.503 (11) | Sn1—Cl5 | 2.4291 (16) |
C1B—H1B1 | 0.97 | Sn1—Cl6 | 2.4118 (16) |
| | | |
N1—C1A—C2A | 113.0 (6) | C1B—C2B—H2B1 | 109.3 |
N1—C1A—H1A1 | 109 | C3B—C2B—H2B2 | 109.2 |
C2A—C1A—H1A1 | 109 | C1B—C2B—H2B2 | 109.2 |
N1—C1A—H1A2 | 109 | H2B1—C2B—H2B2 | 107.9 |
C2A—C1A—H1A2 | 109 | C4B—C3B—C8B | 120 |
H1A1—C1A—H1A2 | 107.8 | C4B—C3B—C2B | 109.7 (6) |
C3A—C2A—C1A | 112.4 (6) | C8B—C3B—C2B | 129.0 (6) |
C3A—C2A—H2A1 | 109.1 | C3B—C4B—C5B | 120 |
C1A—C2A—H2A1 | 109.1 | C3B—C4B—H4B | 120 |
C3A—C2A—H2A2 | 109.1 | C5B—C4B—H4B | 120 |
C1A—C2A—H2A2 | 109.1 | C6B—C5B—C4B | 120 |
H2A1—C2A—H2A2 | 107.9 | C6B—C5B—H5B | 120 |
C4A—C3A—C8A | 120 | C4B—C5B—H5B | 120 |
C4A—C3A—C2A | 120.6 (5) | C5B—C6B—C7B | 120 |
C8A—C3A—C2A | 119.0 (5) | C5B—C6B—H6B | 120 |
C3A—C4A—C5A | 120 | C7B—C6B—H6B | 120 |
C3A—C4A—H4A | 120 | C8B—C7B—C6B | 120 |
C5A—C4A—H4A | 120 | C8B—C7B—H7B | 120 |
C6A—C5A—C4A | 120 | C6B—C7B—H7B | 120 |
C6A—C5A—H5A | 120 | C7B—C8B—C3B | 120 |
C4A—C5A—H5A | 120 | C7B—C8B—H8B | 120 |
C7A—C6A—C5A | 120 | C3B—C8B—H8B | 120 |
C7A—C6A—H6A | 120 | C1B—N2—H2A | 109.5 |
C5A—C6A—H6A | 120 | C1B—N2—H2B | 109.5 |
C6A—C7A—C8A | 120 | H2A—N2—H2B | 109.5 |
C6A—C7A—H7A | 120 | C1B—N2—H2C | 109.5 |
C8A—C7A—H7A | 120 | H2A—N2—H2C | 109.5 |
C7A—C8A—C3A | 120 | H2B—N2—H2C | 109.5 |
C7A—C8A—H8A | 120 | Cl1—Sn1—Cl2 | 178.93 (6) |
C3A—C8A—H8A | 120 | Cl1—Sn1—Cl3 | 89.22 (7) |
C1A—N1—H1A | 109.5 | Cl1—Sn1—Cl4 | 91.61 (7) |
C1A—N1—H1B | 109.5 | Cl1—Sn1—Cl5 | 88.93 (6) |
H1A—N1—H1B | 109.5 | Cl1—Sn1—Cl6 | 90.98 (6) |
C1A—N1—H1C | 109.5 | Cl2—Sn1—Cl3 | 90.48 (6) |
H1A—N1—H1C | 109.5 | Cl2—Sn1—Cl4 | 88.68 (6) |
H1B—N1—H1C | 109.5 | Cl2—Sn1—Cl5 | 90.04 (6) |
N2—C1B—C2B | 115.8 (8) | Cl2—Sn1—Cl6 | 90.05 (6) |
N2—C1B—H1B1 | 108.3 | Cl3—Sn1—Cl4 | 178.98 (6) |
C2B—C1B—H1B1 | 108.3 | Cl3—Sn1—Cl5 | 89.99 (6) |
N2—C1B—H1B2 | 108.3 | Cl3—Sn1—Cl6 | 89.41 (6) |
C2B—C1B—H1B2 | 108.3 | Cl4—Sn1—Cl5 | 89.44 (6) |
H1B1—C1B—H1B2 | 107.4 | Cl4—Sn1—Cl6 | 91.16 (6) |
C3B—C2B—C1B | 111.9 (7) | Cl5—Sn1—Cl6 | 179.39 (6) |
C3B—C2B—H2B1 | 109.2 | | |
| | | |
N1—C1A—C2A—C3A | 174.6 (6) | N2—C1B—C2B—C3B | 178.6 (9) |
C1A—C2A—C3A—C4A | 81.2 (8) | C1B—C2B—C3B—C4B | 139.6 (9) |
C1A—C2A—C3A—C8A | −105.3 (7) | C1B—C2B—C3B—C8B | −53.5 (14) |
C8A—C3A—C4A—C5A | 0 | C8B—C3B—C4B—C5B | 0 |
C2A—C3A—C4A—C5A | 173.4 (5) | C2B—C3B—C4B—C5B | 168.3 (7) |
C3A—C4A—C5A—C6A | 0 | C3B—C4B—C5B—C6B | 0 |
C4A—C5A—C6A—C7A | 0 | C4B—C5B—C6B—C7B | 0 |
C5A—C6A—C7A—C8A | 0 | C5B—C6B—C7B—C8B | 0 |
C6A—C7A—C8A—C3A | 0 | C6B—C7B—C8B—C3B | 0 |
C4A—C3A—C8A—C7A | 0 | C4B—C3B—C8B—C7B | 0 |
C2A—C3A—C8A—C7A | −173.5 (5) | C2B—C3B—C8B—C7B | −165.7 (8) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl5 | 0.89 | 2.80 | 3.421 (6) | 128 |
N1—H1B···Cl5i | 0.89 | 2.74 | 3.548 (6) | 152 |
N1—H1C···Cl2ii | 0.89 | 2.92 | 3.606 (6) | 135 |
N2—H2A···Cl3 | 0.89 | 2.81 | 3.362 (6) | 122 |
N2—H2B···Cl3iii | 0.89 | 2.56 | 3.443 (6) | 171 |
N2—H2C···Cl6iv | 0.89 | 2.70 | 3.546 (6) | 159 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | (C8H12N)2[SnCl6] | (C8H12N)2[SnCl6] |
Mr | 575.76 | 575.76 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 12.243 (2), 7.1124 (13), 13.777 (3) | 7.335 (3), 25.695 (4), 11.974 (2) |
β (°) | 93.697 (3) | 90.03 (2) |
V (Å3) | 1197.2 (4) | 2256.8 (11) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.74 | 1.85 |
Crystal size (mm) | 0.48 × 0.28 × 0.13 | 0.2 × 0.2 × 0.15 |
|
Data collection |
Diffractometer | Bruker APEX II CCD area-detector diffractometer | Oxford Excalibur2 CCD area detector diffractometer |
Absorption correction | Integration (XPREP; Bruker, 1999) | Multi-scan (WinGX; Farrugia, 1999) |
Tmin, Tmax | 0.443, 0.821 | 0.709, 0.753 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6461, 2228, 1736 | 14565, 4159, 3144 |
Rint | 0.067 | 0.038 |
(sin θ/λ)max (Å−1) | 0.606 | 0.606 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.097, 1.30 | 0.050, 0.122, 1.05 |
No. of reflections | 2228 | 4159 |
No. of parameters | 103 | 202 |
No. of restraints | 0 | 150 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.96, −0.50 | 1.01, −1.00 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl2i | 0.89 | 2.68 | 3.302 (4) | 128 |
N1—H1A···Cl1 | 0.89 | 2.76 | 3.331 (4) | 123 |
N1—H1B···Cl2ii | 0.89 | 2.41 | 3.289 (4) | 170 |
N1—H1C···Cl3 | 0.89 | 2.54 | 3.302 (5) | 144 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl5 | 0.89 | 2.80 | 3.421 (6) | 128 |
N1—H1B···Cl5i | 0.89 | 2.74 | 3.548 (6) | 152 |
N1—H1C···Cl2ii | 0.89 | 2.92 | 3.606 (6) | 135 |
N2—H2A···Cl3 | 0.89 | 2.81 | 3.362 (6) | 122 |
N2—H2B···Cl3iii | 0.89 | 2.56 | 3.443 (6) | 171 |
N2—H2C···Cl6iv | 0.89 | 2.70 | 3.546 (6) | 159 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) x+1, y, z. |
Comparative geometric parameters (Å ,° ) in (I), (II) and (III)
that have related aromatic cations. topParameter | (I) | (II) | (III)a |
Sn1—Cl1 | 2.4270 (11) | 2.4244 (16) | 2.4242 (12) |
Sn1—Cl2 | 2.4557 (12) | 2.4316 (16) | 2.4590 (12) |
Sn1—Cl3 | 2.4310 (11) | 2.4342 (16) | 2.4064 (14) |
Sn1—Cl4 | - | 2.4257 (16) | 2.4244 (14) |
Sn1—Cl5 | - | 2.4291 (16) | 2.4415 (12) |
Sn1—Cl6 | - | 2.4118 (16) | 2.4271 (13) |
Interplanar spacing | 12.243 (2) | 12.848 (4) | 11.016 (7) |
Packing efficiency | 0.648 | 0.689 | 0.689 |
a (C6H5CH2NH3)2[SnCl6] [Rademeyer, 2004a; Cambridge
Structural
Database (Allen, 2002) refcode INIXOS]. |
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A significant number of organic/inorganic compounds of the formula (R–NH3)2SnX4 (where X is F, Cl, Br or I) have previously been investigated structurally because of their interesting magnetic and optical properties (Mitzi et al., 1998; Raptopoulou et al., 2002). In contrast, compounds of the formula (R–NH3)2SnX6 have not been studied extensively. The crystal structures of only four primary n-alkylammonium hexachlorotin(IV) compounds – with organic chain lengths ranging from one to six (Kitahama et al., 1979; Knop et al., 1983; Eulleuch et al., 1996; Lemmerer et al., 2007) – and two primary arylammonium hexachlorotin(IV) organic–inorganic hybrid compounds (Rademeyer, 2004a,b) have been reported in the literature.
In the present investigation, two novel crystal structures of organic–inorganic hybrid materials are reported, namely bis(1-phenylethylammonium) hexachloridostannate(IV), (I), and bis(2-phenylethylammonium) hexachloridostannate(IV), (II). A comparison of the structures reveals the effect of a slight change in the cation and the introduction of a chiral cation on the packing of molecular ions in the crystal structures.
The structures of (I) and (II), in which the cations are structural isomers, can be compared with that of bis(benzylammonium) hexachloridostannate(IV), (III) (Rademeyer, 2004a), as they form a logical series; relative to (III), (I) has an additional methyl group on the C atom adjacent to the ammonium group, while the arylammonium chain in (II) is longer by one methylene group than that in (III).
The molecular geometry and atomic numbering schemes employed for (I) and (II) are illustrated in Fig. 1. In the solid state, (I) and (II) self-assemble into structures consisting of alternating organic layers, consisting of the ammonium cations bis(1-phenylethylammonium) [for (I)] and bis(2-phenylethylammonium) hexachloridostannate(IV) [(II)], and inorganic layers, made up of isolated SnCl6 octahedra. The layers stack along the a axis in (I) and along the b axis in (II), as illustrated in Figs. 2 and 3, respectively. In both structures, the inorganic layer and organic layer interact via hydrogen bonds to form a two-dimensional network parallel to the bc plane in (I) and parallel to the ac plane in (II).
The inorganic part of the asymmetric unit of (I) contains an Sn atom on a centre of inversion at (1/2, 0, 1/2) and three Cl atoms in general positions. The inversion centre generates an SnCl6 octahedron, in which the three unique Sn—Cl bond lengths are 2.4270 (11), 2.4310 (12) and 2.4557 (12) Å (see Table 3), and the cis Cl—Sn—Cl bond angles range from 89.56 (4)° to 90.44 (4)°, indicating only slight distortion from ideal octahedral geometry. Each unit cell contains one complete inorganic layer [mean plane equation: 12.217 (2) x = 6.109 (1) Å; symmetry operators of atoms used: Sn1 (x, y, z), (x, 1 + y, z), (1 - x, 1/2 + y, 1/2 - z), Sn1 (1 - x, 1/2 + y, 3/2 - z)] and successive layers are separated by the unit cell repeat a of 12.243 (2) Å.
The organic layer of (I) has one independent 1-phenylethylammonium cation on a general position. The aromatic ring plane [C3–C8; mean plane equation: 8.68 (3) x - 2.75 (2) y - 8.75 (6) z = 2.94 (4) Å] is inclined at an angle of 48.0 (2)° to the plane of the inorganic layer. Within the organic layers, adjacent aromatic rings are separated by a centroid-to-centroid distance of 5.268 Å, clearly far too large to be considered as a π-stacking interaction.
The hydrogen-bonding interactions linking the organic layer and the inorganic layer involve the three H atoms on the ammonium group. There are two simple and one bifurcated hydrogen bonds between one cation and three different SnCl6 octahedra (Fig. 4 and Table 1).
The asymmetric unit of (II) comprises two crystallographically independent 2-phenylethylammonium cations, labelled cat1 (containing atom N1) and cat2 (containing atom N2), and one octahedral [SnCl6]2- anion, the atoms of which lie in general positions. Each unit cell contains two complete inorganic layers [mean plane equation: 25.45 (1) y - 1.660 (2) z = 11.893 (5) Å; symmetry operators of atoms used: Sn1 (x, y, z), (1 + x, y, z), (-x, 1 - y, 1 - z), (1 - x, 1 - y, 1 - z)]. The Sn—Cl bond lengths range from 2.4118 (16) to 2.4342 (17) Å (see Table 3) and the cis Cl—Sn—Cl angles from 88.68 (6)° to 91.61 (7)° indicating small distortions from ideal octahedral geometry.
Within the organic layer of (II), the cations pack in an interdigitated fashion. The planes of the aromatic rings of the two cations are tilted by 80.6 (2)° [for C3A–C8A; mean plane equation: 6.66 (1) x - 0.06 (9) y + 5.03 (4) z = 9.90 (8) Å] and 86.5 (2)° [for C3B–C8B; mean plane equation: 6.59 (1) x + 2.72 (8) y - 5.13 (3) z = 2.20 (6) Å] relative to the inorganic layer plane, and by 50.6 (2)° relative to one another. Weak C—H···π interactions are present in this layer, with atom C4A interacting with the centroid Cg2 of the aromatic group C3B–C8B (symmetry operator: x, 3/2 - y, -1/2 + z) through atom H4A (CH···Cg2 = 2.82 Å and C—H···Cg2 = 133°), and atom C7A interacting with the centroid Cg2 of another ring (symmetry operator: -1 + x, y, -1 + z) through atom H7A (CH···Cg = 2.83 Å and C—H···Cg2 = 136°; see Fig. 5).
In (II), the two crystallographically independent cations display the same hydrogen-bonding interactions with the [SnCl6]2- anions. Atoms N1 and N2 interact with three anions each through three simple hydrogen bonds (Fig. 6). The hydrogen bond N1—H1C···Cl2 has a hydrogen–acceptor distance of 2.92 Å and can be classified as a short contact.
A notable difference between the three structures lies in the volume of the unit cell, which is approximately doubled in (II) and (III) compared with (I). The organic cations in (I) and (III) have approximately the same length, but because the cations are non-interdigitated in (I) and interdigitated in (III), the interlayer spacing of (III) is shorter than that of (I) (see the values in Table 1). Although the cation in (II) is longer than that in (I), the two interlayer spacings are similar as a result of the interdigitation of the organic layer of (II), and the fact that the rings are tilted at different angles to the inorganic layer, thus compensating for the different packing arrangements of the organic layer.
In (I), neigbouring cations participate in hydrogen bonding with different inorganic layers, thus alternating in orientation, as shown in Fig. 2. However, in (II) pairs of cations point in the same direction, and neighbouring pairs alternate in orientation (Fig. 3), and the same is observed for (III). In all three structures, the hydrogen bonds give rise to a complex hydrogen-bonded network extending in two-dimensions. The packing efficiency of (I) is slightly lower than that of (II) and (III) (Table 1), possibly because the sterically hindering methyl group prevents more efficient packing.
In summary, slight changes to the cation cause subtle differences in the structures of compounds (I), (II) and (III), involving changes in interdigitation and cation orientation. Overall, however, the structures are still very similar, indicating that self-assembly in the hydrophobic and hydrophilic layers and hydrogen-bond formation are the major driving forces that dictate the packing.