The crystal structures of the two organic-inorganic hybrids bis(4-aminopyridinium) hexachloridostannate(IV), (C5H7N2)2[SnCl6], and bis(p-toluidinium) hexachloridostannate(IV), (C7H10N)2[SnCl6], differ in the way their cations pack in the layered structures. The Sn atom in the 4-aminopyridinium compound lies on an inversion centre.
Supporting information
CCDC references: 655483; 655484
For the preparation of (I), 4-aminopyridinium chloride was prepared by the
dropwise addition of excess HCl (0.52 ml, 37%, Aldrich) to a solution of
4-aminopyridine (0.874 g, 98%, Aldrich) in 15 ml of chloroform (99%,
Saarchem). The resulting precipitate of 4-aminopyridinium chloride was
filtered off. Compound (I) was crystallized from a solution of
4-aminopyridinium (0.421 g) and SnCl4·5H2O (0.571 g, 98%, Aldrich) in
45 ml of water, at room temperature, over a period of five weeks. For the
preparation of (II), p-toluidinium chloride was precipitated by adding
excess HCl (0.48 ml, 37%, Aldrich), dropwise, to a solution of
p-toluidine (0.994 g, 99%, Aldrich) in 40 ml of chloroform (99%,
Saarchem). The precipitate was filtered off. p-Toluidinium chloride
(0.396 g) and SnCl4·5H2O (0.502 g, 98%, Aldrich) were dissolved in 40 ml of water. Compound (II) crystallized from the solution, at room
temperature, over a period of four weeks.
For both compounds, all H atoms were refined using a riding model, with C—H
distances of either 0.93 or 0.96 Å and N—H distances of either 0.86 or
0.89 Å, and with Uiso(H) values of 1.2Ueq(C,N) or
1.5Ueq(C,N).
For both compounds, data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; 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(4-aminopyridinium) hexachloridostannate(IV)
top
Crystal data top
(C5H7N2)2[SnCl6] | Z = 1 |
Mr = 521.64 | F(000) = 254 |
Triclinic, P1 | Dx = 1.904 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.2248 (6) Å | Cell parameters from 940 reflections |
b = 8.3273 (7) Å | θ = 3.6–28.4° |
c = 8.3403 (8) Å | µ = 2.28 mm−1 |
α = 89.100 (6)° | T = 293 K |
β = 87.002 (6)° | Block, colourless |
γ = 65.225 (5)° | 0.34 × 0.26 × 0.18 mm |
V = 454.96 (7) Å3 | |
Data collection top
Bruker SMART 1K CCD area-detector diffractometer | 2197 independent reflections |
Radiation source: fine-focus sealed tube | 2109 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
ω scans | θmax = 28°, θmin = 2.5° |
Absorption correction: integration (XPREP; Bruker, 1999) | h = −9→9 |
Tmin = 0.518, Tmax = 0.690 | k = −10→10 |
6423 measured reflections | l = −11→8 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.051 | w = 1/[σ2(Fo2) + 0.0957P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
2197 reflections | Δρmax = 0.41 e Å−3 |
98 parameters | Δρmin = −0.62 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.037 (2) |
Crystal data top
(C5H7N2)2[SnCl6] | γ = 65.225 (5)° |
Mr = 521.64 | V = 454.96 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.2248 (6) Å | Mo Kα radiation |
b = 8.3273 (7) Å | µ = 2.28 mm−1 |
c = 8.3403 (8) Å | T = 293 K |
α = 89.100 (6)° | 0.34 × 0.26 × 0.18 mm |
β = 87.002 (6)° | |
Data collection top
Bruker SMART 1K CCD area-detector diffractometer | 2197 independent reflections |
Absorption correction: integration (XPREP; Bruker, 1999) | 2109 reflections with I > 2σ(I) |
Tmin = 0.518, Tmax = 0.690 | Rint = 0.074 |
6423 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.020 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.41 e Å−3 |
2197 reflections | Δρmin = −0.62 e Å−3 |
98 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 | 0.6760 (3) | 0.5754 (3) | 0.5511 (3) | 0.0361 (4) | |
C2 | 0.7971 (3) | 0.4945 (3) | 0.4113 (3) | 0.0471 (6) | |
H2 | 0.9018 | 0.3815 | 0.4163 | 0.057* | |
C3 | 0.7597 (4) | 0.5822 (5) | 0.2709 (3) | 0.0616 (8) | |
H3 | 0.841 | 0.5298 | 0.1795 | 0.074* | |
C4 | 0.5183 (3) | 0.7451 (3) | 0.5347 (3) | 0.0440 (5) | |
H4 | 0.4357 | 0.8032 | 0.6237 | 0.053* | |
C5 | 0.4866 (4) | 0.8241 (4) | 0.3894 (4) | 0.0577 (7) | |
H5 | 0.3799 | 0.9352 | 0.379 | 0.069* | |
N1 | 0.6060 (4) | 0.7449 (4) | 0.2612 (3) | 0.0664 (7) | |
H1 | 0.5847 | 0.7984 | 0.1705 | 0.08* | |
N2 | 0.7062 (3) | 0.4962 (3) | 0.6925 (3) | 0.0498 (5) | |
H2A | 0.629 | 0.5487 | 0.775 | 0.06* | |
H2B | 0.8029 | 0.3924 | 0.7019 | 0.06* | |
Cl1 | 0.69151 (7) | 1.27333 (7) | 0.02804 (6) | 0.04090 (13) | |
Cl2 | 0.95519 (7) | 0.93208 (7) | 0.28048 (6) | 0.03919 (12) | |
Cl3 | 0.79724 (8) | 0.84587 (8) | −0.08407 (7) | 0.04406 (13) | |
Sn1 | 1 | 1 | 0 | 0.02716 (8) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0342 (8) | 0.0370 (10) | 0.0387 (11) | −0.0166 (8) | −0.0022 (7) | 0.0013 (8) |
C2 | 0.0427 (10) | 0.0536 (14) | 0.0467 (13) | −0.0226 (10) | 0.0080 (8) | −0.0132 (11) |
C3 | 0.0779 (17) | 0.092 (2) | 0.0384 (14) | −0.0599 (18) | 0.0114 (11) | −0.0128 (14) |
C4 | 0.0425 (10) | 0.0383 (11) | 0.0475 (13) | −0.0135 (9) | −0.0017 (9) | 0.0018 (9) |
C5 | 0.0664 (14) | 0.0520 (15) | 0.0638 (18) | −0.0319 (12) | −0.0255 (13) | 0.0185 (13) |
N1 | 0.0992 (18) | 0.090 (2) | 0.0417 (13) | −0.0685 (17) | −0.0261 (12) | 0.0235 (12) |
N2 | 0.0515 (10) | 0.0463 (11) | 0.0424 (11) | −0.0118 (9) | −0.0016 (8) | 0.0112 (9) |
Cl1 | 0.0359 (2) | 0.0360 (3) | 0.0353 (3) | 0.00001 (19) | −0.00007 (17) | 0.0004 (2) |
Cl2 | 0.0397 (2) | 0.0427 (3) | 0.0273 (2) | −0.0102 (2) | 0.00196 (16) | 0.00599 (19) |
Cl3 | 0.0497 (3) | 0.0512 (3) | 0.0408 (3) | −0.0302 (2) | −0.0055 (2) | 0.0028 (2) |
Sn1 | 0.02590 (9) | 0.02714 (11) | 0.02442 (11) | −0.00732 (7) | −0.00045 (6) | 0.00217 (7) |
Geometric parameters (Å, º) top
C1—N2 | 1.325 (3) | C5—H5 | 0.93 |
C1—C4 | 1.405 (3) | N1—H1 | 0.86 |
C1—C2 | 1.415 (3) | N2—H2A | 0.86 |
C2—C3 | 1.348 (4) | N2—H2B | 0.86 |
C2—H2 | 0.93 | Cl1—Sn1 | 2.4317 (5) |
C3—N1 | 1.349 (4) | Cl2—Sn1 | 2.4351 (5) |
C3—H3 | 0.93 | Cl3—Sn1 | 2.4487 (5) |
C4—C5 | 1.353 (4) | Sn1—Cl1i | 2.4317 (5) |
C4—H4 | 0.93 | Sn1—Cl2i | 2.4351 (6) |
C5—N1 | 1.331 (4) | Sn1—Cl3i | 2.4487 (5) |
| | | |
N2—C1—C4 | 120.4 (2) | C1—N2—H2A | 120 |
N2—C1—C2 | 122.3 (2) | C1—N2—H2B | 120 |
C4—C1—C2 | 117.3 (2) | H2A—N2—H2B | 120 |
C3—C2—C1 | 119.6 (2) | Cl1i—Sn1—Cl1 | 180 |
C3—C2—H2 | 120.2 | Cl1i—Sn1—Cl2i | 89.946 (19) |
C1—C2—H2 | 120.2 | Cl1—Sn1—Cl2i | 90.054 (19) |
C2—C3—N1 | 120.9 (3) | Cl1i—Sn1—Cl2 | 90.054 (19) |
C2—C3—H3 | 119.6 | Cl1—Sn1—Cl2 | 89.946 (19) |
N1—C3—H3 | 119.6 | Cl2i—Sn1—Cl2 | 180.0000 (10) |
C5—C4—C1 | 120.1 (2) | Cl1i—Sn1—Cl3i | 89.86 (2) |
C5—C4—H4 | 120 | Cl1—Sn1—Cl3i | 90.14 (2) |
C1—C4—H4 | 120 | Cl2i—Sn1—Cl3i | 91.220 (19) |
N1—C5—C4 | 120.9 (3) | Cl2—Sn1—Cl3i | 88.780 (19) |
N1—C5—H5 | 119.6 | Cl1i—Sn1—Cl3 | 90.14 (2) |
C4—C5—H5 | 119.6 | Cl1—Sn1—Cl3 | 89.86 (2) |
C5—N1—C3 | 121.3 (2) | Cl2i—Sn1—Cl3 | 88.780 (19) |
C5—N1—H1 | 119.4 | Cl2—Sn1—Cl3 | 91.220 (19) |
C3—N1—H1 | 119.4 | Cl3i—Sn1—Cl3 | 180 |
| | | |
N2—C1—C2—C3 | −179.6 (2) | C2—C1—C4—C5 | 0.4 (3) |
C4—C1—C2—C3 | 1.0 (3) | C1—C4—C5—N1 | −1.5 (4) |
C1—C2—C3—N1 | −1.2 (3) | C4—C5—N1—C3 | 1.3 (4) |
N2—C1—C4—C5 | −179.1 (2) | C2—C3—N1—C5 | 0.0 (4) |
Symmetry code: (i) −x+2, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl3 | 0.86 | 2.68 | 3.375 (3) | 139 |
N1—H1···Cl1ii | 0.86 | 2.91 | 3.3602 (19) | 115 |
N2—H2A···Cl1iii | 0.86 | 2.66 | 3.491 (2) | 164 |
N2—H2B···Cl2iv | 0.86 | 2.54 | 3.388 (2) | 171 |
Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x+1, −y+2, −z+1; (iv) −x+2, −y+1, −z+1. |
(II) bis(
p-toluidinium)hexachloridostannate(IV)
top
Crystal data top
(C7H10N)2[SnCl6] | F(000) = 1080 |
Mr = 547.71 | Dx = 1.729 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 929 reflections |
a = 7.1166 (5) Å | θ = 3.3–28.3° |
b = 25.304 (2) Å | µ = 1.98 mm−1 |
c = 11.6862 (9) Å | T = 293 K |
β = 90.239 (4)° | Plate, colourless |
V = 2104.4 (3) Å3 | 0.4 × 0.16 × 0.07 mm |
Z = 4 | |
Data collection top
Bruker SMART 1K CCD area-detector diffractometer | 5075 independent reflections |
Radiation source: fine-focus sealed tube | 4041 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 28°, θmin = 1.9° |
Absorption correction: integration (XPREP; Bruker, 1999) | h = −9→9 |
Tmin = 0.583, Tmax = 0.879 | k = −30→33 |
15513 measured reflections | l = −15→15 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0399P)2 + 0.1137P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.082 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.65 e Å−3 |
5075 reflections | Δρmin = −0.85 e Å−3 |
212 parameters | |
Crystal data top
(C7H10N)2[SnCl6] | V = 2104.4 (3) Å3 |
Mr = 547.71 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.1166 (5) Å | µ = 1.98 mm−1 |
b = 25.304 (2) Å | T = 293 K |
c = 11.6862 (9) Å | 0.4 × 0.16 × 0.07 mm |
β = 90.239 (4)° | |
Data collection top
Bruker SMART 1K CCD area-detector diffractometer | 5075 independent reflections |
Absorption correction: integration (XPREP; Bruker, 1999) | 4041 reflections with I > 2σ(I) |
Tmin = 0.583, Tmax = 0.879 | Rint = 0.052 |
15513 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.082 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.65 e Å−3 |
5075 reflections | Δρmin = −0.85 e Å−3 |
212 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 | 0.2702 (4) | 0.62050 (13) | 0.3467 (3) | 0.0370 (7) | |
C2 | 0.2218 (6) | 0.63635 (15) | 0.2381 (3) | 0.0536 (10) | |
H2 | 0.1738 | 0.6121 | 0.1858 | 0.064* | |
C3 | 0.2453 (6) | 0.68896 (15) | 0.2075 (3) | 0.0562 (10) | |
H3 | 0.2133 | 0.6996 | 0.1338 | 0.067* | |
C4 | 0.3148 (5) | 0.72571 (14) | 0.2835 (3) | 0.0477 (9) | |
C5 | 0.3635 (6) | 0.70826 (16) | 0.3911 (4) | 0.0633 (11) | |
H5 | 0.4124 | 0.7323 | 0.4435 | 0.076* | |
C6 | 0.3417 (6) | 0.65569 (17) | 0.4239 (3) | 0.0594 (11) | |
H6 | 0.3753 | 0.6448 | 0.4972 | 0.071* | |
C7 | 0.3397 (7) | 0.78281 (16) | 0.2500 (4) | 0.0729 (13) | |
H7A | 0.4569 | 0.7957 | 0.2801 | 0.109* | |
H7B | 0.2383 | 0.8034 | 0.2806 | 0.109* | |
H7C | 0.34 | 0.7857 | 0.1681 | 0.109* | |
N1 | 0.2490 (4) | 0.56445 (11) | 0.3804 (2) | 0.0462 (7) | |
H1A | 0.1846 | 0.5472 | 0.3266 | 0.069* | |
H1B | 0.1875 | 0.5626 | 0.4465 | 0.069* | |
H1C | 0.362 | 0.5498 | 0.3885 | 0.069* | |
C8 | 0.2265 (4) | 0.36280 (13) | 0.0386 (3) | 0.0364 (7) | |
C9 | 0.1565 (5) | 0.33011 (15) | 0.1200 (3) | 0.0487 (9) | |
H9 | 0.1232 | 0.3433 | 0.1914 | 0.058* | |
C10 | 0.1353 (6) | 0.27710 (16) | 0.0956 (4) | 0.0577 (10) | |
H10 | 0.0863 | 0.2547 | 0.151 | 0.069* | |
C11 | 0.1855 (5) | 0.25662 (14) | −0.0096 (4) | 0.0535 (10) | |
C12 | 0.2569 (6) | 0.29089 (16) | −0.0894 (4) | 0.0606 (11) | |
H12 | 0.2918 | 0.278 | −0.1608 | 0.073* | |
C13 | 0.2781 (6) | 0.34431 (16) | −0.0659 (3) | 0.0573 (10) | |
H13 | 0.3268 | 0.3671 | −0.1207 | 0.069* | |
C14 | 0.1609 (7) | 0.19865 (17) | −0.0349 (5) | 0.0863 (16) | |
H14A | 0.1695 | 0.1789 | 0.035 | 0.13* | |
H14B | 0.2575 | 0.1872 | −0.0864 | 0.13* | |
H14C | 0.04 | 0.1929 | −0.0695 | 0.13* | |
N2 | 0.2454 (4) | 0.41964 (11) | 0.0638 (2) | 0.0445 (7) | |
H2A | 0.3194 | 0.4346 | 0.0119 | 0.067* | |
H2B | 0.2955 | 0.4238 | 0.1332 | 0.067* | |
H2C | 0.1326 | 0.4348 | 0.0617 | 0.067* | |
Cl1 | 0.73767 (12) | 0.41018 (3) | 0.08675 (6) | 0.03974 (18) | |
Cl2 | 0.71968 (14) | 0.53261 (4) | 0.40523 (7) | 0.0521 (2) | |
Cl3 | 0.50048 (11) | 0.52603 (3) | 0.14627 (6) | 0.03698 (17) | |
Cl4 | 0.45906 (11) | 0.42230 (4) | 0.32560 (7) | 0.0481 (2) | |
Cl5 | 0.94557 (12) | 0.41728 (4) | 0.35579 (7) | 0.0468 (2) | |
Cl6 | 0.98387 (11) | 0.51894 (3) | 0.16011 (7) | 0.0435 (2) | |
Sn1 | 0.72437 (3) | 0.470019 (8) | 0.247759 (15) | 0.02851 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0418 (17) | 0.0309 (17) | 0.0383 (17) | 0.0023 (14) | 0.0043 (13) | 0.0011 (14) |
C2 | 0.082 (3) | 0.038 (2) | 0.0405 (19) | −0.0061 (19) | −0.0115 (19) | −0.0023 (16) |
C3 | 0.079 (3) | 0.043 (2) | 0.047 (2) | −0.002 (2) | −0.0123 (19) | 0.0082 (18) |
C4 | 0.050 (2) | 0.034 (2) | 0.059 (2) | 0.0022 (16) | 0.0062 (17) | 0.0028 (17) |
C5 | 0.087 (3) | 0.050 (3) | 0.053 (2) | −0.017 (2) | −0.008 (2) | −0.0103 (19) |
C6 | 0.077 (3) | 0.058 (3) | 0.043 (2) | −0.009 (2) | −0.0151 (19) | 0.0016 (18) |
C7 | 0.090 (3) | 0.035 (2) | 0.094 (3) | −0.003 (2) | 0.015 (3) | 0.003 (2) |
N1 | 0.0606 (18) | 0.0389 (17) | 0.0393 (15) | 0.0055 (14) | 0.0073 (13) | 0.0036 (13) |
C8 | 0.0332 (15) | 0.0335 (18) | 0.0424 (17) | 0.0000 (13) | 0.0001 (13) | −0.0074 (14) |
C9 | 0.057 (2) | 0.046 (2) | 0.0433 (19) | −0.0007 (18) | 0.0112 (16) | −0.0031 (17) |
C10 | 0.063 (2) | 0.042 (2) | 0.068 (3) | −0.0075 (19) | 0.009 (2) | 0.006 (2) |
C11 | 0.046 (2) | 0.037 (2) | 0.077 (3) | −0.0037 (17) | 0.0006 (19) | −0.014 (2) |
C12 | 0.072 (3) | 0.052 (3) | 0.058 (2) | −0.006 (2) | 0.014 (2) | −0.022 (2) |
C13 | 0.074 (3) | 0.053 (2) | 0.045 (2) | −0.010 (2) | 0.0138 (19) | −0.0062 (18) |
C14 | 0.087 (3) | 0.045 (3) | 0.127 (5) | −0.009 (2) | 0.003 (3) | −0.027 (3) |
N2 | 0.0508 (16) | 0.0353 (17) | 0.0474 (16) | 0.0036 (13) | −0.0016 (13) | −0.0029 (13) |
Cl1 | 0.0498 (4) | 0.0352 (4) | 0.0342 (4) | 0.0059 (4) | −0.0011 (3) | −0.0067 (3) |
Cl2 | 0.0632 (5) | 0.0543 (6) | 0.0388 (4) | 0.0100 (4) | −0.0056 (4) | −0.0198 (4) |
Cl3 | 0.0386 (4) | 0.0351 (4) | 0.0372 (4) | 0.0077 (3) | −0.0032 (3) | 0.0037 (3) |
Cl4 | 0.0408 (4) | 0.0601 (6) | 0.0435 (4) | −0.0085 (4) | 0.0091 (3) | 0.0118 (4) |
Cl5 | 0.0447 (4) | 0.0580 (6) | 0.0377 (4) | 0.0174 (4) | −0.0064 (3) | 0.0048 (4) |
Cl6 | 0.0372 (4) | 0.0428 (5) | 0.0506 (5) | −0.0103 (3) | 0.0060 (3) | 0.0023 (4) |
Sn1 | 0.02847 (11) | 0.03138 (12) | 0.02569 (11) | 0.00169 (8) | 0.00056 (7) | −0.00006 (8) |
Geometric parameters (Å, º) top
C1—C6 | 1.365 (5) | C9—C10 | 1.379 (5) |
C1—C2 | 1.373 (4) | C9—H9 | 0.93 |
C1—N1 | 1.480 (4) | C10—C11 | 1.382 (6) |
C2—C3 | 1.389 (5) | C10—H10 | 0.93 |
C2—H2 | 0.93 | C11—C12 | 1.373 (6) |
C3—C4 | 1.377 (5) | C11—C14 | 1.506 (5) |
C3—H3 | 0.93 | C12—C13 | 1.388 (5) |
C4—C5 | 1.375 (5) | C12—H12 | 0.93 |
C4—C7 | 1.508 (5) | C13—H13 | 0.93 |
C5—C6 | 1.393 (5) | C14—H14A | 0.96 |
C5—H5 | 0.93 | C14—H14B | 0.96 |
C6—H6 | 0.93 | C14—H14C | 0.96 |
C7—H7A | 0.96 | N2—H2A | 0.89 |
C7—H7B | 0.96 | N2—H2B | 0.89 |
C7—H7C | 0.96 | N2—H2C | 0.89 |
N1—H1A | 0.89 | Cl1—Sn1 | 2.4173 (8) |
N1—H1B | 0.89 | Cl2—Sn1 | 2.4282 (8) |
N1—H1C | 0.89 | Cl3—Sn1 | 2.4369 (7) |
C8—C9 | 1.357 (5) | Cl4—Sn1 | 2.4217 (8) |
C8—C13 | 1.360 (5) | Cl5—Sn1 | 2.4158 (8) |
C8—N2 | 1.474 (4) | Cl6—Sn1 | 2.4510 (8) |
| | | |
C6—C1—C2 | 120.8 (3) | C11—C10—H10 | 119.3 |
C6—C1—N1 | 119.1 (3) | C12—C11—C10 | 117.7 (4) |
C2—C1—N1 | 120.0 (3) | C12—C11—C14 | 121.7 (4) |
C1—C2—C3 | 119.2 (3) | C10—C11—C14 | 120.6 (4) |
C1—C2—H2 | 120.4 | C11—C12—C13 | 121.4 (4) |
C3—C2—H2 | 120.4 | C11—C12—H12 | 119.3 |
C4—C3—C2 | 121.6 (4) | C13—C12—H12 | 119.3 |
C4—C3—H3 | 119.2 | C8—C13—C12 | 118.9 (4) |
C2—C3—H3 | 119.2 | C8—C13—H13 | 120.5 |
C5—C4—C3 | 117.5 (4) | C12—C13—H13 | 120.5 |
C5—C4—C7 | 121.1 (4) | C11—C14—H14A | 109.5 |
C3—C4—C7 | 121.4 (4) | C11—C14—H14B | 109.5 |
C4—C5—C6 | 122.0 (4) | H14A—C14—H14B | 109.5 |
C4—C5—H5 | 119 | C11—C14—H14C | 109.5 |
C6—C5—H5 | 119 | H14A—C14—H14C | 109.5 |
C1—C6—C5 | 118.8 (4) | H14B—C14—H14C | 109.5 |
C1—C6—H6 | 120.6 | C8—N2—H2A | 109.5 |
C5—C6—H6 | 120.6 | C8—N2—H2B | 109.5 |
C4—C7—H7A | 109.5 | H2A—N2—H2B | 109.5 |
C4—C7—H7B | 109.5 | C8—N2—H2C | 109.5 |
H7A—C7—H7B | 109.5 | H2A—N2—H2C | 109.5 |
C4—C7—H7C | 109.5 | H2B—N2—H2C | 109.5 |
H7A—C7—H7C | 109.5 | Cl5—Sn1—Cl1 | 91.90 (3) |
H7B—C7—H7C | 109.5 | Cl5—Sn1—Cl4 | 92.04 (3) |
C1—N1—H1A | 109.5 | Cl1—Sn1—Cl4 | 90.76 (3) |
C1—N1—H1B | 109.5 | Cl5—Sn1—Cl2 | 88.58 (3) |
H1A—N1—H1B | 109.5 | Cl1—Sn1—Cl2 | 177.61 (3) |
C1—N1—H1C | 109.5 | Cl4—Sn1—Cl2 | 91.57 (3) |
H1A—N1—H1C | 109.5 | Cl5—Sn1—Cl3 | 177.34 (3) |
H1B—N1—H1C | 109.5 | Cl1—Sn1—Cl3 | 90.75 (3) |
C9—C8—C13 | 121.4 (3) | Cl4—Sn1—Cl3 | 87.91 (3) |
C9—C8—N2 | 119.2 (3) | Cl2—Sn1—Cl3 | 88.77 (3) |
C13—C8—N2 | 119.4 (3) | Cl5—Sn1—Cl6 | 90.39 (3) |
C8—C9—C10 | 119.2 (3) | Cl1—Sn1—Cl6 | 87.65 (3) |
C8—C9—H9 | 120.4 | Cl4—Sn1—Cl6 | 177.13 (3) |
C10—C9—H9 | 120.4 | Cl2—Sn1—Cl6 | 90.00 (3) |
C9—C10—C11 | 121.3 (4) | Cl3—Sn1—Cl6 | 89.72 (3) |
C9—C10—H10 | 119.3 | | |
| | | |
C6—C1—C2—C3 | −0.4 (6) | C13—C8—C9—C10 | −0.8 (6) |
N1—C1—C2—C3 | −179.0 (3) | N2—C8—C9—C10 | 178.7 (3) |
C1—C2—C3—C4 | −0.5 (6) | C8—C9—C10—C11 | 0.6 (6) |
C2—C3—C4—C5 | 1.1 (6) | C9—C10—C11—C12 | −0.2 (6) |
C2—C3—C4—C7 | −179.8 (4) | C9—C10—C11—C14 | −179.8 (4) |
C3—C4—C5—C6 | −0.9 (6) | C10—C11—C12—C13 | −0.1 (6) |
C7—C4—C5—C6 | 180.0 (4) | C14—C11—C12—C13 | 179.6 (4) |
C2—C1—C6—C5 | 0.5 (6) | C9—C8—C13—C12 | 0.5 (6) |
N1—C1—C6—C5 | 179.2 (4) | N2—C8—C13—C12 | −179.0 (3) |
C4—C5—C6—C1 | 0.1 (7) | C11—C12—C13—C8 | −0.1 (7) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl6i | 0.89 | 2.51 | 3.387 (3) | 167 |
N1—H1B···Cl5ii | 0.89 | 2.55 | 3.416 (3) | 164 |
N1—H1C···Cl2 | 0.89 | 2.59 | 3.456 (3) | 165 |
N2—H2A···Cl3iii | 0.89 | 2.46 | 3.351 (3) | 174 |
N2—H2B···Cl4 | 0.89 | 2.53 | 3.411 (3) | 172 |
N2—H2C···Cl6i | 0.89 | 2.64 | 3.326 (3) | 134 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | (C5H7N2)2[SnCl6] | (C7H10N)2[SnCl6] |
Mr | 521.64 | 547.71 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 7.2248 (6), 8.3273 (7), 8.3403 (8) | 7.1166 (5), 25.304 (2), 11.6862 (9) |
α, β, γ (°) | 89.100 (6), 87.002 (6), 65.225 (5) | 90, 90.239 (4), 90 |
V (Å3) | 454.96 (7) | 2104.4 (3) |
Z | 1 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 2.28 | 1.98 |
Crystal size (mm) | 0.34 × 0.26 × 0.18 | 0.4 × 0.16 × 0.07 |
|
Data collection |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Integration (XPREP; Bruker, 1999) | Integration (XPREP; Bruker, 1999) |
Tmin, Tmax | 0.518, 0.690 | 0.583, 0.879 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6423, 2197, 2109 | 15513, 5075, 4041 |
Rint | 0.074 | 0.052 |
(sin θ/λ)max (Å−1) | 0.661 | 0.661 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.051, 1.09 | 0.033, 0.082, 1.03 |
No. of reflections | 2197 | 5075 |
No. of parameters | 98 | 212 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.62 | 0.65, −0.85 |
Selected bond lengths (Å) for (I) topCl1—Sn1 | 2.4317 (5) | Sn1—Cl1i | 2.4317 (5) |
Cl2—Sn1 | 2.4351 (5) | Sn1—Cl2i | 2.4351 (6) |
Cl3—Sn1 | 2.4487 (5) | Sn1—Cl3i | 2.4487 (5) |
Symmetry code: (i) −x+2, −y+2, −z. |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl3 | 0.86 | 2.68 | 3.375 (3) | 139 |
N1—H1···Cl1ii | 0.86 | 2.91 | 3.3602 (19) | 115 |
N2—H2A···Cl1iii | 0.86 | 2.66 | 3.491 (2) | 164 |
N2—H2B···Cl2iv | 0.86 | 2.54 | 3.388 (2) | 171 |
Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x+1, −y+2, −z+1; (iv) −x+2, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (II) topCl1—Sn1 | 2.4173 (8) | Cl4—Sn1 | 2.4217 (8) |
Cl2—Sn1 | 2.4282 (8) | Cl5—Sn1 | 2.4158 (8) |
Cl3—Sn1 | 2.4369 (7) | Cl6—Sn1 | 2.4510 (8) |
| | | |
Cl1—Sn1—Cl2 | 177.61 (3) | Cl4—Sn1—Cl6 | 177.13 (3) |
Cl5—Sn1—Cl3 | 177.34 (3) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Cl6i | 0.89 | 2.51 | 3.387 (3) | 167 |
N1—H1B···Cl5ii | 0.89 | 2.55 | 3.416 (3) | 164 |
N1—H1C···Cl2 | 0.89 | 2.59 | 3.456 (3) | 165 |
N2—H2A···Cl3iii | 0.89 | 2.46 | 3.351 (3) | 174 |
N2—H2B···Cl4 | 0.89 | 2.53 | 3.411 (3) | 172 |
N2—H2C···Cl6i | 0.89 | 2.64 | 3.326 (3) | 134 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z. |
As part of a study of the effect of cations on the crystal structures of organic–inorganic ammonium hexachloridostannate(IV) hybrids, we report here two new structures with different aromatic organic ammonium cations. This type of hybrid generally exhibits a structure consisting of alternating inorganic layers, characterized by isolated octahedra of [SnCl6]2- anions, and organic layers, made up of alkylammonium (CnH2n + 1NH3+) or aromatic ammonium (C6H5—R—NH3+) cations (Lemmerer et al., 2007; Billing et al., 2007, and references therein). The two title compounds, bis(4-aminopyridinium) hexachloridostannate(IV), (I), and bis(p-toluidinium) hexachloridostannate(IV), (II), differ in their cation's hydrogen-bonding capability, with the cation in (I) able to hydrogen bond at both ends of the molecule, whereas the cation in (II) only has hydrogen-bonding capability at one end of the molecule. The two structures exhibit similarities and differences to previously reported crystal structures of this type. The asymmetric unit and atomic numbering schemes of (I) and (II) are shown in Fig. 1.
The organic–inorganic hybrid structure of (I) has SnCl6 octahedra at each of the eight vertices of the triclinic unit cell, encapsulating two 4-aminopyridinium cations in the centre of the unit cell (Fig. 2). A layered structure results, with the SnCl6 octahedra forming the inorganic layer and the cations packing in the organic layer. The asymmetric unit of the inorganic part contains an SnIV atom on an inversion centre and three Cl atoms on general positions, labelled Cl1, Cl2 and Cl3. The inversion symmetry operator generates the full octahedral coordination. Sn—Cl bond lengths are given in Table 1 and average out to 2.439 (9) Å. The bond angles between trans-related Cl atoms are exactly 180° and cis angles range from 88.78 (2) to 91.22 (2)°.
The organic part of (I) has one 4-aminopyridinum cation in the asymmetric unit. In the organic layer, these cations pack in an interdigitated fashion so that opposite ends of the cation hydrogen bond to inorganic layers. This results in a short inter-layer spacing of 8.3403 (8) Å. Adjacent cations are stacked antiparallel, with a centroid-to-centroid distance of 4.244 Å [s.u. value available?]. This distance is significantly greater than the 3.8 Å commonly used as the cut-off distance for accepted π—π interactions (Janiak, 2000). Closer contacts have been found for this cation in molecular crystals (3.473 Å; Kennedy & Kittner, 2005).
The interactions between the inorganic and organic parts are dominated by N—H···Cl—Sn charge-assisted hydrogen bonds, viz. two hydrogen bonds involving atom N2 of the ammonium group, being 2.54 and 2.66 Å long, and another hydrogen bond involving atom N1 of the pyridine ring, being 2.68 Å long. In addition, there is a short contact interaction between atoms N1 and Cl1(-x + 1, -y + 2, -z) (2.91 Å). These interactions result in a two-dimensional hydrogen-bond network parallel to (111). Fig. 3 illustrates the various interactions and Table 2 summarizes the geometric parameters. There is also an X—Y···π short contact between the ring centroid and atom Cl1 on the SnCl6 octahedra [Cl1···Cg = 3.910 (2) Å and Sn1—Cl1···Cg = 120.71 (2)°].
The packing of (II) is different from that of (I) (Fig. 4) in that it exhibits a more distinct organic layer, similar to what was observed for the previously reported hexachloridostannate(IV) hybrid structures. This is because the cations in the inorganic layer are more offset than in (I), and thus only slightly interdigitated, with only one end of the cation interacting with a single inorganic layer via hydrogen bonds. The interlayer spacing is larger than for structure (I), with a value of 12.652 (2) Å along the b axis. The p-toluidinium cations pack antiparallel, with a centroid-to-centroid distance of 5.251 (2) Å. The asymmetric unit is roughly twice that of (I), the inorganic part consisting of a complete [SnCl6]2- octahedron, where the SnIV atom and atoms Cl1 through to Cl6 are on general positions. The six unique Sn—Cl bond lengths average out to 2.429 (14) Å. The bond angles between trans-related Cl atoms deviate from 180° (Table 3) and cis angles range from 87.65 (3) to 92.04 (3)°. To balance the charge, two independent toluidinium cations are found in the asymmetric unit of the organic part.
In (II), hydrogen-bonding interactions between the Cl atoms and the ammonium group form a two-dimensional hydrogen-bonded sheet parallel to the ac plane. All six H atoms form simple hydrogen bonds, with no bifurcated geometries observed (Fig. 5 and Table 4).
In conclusion, by increasing the hydrogen-bonding capability of the cation from only one end of the cation in (II) to both, opposite ends of the cation in (I) the dimensionality of the hydrogen-bonding network is not changed. However, the inorganic layer changes from only slightly interdigitated in (II) to completely interdigitated in (I), allowing both ends of the cation to hydrogen bond to inorganic layers on opposite sides of the cation. This behaviour illustrates that the hydrogen-bonding capability of the cation can be utilized to give some control over the degree of overlap or interdigitation in the organic layer of this type of organic–inorganic hybrid.