Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106016167/gd3019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106016167/gd3019Isup2.hkl |
CCDC reference: 612444
PbI2 (0.126 g, 0.273 mmol) was dissolved in 47% HI (2 ml) in a sample vial. Thereafter, C(CH3)3NH2 (0.050 g, 0.684 mmol) was added and the precipitate was dissolved by refluxing for 12 h at 363 K. The solution was slowly cooled at 2 K h−1 to room temperature. A yellow single-crystal suitable for X-ray diffraction analysis was selected and studied. Analysis calculated for C8H28I4N2O2Pb: C 10.7, H 3.1, N 3.1%; found: C 10.8, H 3.3, N 3.2%
All H were found in a difference map. For the H atoms bonded to O atoms, restraints were used to obtain reasonable details of O—H distances and H—O—H angles. Finally these H atoms were refined using a riding model, with Uiso(H) = 1.2Uiso(O). H atoms bonded to C and N atoms were refined in idealized positions in the riding-model approximation, with C—H = 0.98 Å and N—H = 0.91 Å, and with Uiso(H) = 1.5Ueq(C,N). The highest residual peak is 0.83 Å from atom Pb1.
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).
(C4H12N)2[PbI3]I·2H2O | F(000) = 800 |
Mr = 899.11 | Dx = 2.673 Mg m−3 |
Monoclinic, P21/m | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yb | Cell parameters from 927 reflections |
a = 9.7917 (10) Å | θ = 4.0–28.1° |
b = 7.9649 (8) Å | µ = 13.08 mm−1 |
c = 15.0594 (16) Å | T = 173 K |
β = 107.985 (3)° | Needle, white |
V = 1117.1 (2) Å3 | 0.28 × 0.1 × 0.09 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2416 reflections with I > 2σ(I) |
ϕ and ω scans | Rint = 0.074 |
Absorption correction: integration (XPREP; Bruker, 1999) | θmax = 28°, θmin = 1.4° |
Tmin = 0.174, Tmax = 0.388 | h = −12→12 |
5842 measured reflections | k = −10→10 |
2878 independent reflections | l = −19→12 |
Refinement on F2 | 2 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0497P)2 + 0.2377P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.101 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 2.67 e Å−3 |
2878 reflections | Δρmin = −2.32 e Å−3 |
96 parameters |
(C4H12N)2[PbI3]I·2H2O | V = 1117.1 (2) Å3 |
Mr = 899.11 | Z = 2 |
Monoclinic, P21/m | Mo Kα radiation |
a = 9.7917 (10) Å | µ = 13.08 mm−1 |
b = 7.9649 (8) Å | T = 173 K |
c = 15.0594 (16) Å | 0.28 × 0.1 × 0.09 mm |
β = 107.985 (3)° |
Bruker SMART CCD area-detector diffractometer | 2878 independent reflections |
Absorption correction: integration (XPREP; Bruker, 1999) | 2416 reflections with I > 2σ(I) |
Tmin = 0.174, Tmax = 0.388 | Rint = 0.074 |
5842 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 2 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.07 | Δρmax = 2.67 e Å−3 |
2878 reflections | Δρmin = −2.32 e Å−3 |
96 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Pb1 | 0.5 | 0.5 | 0.5 | 0.02074 (12) | |
I1 | 0.23893 (7) | 0.75 | 0.39913 (5) | 0.02601 (18) | |
I2 | 0.45960 (7) | 0.25 | 0.32440 (5) | 0.02323 (17) | |
I3 | 0.70541 (7) | 0.75 | 0.43448 (5) | 0.02369 (17) | |
I4 | 0.15583 (8) | 0.25 | −0.02974 (6) | 0.0324 (2) | |
N1 | 0.3639 (11) | 0.75 | 0.2031 (7) | 0.029 (2) | |
H1A | 0.421 | 0.7908 | 0.2586 | 0.044* | 0.5 |
H1B | 0.3367 | 0.6433 | 0.2112 | 0.044* | 0.5 |
H1C | 0.2846 | 0.8159 | 0.1818 | 0.044* | 0.5 |
N2 | 0.9123 (9) | 0.75 | 0.7016 (7) | 0.026 (2) | |
H2A | 0.9082 | 0.7123 | 0.7577 | 0.04* | 0.5 |
H2B | 0.8592 | 0.6814 | 0.6554 | 0.04* | 0.5 |
H2C | 0.8766 | 0.8562 | 0.6917 | 0.04* | 0.5 |
O1 | 0.1355 (6) | 0.4963 (7) | 0.1640 (4) | 0.0310 (13) | |
H2 | 0.1381 | 0.4198 | 0.1239 | 0.037* | |
H1 | 0.0874 | 0.5843 | 0.1395 | 0.037* | |
C1 | 0.4482 (11) | 0.75 | 0.1311 (7) | 0.021 (2) | |
C2 | 0.5367 (9) | 0.5936 (11) | 0.1486 (6) | 0.0331 (19) | |
H2D | 0.4735 | 0.4955 | 0.1327 | 0.05* | |
H2E | 0.5938 | 0.5883 | 0.2147 | 0.05* | |
H2F | 0.601 | 0.5944 | 0.11 | 0.05* | |
C3 | 0.3394 (13) | 0.75 | 0.0346 (8) | 0.036 (3) | |
H3A | 0.3892 | 0.7382 | −0.0124 | 0.053* | 0.5 |
H3B | 0.2857 | 0.8558 | 0.0245 | 0.053* | 0.5 |
H3C | 0.2727 | 0.656 | 0.0291 | 0.053* | 0.5 |
C4 | 1.0871 (9) | 0.5933 (12) | 0.6483 (7) | 0.038 (2) | |
H4A | 1.0754 | 0.4932 | 0.6831 | 0.057* | |
H4B | 1.1833 | 0.5933 | 0.6413 | 0.057* | |
H4C | 1.0148 | 0.5925 | 0.5865 | 0.057* | |
C5 | 1.0681 (11) | 0.75 | 0.7013 (8) | 0.028 (3) | |
C6 | 1.1670 (13) | 0.75 | 0.8006 (9) | 0.035 (3) | |
H6A | 1.1593 | 0.8578 | 0.8301 | 0.053* | 0.5 |
H6B | 1.2662 | 0.7332 | 0.8007 | 0.053* | 0.5 |
H6C | 1.1396 | 0.659 | 0.8355 | 0.053* | 0.5 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pb1 | 0.0247 (2) | 0.0156 (2) | 0.0211 (2) | −0.00140 (15) | 0.00596 (15) | 0.00049 (16) |
I1 | 0.0222 (3) | 0.0296 (4) | 0.0243 (4) | 0 | 0.0045 (3) | 0 |
I2 | 0.0241 (3) | 0.0261 (4) | 0.0195 (3) | 0 | 0.0069 (3) | 0 |
I3 | 0.0253 (3) | 0.0214 (4) | 0.0278 (4) | 0 | 0.0134 (3) | 0 |
I4 | 0.0335 (4) | 0.0302 (4) | 0.0357 (4) | 0 | 0.0141 (3) | 0 |
N1 | 0.037 (5) | 0.023 (5) | 0.032 (5) | 0 | 0.016 (4) | 0 |
N2 | 0.021 (5) | 0.032 (6) | 0.029 (5) | 0 | 0.011 (4) | 0 |
O1 | 0.040 (3) | 0.026 (3) | 0.030 (3) | 0.003 (2) | 0.015 (3) | 0.003 (3) |
C1 | 0.025 (5) | 0.021 (6) | 0.015 (5) | 0 | 0.003 (4) | 0 |
C2 | 0.038 (4) | 0.032 (5) | 0.031 (4) | 0.008 (4) | 0.014 (4) | 0.011 (4) |
C3 | 0.039 (7) | 0.048 (8) | 0.019 (6) | 0 | 0.007 (5) | 0 |
C4 | 0.029 (4) | 0.032 (5) | 0.052 (6) | −0.001 (4) | 0.012 (4) | −0.015 (5) |
C5 | 0.014 (5) | 0.041 (7) | 0.030 (6) | 0 | 0.008 (4) | 0 |
C6 | 0.030 (6) | 0.042 (8) | 0.028 (6) | 0 | 0.002 (5) | 0 |
Pb1—I3 | 3.1953 (5) | C1—C2iv | 1.494 (10) |
Pb1—I3i | 3.1953 (5) | C1—C2 | 1.494 (10) |
Pb1—I1i | 3.2263 (6) | C1—C3 | 1.513 (15) |
Pb1—I1 | 3.2263 (6) | C2—H2D | 0.98 |
Pb1—I2i | 3.2355 (6) | C2—H2E | 0.98 |
Pb1—I2 | 3.2355 (6) | C2—H2F | 0.98 |
I1—Pb1ii | 3.2263 (6) | C3—H3A | 0.98 |
I2—Pb1iii | 3.2355 (6) | C3—H3B | 0.98 |
I3—Pb1ii | 3.1953 (5) | C3—H3C | 0.98 |
N1—C1 | 1.553 (13) | C4—C5 | 1.523 (10) |
N1—H1A | 0.91 | C4—H4A | 0.98 |
N1—H1B | 0.91 | C4—H4B | 0.98 |
N1—H1C | 0.91 | C4—H4C | 0.98 |
N2—C5 | 1.527 (12) | C5—C6 | 1.510 (16) |
N2—H2A | 0.91 | C5—C4iv | 1.523 (10) |
N2—H2B | 0.91 | C6—H6A | 0.98 |
N2—H2C | 0.91 | C6—H6B | 0.98 |
O1—H2 | 0.8633 | C6—H6C | 0.98 |
O1—H1 | 0.8616 | ||
I1i—Pb1—I1 | 180 | C1—C2—H2D | 109.5 |
I2i—Pb1—I2 | 180 | C1—C2—H2E | 109.5 |
I3—Pb1—I3i | 180 | H2D—C2—H2E | 109.5 |
I3—Pb1—I1i | 92.706 (16) | C1—C2—H2F | 109.5 |
I3—Pb1—I1 | 87.294 (16) | H2D—C2—H2F | 109.5 |
I3—Pb1—I2i | 86.509 (15) | H2E—C2—H2F | 109.5 |
I3—Pb1—I2 | 93.491 (15) | C1—C3—H3A | 109.5 |
I1—Pb1—I2 | 96.654 (16) | C1—C3—H3B | 109.5 |
I1—Pb1—I2i | 83.346 (16) | H3A—C3—H3B | 109.5 |
Pb1ii—I1—Pb1 | 76.221 (17) | C1—C3—H3C | 109.5 |
Pb1—I2—Pb1iii | 75.966 (17) | H3A—C3—H3C | 109.5 |
Pb1—I3—Pb1ii | 77.097 (16) | H3B—C3—H3C | 109.5 |
C1—N1—H1A | 109.5 | C5—C4—H4A | 109.5 |
C1—N1—H1B | 109.5 | C5—C4—H4B | 109.5 |
H1A—N1—H1B | 109.5 | H4A—C4—H4B | 109.5 |
C1—N1—H1C | 109.5 | C5—C4—H4C | 109.5 |
H1A—N1—H1C | 109.5 | H4A—C4—H4C | 109.5 |
H1B—N1—H1C | 109.5 | H4B—C4—H4C | 109.5 |
C5—N2—H2A | 109.5 | C6—C5—C4 | 112.0 (6) |
C5—N2—H2B | 109.5 | C6—C5—C4iv | 112.0 (6) |
H2A—N2—H2B | 109.5 | C4—C5—C4iv | 110.1 (10) |
C5—N2—H2C | 109.5 | C6—C5—N2 | 109.5 (9) |
H2A—N2—H2C | 109.5 | C4—C5—N2 | 106.6 (6) |
H2B—N2—H2C | 109.5 | C4iv—C5—N2 | 106.6 (6) |
H2—O1—H1 | 113.9 | C5—C6—H6A | 109.5 |
C2iv—C1—C2 | 113.0 (10) | C5—C6—H6B | 109.5 |
C2iv—C1—C3 | 111.6 (6) | H6A—C6—H6B | 109.5 |
C2—C1—C3 | 111.6 (6) | C5—C6—H6C | 109.5 |
C2iv—C1—N1 | 106.3 (6) | H6A—C6—H6C | 109.5 |
C2—C1—N1 | 106.3 (6) | H6B—C6—H6C | 109.5 |
C3—C1—N1 | 107.6 (9) | ||
I3—Pb1—I1—Pb1ii | −40.902 (15) | I1i—Pb1—I2—Pb1iii | 45.793 (14) |
I3i—Pb1—I1—Pb1ii | 139.098 (15) | I1—Pb1—I2—Pb1iii | −134.207 (14) |
I2i—Pb1—I1—Pb1ii | 45.896 (13) | I1i—Pb1—I3—Pb1ii | −138.796 (16) |
I2—Pb1—I1—Pb1ii | −134.104 (13) | I1—Pb1—I3—Pb1ii | 41.204 (16) |
I3—Pb1—I2—Pb1iii | 138.114 (14) | I2i—Pb1—I3—Pb1ii | −42.289 (14) |
I3i—Pb1—I2—Pb1iii | −41.886 (14) | I2—Pb1—I3—Pb1ii | 137.711 (14) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1; (iii) −x+1, y−1/2, −z+1; (iv) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I3 | 0.91 | 3.21 | 4.016 (10) | 148 |
N1—H1B···O1 | 0.91 | 2.21 | 2.936 (9) | 136 |
N1—H1C···O1iv | 0.91 | 2.05 | 2.936 (9) | 164 |
N2—H2A···O1i | 0.91 | 2.16 | 2.958 (9) | 147 |
N2—H2B···I3 | 0.91 | 3.25 | 3.905 (10) | 131 |
N2—H2C···O1ii | 0.91 | 2.48 | 2.958 (9) | 113 |
O1—H2···I4 | 0.86 | 2.73 | 3.572 (6) | 165 |
O1—H1···I4v | 0.86 | 2.78 | 3.570 (6) | 154 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+1; (iv) x, −y+3/2, z; (v) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | (C4H12N)2[PbI3]I·2H2O |
Mr | 899.11 |
Crystal system, space group | Monoclinic, P21/m |
Temperature (K) | 173 |
a, b, c (Å) | 9.7917 (10), 7.9649 (8), 15.0594 (16) |
β (°) | 107.985 (3) |
V (Å3) | 1117.1 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 13.08 |
Crystal size (mm) | 0.28 × 0.1 × 0.09 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Integration (XPREP; Bruker, 1999) |
Tmin, Tmax | 0.174, 0.388 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5842, 2878, 2416 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.101, 1.07 |
No. of reflections | 2878 |
No. of parameters | 96 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.67, −2.32 |
Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 1999), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
Pb1—I3 | 3.1953 (5) | Pb1—I2 | 3.2355 (6) |
Pb1—I1 | 3.2263 (6) | ||
I3—Pb1—I1i | 92.706 (16) | I3—Pb1—I2 | 93.491 (15) |
I3—Pb1—I1 | 87.294 (16) | I1—Pb1—I2 | 96.654 (16) |
I3—Pb1—I2i | 86.509 (15) | I1—Pb1—I2i | 83.346 (16) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I3 | 0.91 | 3.21 | 4.016 (10) | 148 |
N1—H1B···O1 | 0.91 | 2.21 | 2.936 (9) | 136 |
N1—H1C···O1ii | 0.91 | 2.05 | 2.936 (9) | 164 |
N2—H2A···O1i | 0.91 | 2.16 | 2.958 (9) | 147 |
N2—H2B···I3 | 0.91 | 3.25 | 3.905 (10) | 131 |
N2—H2C···O1iii | 0.91 | 2.48 | 2.958 (9) | 113 |
O1—H2···I4 | 0.86 | 2.73 | 3.572 (6) | 165 |
O1—H1···I4iv | 0.86 | 2.78 | 3.570 (6) | 154 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+3/2, z; (iii) −x+1, y+1/2, −z+1; (iv) −x, −y+1, −z. |
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In recent years, a significant number of organic–inorganic hybrid materials based on metal halide units have been prepared and studied. For reviews see Papavassiliou (1997) and Mitzi (1999). Haloplumbates in particular have demonstrated a propensity for forming a great variety of crystalline structures by self-assembling from suitable solution mixtures. It has been shown that their structures can vary considerably, ranging from systems based on isolated molecules to systems containing extended chains as in [Me4N][PbI3] (Contreras et al., 1983) and right up to two- or three-dimensional networks (Mitzi, 1999). For systems containing extended chains, the extended chains may be formed by one, two or three bridging halides. A search of the Cambridge Structural Database (Version 5.27, November 2005 release; Allen 2002) indicated that most crystal structures with tertiary butylammonium groups have isolated octahedra, as in SnCl6 (Ghozlen et al., 1991), TeCl6 (Ishida & Kashino, 1992) and TeBr6 (Baker et al., 1995), or isolated SnCl4 tetrahedra (Ishida & Kashino, 1993). To the best of our knowledgwe, only two structures have a one-dimensional system, viz. (C4H12N)2Sb2Cl8, which has edge-sharing chains of square–pyramidal SbCl5 (Belz et al., 1992) and [(t-C4H12N)CdBr3]2·H2O, which has edge-sharing chains of trigonal–bipyramidal CdBr5 (Ishihara et al., 1999).
The title compound has a one-dimensional arrangement in which chains of face-sharing PbI6 octahedra run along the unit cell (see Fig. 1). The channels in between the chains are occupied by t-butylammonium molecules, an isolated I atom on a mirror plane at y = 1/4 (I4), and water moleucles of hydration. In the direction perpendicular to the chains, the crystal cohesion is achieved by N—H···I, N—H···O and O—H···I hydrogen bridges. In the direction parallel to the chains, the cohesion is archieved by strong ionic bonds between the I and Pb atoms.
The inorganic motif is built up from characteristic face-sharing PbI6 octahedra, which form infinite chains along the b axis. One unique inorganic chain runs through the centre of the unit cell. The asymmetric unit consists of a Pb atom on a centre of inversion and three I atoms, all on special positions, with I1 and I3 lying on the mirror plane at y = 0.75 and I2 on the mirror plane at y = 0.25. Within the chains, the shared face consists of these three halides. The octahedra are somewhat distorted, with all three unique Pb—I distances different (Table 1), while the bond angles between cis ligands range from 83.346 (16) to 96.654 (16)°.
There are two unique t-butylammonium cations in the asymmetric unit, labeled cat1 (containing atom N1) and cat2 (containing atom N2). In cat1, atoms N1, C1 and C3 lie on the mirror plane at y = 3/4; atom C2 occupies a general position. In cat2, atoms N2, C5 and C6 lie on the mirror plane at y = 1/4, with atom C4 in a general position.
The two unique cations in the asymmetric unit interact with the inorganic chains via long N—H···I3 hydrogen bridges; the distances are 3.21 Å and 3.25 Å, respectively, for cat1 and cat2 (Table 2). The last two H atoms on the ammonium head groups bridge to the O atom of the water molecule of hydration. The N—H···O distances range from 2.05 to 2.48 Å. Lastly, the H atoms on the water molecule bridge towards the isolated I atom to form a symmetrical ring with graph-set notation R22(8), with donor–acceptor distances of 2.73 and 2.78 Å.