Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104007553/fg1746sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007553/fg1746Isup2.hkl |
CCDC reference: 241218
PbI2 (0.125 g, 0.271 mmol) and C5H16N2 (0.031 g, 0.507 mmol) were added to HI (3 ml) and the mixture was heated until all the components dissolved. The solution was allowed to cool to room temperature, whereupon yellow plate-like crystals formed. A crystal suitable for X-ray diffraction analysis was selected and studied. Analysis calculated for C10H32N4Pb3I10: C 5.72, H 1.54, N 2.67%; found: C 5.74, H 1.63, N 2.73%.
All H atoms were allowed for in idealized positions in the riding-model approximation [C—H = 0.97 Å, N—H = 0.89 Å and Uiso(H) = 1.2Ueq(C,N)].
Data collection: SMART-NT (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: XPREP (Bruker, 1999); 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).
(C5H16N2)2[Pb3I10] | Z = 1 |
Mr = 2098.97 | F(000) = 896 |
Triclinic, P1 | Dx = 3.742 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8543 (15) Å | Cell parameters from 849 reflections |
b = 11.1457 (19) Å | θ = 2.6–25° |
c = 11.5725 (19) Å | µ = 21.82 mm−1 |
α = 109.624 (3)° | T = 293 K |
β = 106.173 (3)° | Plate, yellow |
γ = 107.339 (3)° | 0.30 × 0.24 × 0.03 mm |
V = 931.4 (3) Å3 |
Bruker SMART CCD area-detector diffractometer | 3257 independent reflections |
Radiation source: fine-focus sealed tube | 2593 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ϕ and ω scans | θmax = 25°, θmin = 2.1° |
Absorption correction: integration (XPREP in SAINT-Plus; Bruker, 1999) | h = −10→7 |
Tmin = 0.026, Tmax = 0.643 | k = −13→13 |
5061 measured reflections | l = −11→13 |
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)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.104 | w = 1/[σ2(Fo2) + (0.0464P)2 + 4.4173P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
3257 reflections | Δρmax = 1.25 e Å−3 |
127 parameters | Δρmin = −1.19 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: 0.00170 (19) |
(C5H16N2)2[Pb3I10] | γ = 107.339 (3)° |
Mr = 2098.97 | V = 931.4 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.8543 (15) Å | Mo Kα radiation |
b = 11.1457 (19) Å | µ = 21.82 mm−1 |
c = 11.5725 (19) Å | T = 293 K |
α = 109.624 (3)° | 0.30 × 0.24 × 0.03 mm |
β = 106.173 (3)° |
Bruker SMART CCD area-detector diffractometer | 3257 independent reflections |
Absorption correction: integration (XPREP in SAINT-Plus; Bruker, 1999) | 2593 reflections with I > 2σ(I) |
Tmin = 0.026, Tmax = 0.643 | Rint = 0.052 |
5061 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.104 | H-atom parameters constrained |
S = 1.10 | Δρmax = 1.25 e Å−3 |
3257 reflections | Δρmin = −1.19 e Å−3 |
127 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Pb1 | 0.5000 | 0.5000 | 0.5000 | 0.0392 (2) | |
Pb2 | 0.17920 (6) | 0.10698 (5) | 0.21099 (5) | 0.03863 (18) | |
I1 | 0.14443 (11) | 0.29176 (9) | 0.48552 (10) | 0.0443 (3) | |
I2 | 0.27005 (11) | 0.40849 (10) | 0.19085 (10) | 0.0477 (3) | |
I3 | 0.60509 (11) | 0.24323 (10) | 0.39754 (11) | 0.0503 (3) | |
I4 | −0.21829 (10) | 0.03520 (9) | 0.06001 (9) | 0.0426 (2) | |
I5 | 0.08075 (13) | −0.14724 (10) | 0.27750 (11) | 0.0523 (3) | |
N1 | −0.7421 (18) | 0.0562 (15) | −0.3538 (16) | 0.075 (4) | |
H1A | −0.7447 | −0.0237 | −0.3522 | 0.113* | |
H1B | −0.8099 | 0.0372 | −0.4366 | 0.113* | |
H1C | −0.7807 | 0.0967 | −0.2954 | 0.113* | |
N5 | −0.0792 (18) | 0.4487 (18) | 0.2629 (14) | 0.082 (5) | |
H5A | −0.1113 | 0.5038 | 0.3167 | 0.123* | |
H5B | 0.0352 | 0.4922 | 0.2887 | 0.123* | |
H5C | −0.1052 | 0.3677 | 0.2681 | 0.123* | |
C1 | −0.563 (2) | 0.152 (2) | −0.316 (2) | 0.088 (7) | |
H1D | −0.5640 | 0.2312 | −0.3333 | 0.106* | |
H1E | −0.5166 | 0.1028 | −0.3724 | 0.106* | |
C2 | −0.443 (2) | 0.2082 (19) | −0.1659 (16) | 0.064 (5) | |
H2A | −0.3229 | 0.2531 | −0.1515 | 0.077* | |
H2B | −0.4568 | 0.1290 | −0.1455 | 0.077* | |
C3 | −0.482 (2) | 0.3170 (18) | −0.0656 (18) | 0.062 (4) | |
H3A | −0.4559 | 0.4018 | −0.0775 | 0.074* | |
H3B | −0.6051 | 0.2764 | −0.0844 | 0.074* | |
C4 | −0.370 (2) | 0.354 (2) | 0.0812 (18) | 0.076 (5) | |
H4A | −0.3959 | 0.4205 | 0.1425 | 0.091* | |
H4B | −0.4014 | 0.2694 | 0.0926 | 0.091* | |
C5 | −0.174 (2) | 0.419 (2) | 0.120 (2) | 0.071 (5) | |
H5D | −0.1456 | 0.3542 | 0.0595 | 0.085* | |
H5E | −0.1395 | 0.5061 | 0.1117 | 0.085* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pb1 | 0.0344 (4) | 0.0359 (4) | 0.0435 (4) | 0.0131 (3) | 0.0162 (3) | 0.0162 (3) |
Pb2 | 0.0381 (3) | 0.0398 (3) | 0.0365 (3) | 0.0161 (2) | 0.0156 (2) | 0.0164 (2) |
I1 | 0.0439 (5) | 0.0441 (5) | 0.0451 (5) | 0.0152 (4) | 0.0257 (4) | 0.0183 (4) |
I2 | 0.0477 (5) | 0.0574 (6) | 0.0494 (6) | 0.0240 (4) | 0.0249 (4) | 0.0321 (5) |
I3 | 0.0456 (5) | 0.0488 (5) | 0.0621 (6) | 0.0288 (4) | 0.0223 (4) | 0.0242 (5) |
I4 | 0.0402 (4) | 0.0487 (5) | 0.0421 (5) | 0.0211 (4) | 0.0194 (4) | 0.0209 (4) |
I5 | 0.0645 (6) | 0.0468 (6) | 0.0547 (6) | 0.0253 (5) | 0.0310 (5) | 0.0271 (5) |
N1 | 0.077 (9) | 0.069 (10) | 0.071 (10) | 0.034 (8) | 0.024 (8) | 0.027 (8) |
N5 | 0.067 (9) | 0.103 (12) | 0.053 (9) | 0.049 (9) | 0.017 (7) | 0.007 (9) |
C1 | 0.060 (10) | 0.096 (15) | 0.084 (14) | 0.003 (10) | −0.001 (9) | 0.068 (13) |
C2 | 0.057 (9) | 0.071 (12) | 0.053 (10) | 0.024 (8) | 0.016 (8) | 0.028 (9) |
C3 | 0.069 (10) | 0.062 (10) | 0.077 (12) | 0.042 (8) | 0.039 (9) | 0.038 (9) |
C4 | 0.078 (12) | 0.077 (13) | 0.061 (12) | 0.037 (10) | 0.029 (9) | 0.017 (10) |
C5 | 0.061 (10) | 0.072 (12) | 0.094 (14) | 0.037 (9) | 0.036 (10) | 0.041 (11) |
Pb1—I2i | 3.1998 (11) | N5—H5A | 0.89 |
Pb1—I2 | 3.1998 (11) | N5—H5B | 0.89 |
Pb1—I3i | 3.2226 (10) | N5—H5C | 0.89 |
Pb1—I3 | 3.2226 (10) | C1—C2 | 1.54 (2) |
Pb1—I1i | 3.2275 (10) | C1—H1D | 0.97 |
Pb1—I1 | 3.2275 (10) | C1—H1E | 0.97 |
Pb2—I5 | 3.1221 (12) | C2—C3 | 1.57 (2) |
Pb2—I4 | 3.1680 (10) | C2—H2A | 0.97 |
Pb2—I4ii | 3.1718 (12) | C2—H2B | 0.97 |
Pb2—I1 | 3.3102 (12) | C3—C4 | 1.54 (2) |
Pb2—I2 | 3.3187 (12) | C3—H3A | 0.97 |
Pb2—I3 | 3.3222 (11) | C3—H3B | 0.97 |
N1—C1 | 1.46 (2) | C4—C5 | 1.53 (2) |
N1—H1A | 0.89 | C4—H4A | 0.97 |
N1—H1B | 0.89 | C4—H4B | 0.97 |
N1—H1C | 0.89 | C5—H5D | 0.97 |
N5—C5 | 1.50 (2) | C5—H5E | 0.97 |
I2i—Pb1—I2 | 180 | H1A—N1—H1C | 109.5 |
I2i—Pb1—I3i | 88.76 (3) | H1B—N1—H1C | 109.5 |
I2—Pb1—I3i | 91.24 (3) | C5—N5—H5A | 109.5 |
I2i—Pb1—I3 | 91.24 (3) | C5—N5—H5B | 109.5 |
I2—Pb1—I3 | 88.76 (3) | H5A—N5—H5B | 109.5 |
I3i—Pb1—I3 | 180 | C5—N5—H5C | 109.5 |
I2i—Pb1—I1i | 84.82 (3) | H5A—N5—H5C | 109.5 |
I2—Pb1—I1i | 95.18 (3) | H5B—N5—H5C | 109.5 |
I3i—Pb1—I1i | 91.17 (3) | N1—C1—C2 | 112.5 (16) |
I3—Pb1—I1i | 88.83 (3) | N1—C1—H1D | 109.1 |
I2i—Pb1—I1 | 95.18 (3) | C2—C1—H1D | 109.1 |
I2—Pb1—I1 | 84.82 (3) | N1—C1—H1E | 109.1 |
I3i—Pb1—I1 | 88.83 (3) | C2—C1—H1E | 109.1 |
I3—Pb1—I1 | 91.17 (3) | H1D—C1—H1E | 107.8 |
I1i—Pb1—I1 | 180 | C1—C2—C3 | 113.3 (15) |
I5—Pb2—I4 | 91.83 (3) | C1—C2—H2A | 108.9 |
I5—Pb2—I4ii | 100.21 (3) | C3—C2—H2A | 108.9 |
I4—Pb2—I4ii | 94.16 (3) | C1—C2—H2B | 108.9 |
I5—Pb2—I1 | 87.33 (3) | C3—C2—H2B | 108.9 |
I4—Pb2—I1 | 84.54 (3) | H2A—C2—H2B | 107.7 |
I4ii—Pb2—I1 | 172.40 (3) | C4—C3—C2 | 109.3 (12) |
I5—Pb2—I2 | 168.97 (3) | C4—C3—H3A | 109.8 |
I4—Pb2—I2 | 86.31 (3) | C2—C3—H3A | 109.8 |
I4ii—Pb2—I2 | 90.77 (3) | C4—C3—H3B | 109.8 |
I1—Pb2—I2 | 81.67 (3) | C2—C3—H3B | 109.8 |
I5—Pb2—I3 | 95.38 (3) | H3A—C3—H3B | 108.3 |
I4—Pb2—I3 | 169.37 (3) | C5—C4—C3 | 113.5 (16) |
I4ii—Pb2—I3 | 92.25 (3) | C5—C4—H4A | 108.9 |
I1—Pb2—I3 | 88.00 (3) | C3—C4—H4A | 108.9 |
I2—Pb2—I3 | 85.13 (3) | C5—C4—H4B | 108.9 |
Pb1—I1—Pb2 | 75.14 (2) | C3—C4—H4B | 108.9 |
Pb1—I2—Pb2 | 75.38 (2) | H4A—C4—H4B | 107.7 |
Pb1—I3—Pb2 | 75.04 (2) | N5—C5—C4 | 108.5 (16) |
Pb2—I4—Pb2ii | 85.84 (3) | N5—C5—H5D | 110.0 |
C1—N1—H1A | 109.5 | C4—C5—H5D | 110.0 |
C1—N1—H1B | 109.5 | N5—C5—H5E | 110.0 |
H1A—N1—H1B | 109.5 | C4—C5—H5E | 110.0 |
C1—N1—H1C | 109.5 | H5D—C5—H5E | 108.4 |
I2i—Pb1—I1—Pb2 | −132.37 (2) | I2i—Pb1—I3—Pb2 | 136.08 (2) |
I2—Pb1—I1—Pb2 | 47.63 (2) | I2—Pb1—I3—Pb2 | −43.92 (2) |
I3i—Pb1—I1—Pb2 | 138.97 (2) | I1i—Pb1—I3—Pb2 | −139.13 (3) |
I3—Pb1—I1—Pb2 | −41.03 (2) | I1—Pb1—I3—Pb2 | 40.87 (3) |
I5—Pb2—I1—Pb1 | 135.05 (2) | I5—Pb2—I3—Pb1 | −126.79 (3) |
I4—Pb2—I1—Pb1 | −132.86 (3) | I4—Pb2—I3—Pb1 | 5.68 (18) |
I2—Pb2—I1—Pb1 | −45.80 (2) | I4ii—Pb2—I3—Pb1 | 132.74 (2) |
I3—Pb2—I1—Pb1 | 39.57 (2) | I1—Pb2—I3—Pb1 | −39.66 (2) |
I3i—Pb1—I2—Pb2 | −136.11 (3) | I2—Pb2—I3—Pb1 | 42.15 (3) |
I3—Pb1—I2—Pb2 | 43.89 (3) | I5—Pb2—I4—Pb2ii | −100.38 (3) |
I1i—Pb1—I2—Pb2 | 132.61 (2) | I1—Pb2—I4—Pb2ii | 172.48 (3) |
I1—Pb1—I2—Pb2 | −47.39 (2) | I2—Pb2—I4—Pb2ii | 90.51 (3) |
I5—Pb2—I2—Pb1 | 50.68 (15) | I3—Pb2—I4—Pb2ii | 126.92 (17) |
I4—Pb2—I2—Pb1 | 131.26 (2) | N1—C1—C2—C3 | −71 (2) |
I4ii—Pb2—I2—Pb1 | −134.62 (2) | C1—C2—C3—C4 | 174.0 (15) |
I1—Pb2—I2—Pb1 | 46.25 (2) | C2—C3—C4—C5 | 59 (2) |
I3—Pb2—I2—Pb1 | −42.44 (2) | C3—C4—C5—N5 | −179.2 (14) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I3ii | 0.89 | 3.02 | 3.806 (15) | 149 |
N1—H1B···I5iii | 0.89 | 2.93 | 3.669 (16) | 142 |
N1—H1C···I5iv | 0.89 | 2.92 | 3.672 (15) | 143 |
N5—H5A···I1v | 0.89 | 2.79 | 3.668 (14) | 169 |
N5—H5B···I2 | 0.89 | 2.87 | 3.531 (14) | 132 |
N5—H5C···I4 | 0.89 | 3.31 | 4.001 (16) | 136 |
Symmetry codes: (ii) −x, −y, −z; (iii) x−1, y, z−1; (iv) −x−1, −y, −z; (v) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C5H16N2)2[Pb3I10] |
Mr | 2098.97 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.8543 (15), 11.1457 (19), 11.5725 (19) |
α, β, γ (°) | 109.624 (3), 106.173 (3), 107.339 (3) |
V (Å3) | 931.4 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 21.82 |
Crystal size (mm) | 0.30 × 0.24 × 0.03 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Integration (XPREP in SAINT-Plus; Bruker, 1999) |
Tmin, Tmax | 0.026, 0.643 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5061, 3257, 2593 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.104, 1.10 |
No. of reflections | 3257 |
No. of parameters | 127 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.25, −1.19 |
Computer programs: SMART-NT (Bruker, 1998), SAINT-Plus (Bruker, 1999), XPREP (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
Pb1—I2 | 3.1998 (11) | Pb2—I4i | 3.1718 (12) |
Pb1—I3 | 3.2226 (10) | Pb2—I1 | 3.3102 (12) |
Pb1—I1 | 3.2275 (10) | Pb2—I2 | 3.3187 (12) |
Pb2—I5 | 3.1221 (12) | Pb2—I3 | 3.3222 (11) |
Pb2—I4 | 3.1680 (10) | ||
I4i—Pb2—I1 | 172.40 (3) | I4—Pb2—I3 | 169.37 (3) |
I5—Pb2—I2 | 168.97 (3) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···I3i | 0.89 | 3.02 | 3.806 (15) | 149 |
N1—H1B···I5ii | 0.89 | 2.93 | 3.669 (16) | 142 |
N1—H1C···I5iii | 0.89 | 2.92 | 3.672 (15) | 143 |
N5—H5A···I1iv | 0.89 | 2.79 | 3.668 (14) | 169 |
N5—H5B···I2 | 0.89 | 2.87 | 3.531 (14) | 132 |
N5—H5C···I4 | 0.89 | 3.31 | 4.001 (16) | 136 |
Symmetry codes: (i) −x, −y, −z; (ii) x−1, y, z−1; (iii) −x−1, −y, −z; (iv) −x, −y+1, −z+1. |
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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 crystaline structures by self-assembling from suitable solution mixtures. It has been shown that these structures can vary considerably, ranging from systems based on isolated molecules, to those containing infinite chains, as in [Me4N][PbI3] (Contreras et al., 1983), right up to two- or three-dimensional networks (Mitzi, 1999). The lead iodide octahedra can be connected in one of three ways, viz. face-sharing between two equatorial and one axial halide, edge-sharing between two equatorial halides, or corner-sharing through a single halide. It is also possible to have combinations of the various types of sharing in one chain, as in [Na(dmf)3]4[Pb6I16] and [PrN(C2H4)3NPr][Pb2I6], where the octahedra simultaneously share common faces, edges and vertices (Krautscheid et al., 2001). The chains formed by the octahedra can be described by the shorthand notation (fme)n for m adjacent face-sharing octahedra, f, connected by octahedra sharing an edge, denoted e. Structures with m = 3 have been synthesized for lead iodide (Maxcy et al., 2003; Krautscheid & Vielsack, 1997) and tin iodide (Lode & Krautscheid, 2001) octahedra. The case with m = 1 has PbI6 octahedra that share a face with PbI5 square pyramids, which in turn share an edge.
Pentadiamine has previously been incorporated into the layered perovskite structure type. For example, single-crystal structures of [NH3C5H10NH3]CuX4 (X = Cl and Br; Garland et al., 1990) have been determined. In general, the hybrid perovskite family displays structural phase transitions resulting from conformational changes within the amines between the layers, as well as the slipping of layers with respect to each other. The temperatures at which the phase changes occur are dependent on the length of the chain, as can be seen for [NH3(CH2)nNH3]CdCl4 (n = 3, 4 and 5; Kind et al., 1981).
We present here an m = 3 case, which has [Pb3I10]n4n- chains approximately extending along [111] with the pentadiammonium ion as counter-cation (Fig. 1). The asymmetric unit contains two crystallographically independent Pb atoms, viz. Pb1 and Pb2. Each face-sharing monomer unit consists of two Pb2 octahedra and one Pb1 octahedron, where the central Pb1 octahedron is connected to the Pb2 octahedra by shared faces. The Pb2 octahedra are linked via edge-sharing at both ends to adjacent monomers. The overall repeat pattern can be represented as (f2e)3 (Fig. 2).
Atom Pb1 is located on a centre of inversion, chosen for convenience as that at the centre of the unit cell, and is bonded to three unique halide atoms, viz. I1, I2 and I3, which then complete the full octahedron through the inversion centre. At the centre of a quadrilateral formed by atoms Pb2, I4, Pb2a and I4a [Pb2a and I4a are at the equivalent position (-x,-y,-z); (Fig. 1)] is a second inversion centre, chosen for convenience as the cell origin. Atom Pb2 is bonded to four unique halides, the extra halide, I4, is responsible for the edge-sharing between the Pb2 octahedra. This second inversion centre then generates the second I4 halide involved in the edge-sharing. The metal–halide bond distances are very similiar, possibly because of the lower strain imposed by the simpler sharing. Atoms I1, I2 and I3 are the three halides that partake in the face-sharing between the Pb1 and Pb2 octahedra. Axial atom I5 is the only halide not involved in any bonding to adjacent octahedra and has the shortest Pb—I distance [3.1221 (12) Å].
Atom Pb1 has a more regular coordination geometry, as it lies on an inversion centre, which ensures that all trans angles are exactly 180°, and shares trans faces with the two adjacent Pb2 octahedra. Atom Pb2, in contrast, has a more distorted environment, with all cis and trans angles different (Table 2).
One unique inorganic chain runs through the unit cell along the body, diagonally from (0,0,0) to (1,1,1). The Pb1 octahedra are located at the centre of the the unit cell, with the two Pb2 octahedra located along the body diagonal and related by the inversion centres at (0,0,0) and (1,1,1). In the crystal structure, the cations occupy channels that run parallel to the anion chains. Each diammonium cation is hydrogen bonded to three different chains in a pseudo-trigonal pattern. One anion chain lies along the body diagonal and the other two run through the corners of the unit cell in a pseudo-hexagonal pattern (Fig. 3).
Both ammonium groups on the cation form three hydrogen bonds to I atoms of the anion chains (details are in Table 2). Ammonium atom N1 connects three chains, atom I5 being a bifurcated acceptor. The ammonium group containing atom N2 bonds to two chains. It connects via a short and a long hydrogen bond to atoms I2 and I4, respectively, and to a second chain via the N2—H2B···I1iv interaction.
The pentadiamine ion exhibits two types of conformational arrangement between the four possible torsion angles. There are antiperiplanar C1—C2—C3—C4 and C3—C4—C5—N5 angles of 174.0 (15) and −179.2 (14)°, and synclinal (gauche) C2—C3—C4—C5 and N1—C1—C2—C3 angles of 59 (2) and −71 (2)°.