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The compounds catena-poly[p-phenyl­enediammonium [[diiodo­lead(II)]-di-μ-iodo] dihydrate], {(C6H10N2)[PbI4]·2H2O}n, (I), and catena-poly[bis­(3,5-dimethyl­anilinium) [[diiodo­lead(II)]-di-μ-iodo]], {(C8H12N)2[PbI4]}n, (II), crystallize as organic–inorganic hybrids. As such, the structures consist of chains of [PbI2] units extending along the c axis in (I) and along the b axis in (II). The asymmetric unit in (I) contains one Pb atom on a site of 2/m symmetry, two I atoms and a water molecule on mirror planes, and a p-phenyl­enediammonium mol­ecule that sits around a site of 2/m symmetry with the C and N atoms on a mirror plane. In (II), the Pb atom is on a twofold axis and the two I atoms are on general positions. Each Pb atom is octa­hedrally coordinated to six I atoms, arranged as chains of edge-sharing octa­hedra. Both compounds undergo hydrogen-bonding inter­actions between the ammonium groups and the I atoms. In addition, there are hydrogen bonds between the water mol­ecules and the ammonium groups and halides in (I), and between the ammonium groups and the ring systems in (II).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106039746/av3041sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106039746/av3041Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106039746/av3041IIsup3.hkl
Contains datablock II

CCDC references: 632922; 632923

Comment top

In recent years, a significant number of organic–inorganic hybrid materials based on metal halide units have been prepared and studied. Haloplumbates in particular have demonstrated a propensity for forming a great variety of crystalline structures by self-assembly from suitable solution mixtures. It has been shown that their structures can vary considerably, ranging from systems based on isolated inorganic polyhedra (Billing & Lemmerer, 2006a) to ones containing extended chains, as in (C4H12)2[PbI3]·I·2H2O (Billing & Lemmerer, 2006b), right up to two- or three-dimensional networks (Billing & Lemmerer, 2006c). For systems containing extended chains, such chains may be formed by one, two or three bridging halides, referred to as corner-, edge- and face-sharing polyhedra, respectively. The most desired structure type, due to its suspected electroluminescence, photoluminescence and non-linear optical properties, is based on the K2NiF4 type system, which has two-dimensional layers of corner-sharing divalent metal halide octahedra, separated by organic compounds with primary ammonium cations, as in (C8H16N)2[PbI4] (Billing & Lemmerer, 2006d). The organic cations can either consist of alkylammonium chains or systems containing aromatic moieties, with either a monoammonium (R—NH3+) or a diammonium (+H3N—R—NH3+) group. One of the simplest aromatic systems with a primary amine is aniline, which has been incorporated into the two-dimensional type system with copper(II) chloride (Larsen, 1974). The diammonium version, para-phenylenediammonium, has also crystallized out in the K2NiF4 type system with a variety of metal halides, as in (H3NC6H4NH3)[CdBr4] (Ishihara et al., 1996) and (H3NC6H4NH3)[CuCl4] (Bourne & Mangombo, 2004). Continuing this work, we wished to investigate the packing of the hybrid compound with para-phenylenediamine and lead(II) iodide, and to study the influence of the methyl groups bonded to the aniline backbone in a second compound with lead(II) iodide.

The two compounds reported here, (H3NC6H4NH3)[PbI4]·2H2O, (I) (Fig. 1a), and (C8H9NH3)2[PbI4], (II) (Fig. 1b), adopt the same one-dimensional inorganic motif, albeit with different counterions to give unique packing arrangements. Other one and two-dimensional motifs that use the para-phenylenediammonium cation and lead(II) halides that have been reported to date include the twin anionic chains of cis edge-sharing [Pb2I62−] (Chakravarthy & Guloy, 1997) and the double-layer sheet of face-sharing square antiprisms of eight-coordinate lead(II) chloride (Bourne & Mangombo, 2004). To the best of our knowledge, there are only two previously reported cases of trans edge-sharing octahedral chains for lead(II) iodide, where square-pyramidal PbI5 units are connected to form infinite one-dimensional chains. The reported counter-ions are tetrahedral (Pr4N)+ and octahedral Mg(dmf)62+ (Krautscheid & Vielsack, 1998). The bridging Pb—I bond distances lie over a larger range with the former counter-ion [3.1017 (9)–3.4553 (9) Å] compared with the more symmetrical bond-length range [3.1836 (5)–3.2407 (6) Å] when the latter, bulkier, counter-ion is included in the hybrid structure (Krautscheid & Vielsack, 1998). Trans edge-sharing has also been reported for mercury; a one-dimensional chain of alternating octahedral and tetrahedral mercury(II) chloride units is formed when the counter-ion is (CH3)3NH+ (Salah et al., 1983), while the lone H atom interacts with the Cl anions via hydrogen bonding.

Fig. 2 clearly displays the one-dimensional inorganic motif adopted by (I), in which each para-phenylenediammonium molecule is surrounded by four one-dimensional chains of inorganic PbI6 octahedra in a chessboard-like pattern. In other words, the cations occupy the channels created by the anionic edge-sharing chains. In the direction of the b axis, crystal cohesion is achieved by a single N—H···I hydrogen bond on either end of the organic molecule, related to the NH3 polar groups. The water molecules are embedded between the organic and inorganic moieties and held in place by O—H···I and N—H···O hydrogen bonds. Within the inorganic chains, cohesion is achieved by strong ionic bonds between equatorial I and Pb2+ ions.

The inorganic chain consists of edge-sharing PbI6 octahedra. The asymmetric unit contains a Pb atom on a centre of inversion and two I atoms on mirror planes. Within a given octahedron, atom I2 occupies the equatorial position and atom I1 the axial. Edge sharing between adjacent octahedra occurs through the equatorial atoms only. The axial I atoms align along the b axis, with an angle of 26.50 (1)° between the I1···I1iii vector and the b axis [symmetry code: (iii) 1 − x, −y, z Please check added text]. The coordination geometry around the Pb atom shows the typical axial compression of the octahedral geometry, with the bridging Pb1—I2 distances [3.2429 (6) Å] longer than the axial Pb1—I1 distances [3.1895 (8) Å]. The angle between all cis-related I atoms deviates by 0.457 (17)° from 90°, with all trans angles equal to 180° (Table 1) [No transangles shown in Table 1?].

There is only one hydrogen bond between the N donor atom and the halide acceptor atom, instead of three as found in the K2NiF4-type systems. Nevertheless, the chains of edge-sharing octahedra are connected by the cations along the b axis in the sequence Ar—N1—H1C···I1—Pb1—I1···H1C—N1—Ar (Fig. 2). The two remaining H atoms of the ammonium head group bond to the O atom of the water molecule. The two hydrogen bonds are related by a mirror plane on which the para-phenylenediammonium cation lies, and hence the O1···H1B—N1—H1A···O1 donor···acceptor distances are almost identical (1.93 and 1.94 Å) (Fig. 3). The H atoms on the water molecule themselves both bond to the equatorial and axial I atoms of the octahedra (Table 2).

The para-phenylenediammonium cation sits on a twofold axis that is perpendicular to the ab plane, and hence the asymmetric unit consists of half the molecule only. The atomic numbering scheme is shown in Fig. 1(a). In addition, the entire para-phenylenediammonium cation is then disordered over a centre of inversion with site occupancy of exactly 0.5. The two parts of the disorder overlap perfectly. The para-phenylenediammonium cations all align along the b axis and are rotated by 16.57 (12)° away from the b axis, measured through the N1···N1 vector. Adjacent aromatic rings are separated by a centroid-to-centroid distance of 4.585 (1) Å, which is too large to be considered as representing ππ stacking interactions.

Compound (II) has a different packing arrangement to (I). In this case, hydrocarbon layers of 3,5-dimethylanilinium molecules alternate with ionic layers of edge-sharing PbI6 octahedra running along the b axis (Fig. 4). In the directions of the a and c axes, crystal cohesion between the inorganic and organic layers is achieved by three N—H···I hydrogen bonds, related to the NH3 polar groups. There are N—H···π interactions between neighbouring ring systems perpendicular to the hydrogen bonds. In the direction parallel to the inorganic chains, cohesion is again achieved by strong ionic bonds between equatorial I and Pb atoms.

The ionic layer consists of chains of edge-sharing PbI6 octahedra. The asymmetric unit consists of a Pb atom on a centre of inversion and two I atoms on general positions. Within a given octahedron, atom I2 occupies the equatorial position and atom I1 the axial. Edge sharing between adjacent octahedra occurs through the equatorial atoms only. The chains are aligned more parallel to one of the axes than the chains in (I), in this case the c axis. The angle is 6.74 (12)°, measured between the c axis and the vector through the axial I atoms. The coordination geometry around the Pb atom shows the typical axial compression of the octahedral geometry seen in (I), with the bridging Pb1—I2 distances longer than the axial Pb1—I1 distances (Table 3). The angles between cis- and trans-related I atoms deviate from 90 and 180°, respectively (Table 3).

The three H atoms form hydrogen bonds between two neighbouring chains. Atom H1C forms a weak hydrogen bond to the equatorial atom I1, but a stronger bond to the ring system of an adjacent 3,5-dimethylanilinium molecule of 2.95 Å. The C—H···π angle is 110.35 (24)°. The remaining two H atoms form hydrogen bonds to two axial halides of adjacent chains, with shorter donor···acceptor distances of 2.57 and 2.84 Å (Fig. 5). The 3,5-xylidinium cation sits on a general position. The atomic numbering scheme is shown in Fig. 1(b). Within the organic layers, the molecules are stacked head-to-tail along the [101] direction at a dihedral angle of 87.3 (1)°, and head-to-head along the [001] direction.

Experimental top

For the preparation of (I), PbI2 (0.200 g, 0.434 mmol) was dissolved in 47% HI (7 ml) in a test tube. NH2C6H4NH2 (0.043 g, 0.398 mmol) was then added and the resulting precipitate dissolved by refluxing for 12 h at 393 K. The solution was then cooled slowly to room temperature at 2 K h−1. A brown single-crystal suitable for X-ray diffraction analysis was selected and studied. Analysis, calculated for C6H14I4N2Pb: C 8.37, H 1.64, N 3.25%; found: C 8.23, H 1.79, N 3.13%.

For the preparation of (II), PbI2 (0.060 g, 0.130 mmol) was dissolved in 47% HI (2 ml) in a round-bottomed flask. C8H9NH2 (0.040 g, 0.330 mmol) was then added and the resulting precipitate dissolved by refluxing for 12 h at 363 K. The solution was then cooled slowly to room temperature at 2 K h−1. A yellow single-crystal suitable for X-ray diffraction analysis was selected and studied. Analysis, calculated for C16H24I4N2Pb: C 20.04, H 2.52, N 2.92%; found: C 19.96, H 2.48, N 2.89%.

Refinement top

For compound (I), all H atoms were found in a difference map. For H atoms bonded to O atoms, restraints were used to obtain reasonable 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 Ar—H = 0.95 Å and N—H = 0.91 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(N). There is a close contact between atom H7 of the water molecule and atoms H1A and H1B of the ammonium group (1.77 and 1.52 Å, respectively). The position of H7 is justified as it then forms a hydrogen bond to atom I1. The short intermolecular H···H contacts are due to the acute angle between the donor atom N1, atom O1 and the I1 acceptor atom. For compound (II), all H atoms were refined using a riding model, with Ar—H = 0.93 Å, C—H = 0.96 Å and N—H = 0.89 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(N). The NH3 and CH3 groups were allowed to rotate but not to tip in both compounds. The highest residual peaks are 0.82 Å from atom Pb1 in (I) and 0.87 Å from I2 in (II).

Computing details top

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, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. The asymmetric units of (a) (I) and (b) (II), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Only one position of disordered NH3+ moiety is shown. [Symmetry codes: (i) 1 − x, 1 − y, z; (ii) x, y, −1 + z; (iii) 1 − x, −y, z; (iv) 1 − x, −y, −1 + z; (v) x, −1 + x, z [Should this be x, −1 + y, z?]; (vi) −x, −1 + y, 1/2 − z; (vii) −x, y, 1/2 − z.]
[Figure 2] Fig. 2. A packing diagram of (I), viewed along the c axis. Hydrogen bonds between the three moieties are shown as dashed lines.
[Figure 3] Fig. 3. A magnified view of the edge-sharing PbI6 octahedra in (I) and the hydrogen bonds (dashed lines). Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (x, y, 1 + z), (1 − x, 1 − y, 1 + z) and (1 − x, 1 − y, z), respectively.
[Figure 4] Fig. 4. A packing diagram of (II), viewed along the b axis, showing the alternating organic–inorganic layers and the N—H···I hydrogen bonds.
[Figure 5] Fig. 5. A magnified view of the edge-sharing PbI6 octahedra in (II) and the N1—H1C···π hydrogen bond between the organic cations along the b axis.
(I) catena-poly[p-phenylenediammonium [[diiodolead(II)]-di-µ-iodo] dihydrate] top
Crystal data top
(C6H10N2)[PbI4]·2H2OF(000) = 748
Mr = 860.98Dx = 3.323 Mg m3
Orthorhombic, PnnmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2 2nCell parameters from 886 reflections
a = 12.952 (3) Åθ = 2.8–28.3°
b = 14.489 (3) ŵ = 16.97 mm1
c = 4.5851 (10) ÅT = 173 K
V = 860.4 (3) Å3Polyhedral, brown
Z = 20.5 × 0.37 × 0.3 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1095 reflections with I > 2σ(I)
ϕ and ω scansRint = 0.056
Absorption correction: integration
(XPREP in SAINT-Plus; Bruker, 1999)
θmax = 28°, θmin = 2.1°
Tmin = 0.012, Tmax = 0.059h = 1716
5460 measured reflectionsk = 1910
1168 independent reflectionsl = 56
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full w = 1/[σ2(Fo2) + (0.0479P)2 + 2.0341P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.032(Δ/σ)max = 0.001
wR(F2) = 0.081Δρmax = 2.36 e Å3
S = 1.11Δρmin = 1.02 e Å3
1168 reflectionsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
49 parametersExtinction coefficient: 0.0204 (9)
24 restraints
Crystal data top
(C6H10N2)[PbI4]·2H2OV = 860.4 (3) Å3
Mr = 860.98Z = 2
Orthorhombic, PnnmMo Kα radiation
a = 12.952 (3) ŵ = 16.97 mm1
b = 14.489 (3) ÅT = 173 K
c = 4.5851 (10) Å0.5 × 0.37 × 0.3 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1168 independent reflections
Absorption correction: integration
(XPREP in SAINT-Plus; Bruker, 1999)
1095 reflections with I > 2σ(I)
Tmin = 0.012, Tmax = 0.059Rint = 0.056
5460 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03224 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.11Δρmax = 2.36 e Å3
1168 reflectionsΔρmin = 1.02 e Å3
49 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
xyzUiso*/UeqOcc. (<1)
C10.5305 (8)0.4084 (7)0.50.0350 (19)
C20.4274 (9)0.4319 (9)0.50.065 (4)
H20.37640.38480.50.078*
C30.6018 (9)0.4776 (8)0.50.055 (3)
H30.67320.46260.50.066*
N10.5624 (7)0.3125 (5)0.50.0338 (16)
H1A0.61540.30470.62790.051*0.5
H1B0.58350.29630.31780.051*0.5
H1C0.50830.27630.55430.051*0.5
O10.6784 (6)0.2750 (6)00.0494 (19)
H60.70470.213700.059*
H70.60490.27300.059*
Pb10.5000.02409 (18)
I10.39010 (4)0.19700 (4)00.0267 (2)
I20.65935 (4)0.06905 (4)0.50.0279 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.031 (4)0.034 (4)0.040 (5)0.008 (3)00
C20.030 (4)0.039 (5)0.126 (11)0.009 (3)00
C30.031 (4)0.032 (4)0.102 (10)0.009 (4)00
N10.038 (4)0.033 (3)0.030 (4)0.008 (3)00
O10.041 (4)0.064 (5)0.043 (4)0.009 (4)00
Pb10.0249 (3)0.0239 (3)0.0235 (3)0.00054 (15)00
I10.0266 (3)0.0258 (3)0.0278 (3)0.00395 (19)00
I20.0257 (3)0.0312 (3)0.0268 (3)0.0036 (2)00
Geometric parameters (Å, º) top
C1—C31.362 (14)O1—H60.9516
C1—C21.378 (16)O1—H70.9516
C1—N11.450 (13)Pb1—I13.1895 (8)
C2—C3i1.365 (17)Pb1—I1ii3.1895 (8)
C2—H20.95Pb1—I2ii3.2429 (6)
C3—C2i1.365 (17)Pb1—I23.2429 (6)
C3—H30.95Pb1—I2iii3.2429 (6)
N1—H1A0.91Pb1—I2iv3.2429 (6)
N1—H1B0.91I2—Pb1v3.2429 (6)
N1—H1C0.91
C3—C1—C2118.4 (10)C1—N1—H1C109.5
C3—C1—N1120.8 (10)H1A—N1—H1C109.5
C2—C1—N1120.8 (9)H1B—N1—H1C109.5
C3i—C2—C1120.4 (10)H6—O1—H7109.3
C3i—C2—H2119.8I1—Pb1—I2ii89.543 (17)
C1—C2—H2119.8I1ii—Pb1—I2ii90.457 (17)
C1—C3—C2i121.3 (11)I1—Pb1—I290.457 (17)
C1—C3—H3119.4I1ii—Pb1—I289.543 (17)
C2i—C3—H3119.4I1—Pb1—I2iii89.543 (17)
C1—N1—H1A109.5I1ii—Pb1—I2iii90.457 (17)
C1—N1—H1B109.5I1—Pb1—I2iv90.457 (17)
H1A—N1—H1B109.5I1ii—Pb1—I2iv89.543 (17)
C3—C1—C2—C3i0I1—Pb1—I2—Pb1v89.543 (17)
N1—C1—C2—C3i180I1ii—Pb1—I2—Pb1v90.457 (16)
C2—C1—C3—C2i0I2iii—Pb1—I2—Pb1v0
N1—C1—C3—C2i180I2iv—Pb1—I2—Pb1v180
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x+1, y, z+1; (iv) x, y, z1; (v) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···I10.913.183.611 (6)111
N1—H1A···O1v0.911.942.794 (7)156
N1—H1B···O10.911.932.794 (7)158
O1—H6···I2iv0.953.163.771 (7)124
O1—H7···I10.952.993.901 (8)160
Symmetry codes: (iv) x, y, z1; (v) x, y, z+1.
(II) catena-poly[bis(3,5-dimethylanilinium) [[diiodolead(II)]-di-µ-iodo]] top
Crystal data top
(C8H12N)2[PbI4]F(000) = 1712
Mr = 959.16Dx = 2.665 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 976 reflections
a = 30.1215 (19) Åθ = 2.4–28.0°
b = 4.6111 (3) ŵ = 12.22 mm1
c = 20.4599 (12) ÅT = 293 K
β = 122.725 (3)°Plate, yellow
V = 2390.7 (3) Å30.2 × 0.13 × 0.02 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2337 reflections with I > 2σ(I)
ϕ and w scansRint = 0.044
Absorption correction: integration
(XPREP in SAINT-Plus; Bruker, 1999)
θmax = 28°, θmin = 1.6°
Tmin = 0.174, Tmax = 0.782h = 3939
11071 measured reflectionsk = 66
2871 independent reflectionsl = 2727
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.024 w = 1/[σ2(Fo2) + (0.0195P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.050(Δ/σ)max = 0.005
S = 1.07Δρmax = 0.59 e Å3
2871 reflectionsΔρmin = 1.08 e Å3
108 parameters
Crystal data top
(C8H12N)2[PbI4]V = 2390.7 (3) Å3
Mr = 959.16Z = 4
Monoclinic, C2/cMo Kα radiation
a = 30.1215 (19) ŵ = 12.22 mm1
b = 4.6111 (3) ÅT = 293 K
c = 20.4599 (12) Å0.2 × 0.13 × 0.02 mm
β = 122.725 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2871 independent reflections
Absorption correction: integration
(XPREP in SAINT-Plus; Bruker, 1999)
2337 reflections with I > 2σ(I)
Tmin = 0.174, Tmax = 0.782Rint = 0.044
11071 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.050H-atom parameters constrained
S = 1.07Δρmax = 0.59 e Å3
2871 reflectionsΔρmin = 1.08 e Å3
108 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
xyzUiso*/Ueq
C10.12526 (16)0.3881 (9)0.0642 (2)0.0340 (9)
C20.15658 (18)0.2804 (9)0.0392 (3)0.0374 (10)
H20.15170.34470.00740.045*
C30.19504 (17)0.0776 (10)0.0835 (3)0.0378 (10)
C40.19935 (17)0.0201 (10)0.1509 (2)0.0375 (10)
H40.22450.16080.18050.045*
C50.16778 (16)0.0829 (9)0.1760 (2)0.0338 (9)
C60.12997 (17)0.2901 (9)0.1316 (2)0.0370 (10)
H60.10810.36240.14680.044*
C70.2302 (2)0.0384 (12)0.0585 (3)0.0564 (13)
H7A0.24370.22460.0820.068*
H7B0.25910.0930.07470.068*
H7C0.21040.05760.0030.068*
C80.1730 (2)0.0303 (12)0.2494 (3)0.0493 (12)
H8A0.14370.15470.23580.059*
H8B0.17340.12980.27970.059*
H8C0.20530.13770.27920.059*
N10.08449 (14)0.6059 (8)0.0165 (2)0.0425 (9)
H1A0.07670.70590.04620.064*
H1B0.05560.5170.02110.064*
H1C0.09650.72620.00450.064*
Pb100.80953 (5)0.250.03638 (8)
I20.089981 (12)1.30490 (7)0.336893 (17)0.04405 (9)
I10.014765 (11)0.86060 (6)0.106928 (15)0.03732 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.029 (2)0.025 (2)0.039 (2)0.0020 (18)0.012 (2)0.0011 (18)
C20.037 (3)0.036 (2)0.042 (2)0.003 (2)0.023 (2)0.0028 (19)
C30.031 (2)0.042 (2)0.042 (2)0.004 (2)0.021 (2)0.003 (2)
C40.027 (2)0.042 (3)0.037 (2)0.003 (2)0.013 (2)0.004 (2)
C50.028 (2)0.034 (2)0.032 (2)0.0020 (18)0.0116 (19)0.0009 (18)
C60.034 (2)0.037 (2)0.041 (2)0.0013 (19)0.021 (2)0.0051 (19)
C70.056 (3)0.069 (3)0.056 (3)0.016 (3)0.037 (3)0.005 (3)
C80.043 (3)0.068 (3)0.037 (2)0.003 (3)0.023 (2)0.000 (2)
N10.039 (2)0.040 (2)0.042 (2)0.0047 (18)0.0171 (18)0.0042 (18)
Pb10.04576 (16)0.03459 (14)0.03240 (12)00.02350 (12)0
I20.04358 (19)0.04435 (19)0.04324 (17)0.00114 (14)0.02282 (15)0.00773 (13)
I10.04195 (18)0.04087 (16)0.03457 (15)0.00026 (13)0.02424 (14)0.00036 (12)
Geometric parameters (Å, º) top
C1—C61.384 (6)C7—H7C0.96
C1—C21.386 (6)C8—H8A0.96
C1—N11.474 (5)C8—H8B0.96
C2—C31.380 (6)C8—H8C0.96
C2—H20.93N1—H1A0.89
C3—C41.388 (6)N1—H1B0.89
C3—C71.502 (6)N1—H1C0.89
C4—C51.387 (6)Pb1—I13.1984 (3)
C4—H40.93Pb1—I1i3.1984 (3)
C5—C61.385 (6)Pb1—I23.2426 (4)
C5—C81.515 (6)Pb1—I2i3.2426 (4)
C6—H60.93Pb1—I2ii3.2728 (4)
C7—H7A0.96Pb1—I2iii3.2728 (4)
C7—H7B0.96I2—Pb1iv3.2728 (4)
C6—C1—C2121.9 (4)H7B—C7—H7C109.5
C6—C1—N1118.8 (4)C5—C8—H8A109.5
C2—C1—N1119.3 (4)C5—C8—H8B109.5
C3—C2—C1119.8 (4)H8A—C8—H8B109.5
C3—C2—H2120.1C5—C8—H8C109.5
C1—C2—H2120.1H8A—C8—H8C109.5
C2—C3—C4117.9 (4)H8B—C8—H8C109.5
C2—C3—C7120.9 (4)C1—N1—H1A109.5
C4—C3—C7121.2 (4)C1—N1—H1B109.5
C5—C4—C3122.8 (4)H1A—N1—H1B109.5
C5—C4—H4118.6C1—N1—H1C109.5
C3—C4—H4118.6H1A—N1—H1C109.5
C6—C5—C4118.6 (4)H1B—N1—H1C109.5
C6—C5—C8119.8 (4)I1—Pb1—I1i171.556 (13)
C4—C5—C8121.6 (4)I1—Pb1—I287.785 (9)
C1—C6—C5119.0 (4)I1i—Pb1—I286.269 (9)
C1—C6—H6120.5I1—Pb1—I2i86.269 (9)
C5—C6—H6120.5I1i—Pb1—I2i87.785 (9)
C3—C7—H7A109.5I1—Pb1—I2ii92.250 (9)
C3—C7—H7B109.5I1i—Pb1—I2ii93.752 (9)
H7A—C7—H7B109.5I1—Pb1—I2iii93.752 (9)
C3—C7—H7C109.5I1i—Pb1—I2iii92.250 (9)
H7A—C7—H7C109.5
C6—C1—C2—C32.4 (7)N1—C1—C6—C5179.2 (4)
N1—C1—C2—C3179.7 (4)C4—C5—C6—C10.4 (6)
C1—C2—C3—C42.6 (6)C8—C5—C6—C1179.1 (4)
C1—C2—C3—C7178.8 (4)I1—Pb1—I2—Pb1iv86.249 (9)
C2—C3—C4—C51.8 (7)I1i—Pb1—I2—Pb1iv87.752 (9)
C7—C3—C4—C5179.6 (5)I2i—Pb1—I2—Pb1iv0
C3—C4—C5—C60.7 (7)I2ii—Pb1—I2—Pb1iv179.991 (9)
C3—C4—C5—C8179.3 (4)I2iii—Pb1—I2—Pb1iv180
C2—C1—C6—C51.3 (6)
Symmetry codes: (i) x, y, z+1/2; (ii) x, y1, z+1/2; (iii) x, y1, z; (iv) x, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.892.843.663 (4)155
N1—H1B···I1v0.892.573.432 (4)165
N1—H1C···I2vi0.893.153.789 (4)131
Symmetry codes: (v) x, y+1, z; (vi) x, y+2, z1/2.

Experimental details

(I)(II)
Crystal data
Chemical formula(C6H10N2)[PbI4]·2H2O(C8H12N)2[PbI4]
Mr860.98959.16
Crystal system, space groupOrthorhombic, PnnmMonoclinic, C2/c
Temperature (K)173293
a, b, c (Å)12.952 (3), 14.489 (3), 4.5851 (10)30.1215 (19), 4.6111 (3), 20.4599 (12)
α, β, γ (°)90, 90, 9090, 122.725 (3), 90
V3)860.4 (3)2390.7 (3)
Z24
Radiation typeMo KαMo Kα
µ (mm1)16.9712.22
Crystal size (mm)0.5 × 0.37 × 0.30.2 × 0.13 × 0.02
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionIntegration
(XPREP in SAINT-Plus; Bruker, 1999)
Integration
(XPREP in SAINT-Plus; Bruker, 1999)
Tmin, Tmax0.012, 0.0590.174, 0.782
No. of measured, independent and
observed [I > 2σ(I)] reflections
5460, 1168, 1095 11071, 2871, 2337
Rint0.0560.044
(sin θ/λ)max1)0.6610.661
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.081, 1.11 0.024, 0.050, 1.07
No. of reflections11682871
No. of parameters49108
No. of restraints240
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)2.36, 1.020.59, 1.08

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, 2001), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) for (I) top
Pb1—I13.1895 (8)Pb1—I23.2429 (6)
I1—Pb1—I2i89.543 (17)I1i—Pb1—I2i90.457 (17)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···I10.913.183.611 (6)111
N1—H1A···O1ii0.911.942.794 (7)156
N1—H1B···O10.911.932.794 (7)158
O1—H6···I2iii0.953.163.771 (7)124
O1—H7···I10.952.993.901 (8)160
Symmetry codes: (ii) x, y, z+1; (iii) x, y, z1.
Selected geometric parameters (Å, º) for (II) top
Pb1—I13.1984 (3)Pb1—I2i3.2728 (4)
Pb1—I23.2426 (4)
I1—Pb1—I1ii171.556 (13)I1—Pb1—I2i92.250 (9)
I1—Pb1—I287.785 (9)I1ii—Pb1—I2i93.752 (9)
I1ii—Pb1—I286.269 (9)
Symmetry codes: (i) x, y1, z+1/2; (ii) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···I10.892.843.663 (4)155
N1—H1B···I1iii0.892.573.432 (4)165
N1—H1C···I2iv0.893.153.789 (4)131
Symmetry codes: (iii) x, y+1, z; (iv) x, y+2, z1/2.
 

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