Synthesis, characterization and phase transitions in the inorganic-organic layered perovskite-type hybrids [(C_nH_2n + 1NH₃)₂PbI₄], n = 4, 5 and 6

Three inorganic-organic layered perovskite-type hybrids of the general formula [(C_nH_2n + 1NH₃)₂PbI₄], n = 4, 5 and 6, display a number of reversible first-order phase transitions in the temperature range from 256 to 393 K. [(C₄H₉NH₃)₂PbI₄] has a single phase transition, [(C₅H₁₁NH₃)₂PbI₄] has two phase transitions and [(C₆H₁₃NH₃)₂PbI₄] has three phase transitions. In all three cases, the lowest-temperature phase transition is thermochromic and the crystals change colour from yellow in their lowest-temperature phase to orange in their higher-temperature phase for [(C₄H₉NH₃)₂PbI₄] and [(C₆H₁₃NH₃)₂PbI₄], and from orange to red for [(C₅H₁₁NH₃)₂PbI₄]. The structural details associated with this phase transition have been investigated via single-crystal X-ray diffraction, SC-XRD, for all three compounds.

Computing details

For all compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999) and PLATON (Spek, 2003).

(1a) bis(butylammonium)tetraiodoplumbate(II)

Crystal data

2(C4H12N)·I4Pb	F(000) = 1520
Mr = 863.08	Dx = 2.886 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3361 reflections
a = 8.4280 (19) Å	θ = 3.1–28.2°
b = 8.986 (2) Å	µ = 14.69 mm^−1
c = 26.233 (6) Å	T = 223 K
V = 1986.7 (8) Å^3	Cube, yellow
Z = 4	0.14 × 0.13 × 0.08 mm

Data collection

Bruker APEX II CCD area detector diffractometer	1745 independent reflections
Radiation source: fine-focus sealed tube	1500 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.083
ω scans	θmax = 25°, θmin = 2.9°
Absorption correction: integration Bruker XPREP (Bruker, 2004)	h = −10→9
Tmin = 0.165, Tmax = 0.339	k = −10→10
7581 measured reflections	l = −31→29

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.101	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.27	H-atom parameters constrained
S = 1.38	w = 1/[σ^2(Fo^2) + (0.P)^2 + 573.3984P] where P = (Fo^2 + 2Fc^2)/3
1745 reflections	(Δ/σ)max < 0.001
70 parameters	Δρmax = 3.92 e Å^−3
31 restraints	Δρmin = −5.68 e Å^−3

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.925 (5)	0.440 (4)	0.8573 (17)	0.033 (7)
H1D	0.8115	0.4325	0.8657	0.04*
H1E	0.9508	0.3574	0.8342	0.04*
C2	0.957 (5)	0.587 (5)	0.8307 (17)	0.038 (7)
H2A	1.0671	0.5885	0.8188	0.045*
H2B	0.9448	0.6682	0.8555	0.045*
C3	0.846 (6)	0.618 (5)	0.7849 (17)	0.042 (8)
H3A	0.8527	0.5345	0.7609	0.051*
H3B	0.7363	0.6246	0.7969	0.051*
C4	0.889 (6)	0.756 (5)	0.7586 (19)	0.046 (10)
H4A	0.817	0.772	0.7303	0.069*
H4B	0.9968	0.7484	0.7459	0.069*
H4C	0.8815	0.8387	0.7822	0.069*
N1	1.016 (4)	0.427 (3)	0.9025 (13)	0.030 (7)
H1A	0.9957	0.3391	0.9175	0.045*
H1B	0.9905	0.5015	0.9239	0.045*
H1C	1.1198	0.4326	0.8947	0.045*
I1	1.0779 (3)	1.0298 (3)	0.88221 (10)	0.0314 (7)
I2	0.6987 (3)	1.2042 (3)	0.97709 (11)	0.0311 (7)
Pb1	1	1	1	0.0237 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.027 (15)	0.023 (13)	0.050 (16)	0.015 (13)	0.004 (12)	−0.003 (11)
C2	0.031 (15)	0.034 (14)	0.049 (15)	0.012 (13)	0.002 (13)	0.005 (11)
C3	0.039 (17)	0.040 (16)	0.048 (17)	0.016 (15)	0.000 (14)	0.002 (13)
C4	0.05 (2)	0.039 (18)	0.05 (2)	0.019 (18)	−0.009 (19)	0.006 (15)
N1	0.036 (18)	0.009 (13)	0.046 (16)	0.000 (13)	0.001 (13)	−0.004 (11)
I1	0.0287 (14)	0.0282 (13)	0.0374 (15)	0.0022 (11)	0.0016 (12)	0.0010 (11)
I2	0.0217 (12)	0.0268 (13)	0.0448 (15)	0.0116 (10)	0.0014 (11)	0.0009 (12)
Pb1	0.0196 (10)	0.0180 (9)	0.0334 (11)	0.0001 (8)	−0.0006 (9)	0.0019 (9)

Geometric parameters (Å, º)

C1—N1	1.42 (5)	C4—H4C	0.97
C1—C2	1.53 (6)	N1—H1A	0.9
C1—H1D	0.98	N1—H1B	0.9
C1—H1E	0.98	N1—H1C	0.9
C2—C3	1.55 (6)	I1—Pb1	3.170 (3)
C2—H2A	0.98	I2—Pb1	3.190 (2)
C2—H2B	0.98	I2—Pb1^i	3.199 (2)
C3—C4	1.46 (6)	Pb1—I1^ii	3.170 (3)
C3—H3A	0.98	Pb1—I2^ii	3.190 (2)
C3—H3B	0.98	Pb1—I2^iii	3.199 (2)
C4—H4A	0.97	Pb1—I2^iv	3.199 (2)
C4—H4B	0.97
N1—C1—C2	111 (4)	H4B—C4—H4C	109.5
N1—C1—H1D	109.5	C1—N1—H1A	109.5
C2—C1—H1D	109.5	C1—N1—H1B	109.5
N1—C1—H1E	109.5	H1A—N1—H1B	109.5
C2—C1—H1E	109.5	C1—N1—H1C	109.5
H1D—C1—H1E	108.1	H1A—N1—H1C	109.5
C1—C2—C3	114 (4)	H1B—N1—H1C	109.5
C1—C2—H2A	108.8	Pb1—I2—Pb1^i	149.24 (10)
C3—C2—H2A	108.8	I1^ii—Pb1—I1	180.0000 (10)
C1—C2—H2B	108.8	I1^ii—Pb1—I2^ii	86.15 (7)
C3—C2—H2B	108.8	I1—Pb1—I2^ii	93.85 (7)
H2A—C2—H2B	107.7	I1^ii—Pb1—I2	93.85 (7)
C4—C3—C2	111 (4)	I1—Pb1—I2	86.15 (7)
C4—C3—H3A	109.3	I2^ii—Pb1—I2	180.0000 (10)
C2—C3—H3A	109.3	I1^ii—Pb1—I2^iii	90.26 (7)
C4—C3—H3B	109.3	I1—Pb1—I2^iii	89.74 (7)
C2—C3—H3B	109.3	I2^ii—Pb1—I2^iii	88.52 (3)
H3A—C3—H3B	108	I2—Pb1—I2^iii	91.48 (3)
C3—C4—H4A	109.5	I1^ii—Pb1—I2^iv	89.74 (7)
C3—C4—H4B	109.5	I1—Pb1—I2^iv	90.26 (7)
H4A—C4—H4B	109.5	I2^ii—Pb1—I2^iv	91.48 (3)
C3—C4—H4C	109.5	I2—Pb1—I2^iv	88.52 (3)
H4A—C4—H4C	109.5	I2^iii—Pb1—I2^iv	180
N1—C1—C2—C3	−173 (3)	Pb1^i—I2—Pb1—I1	−123.18 (19)
C1—C2—C3—C4	−176 (4)	Pb1^i—I2—Pb1—I2^iii	147.18 (15)
Pb1^i—I2—Pb1—I1^ii	56.82 (19)	Pb1^i—I2—Pb1—I2^iv	−32.82 (15)

Symmetry codes: (i) x−1/2, −y+5/2, −z+2; (ii) −x+2, −y+2, −z+2; (iii) −x+3/2, y−1/2, z; (iv) x+1/2, −y+5/2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1^v	0.9	3.01	3.65 (3)	129
N1—H1B···I2^iii	0.9	2.79	3.65 (3)	159
N1—H1C···I1^vi	0.9	2.71	3.58 (3)	163

Symmetry codes: (iii) −x+3/2, y−1/2, z; (v) x, y−1, z; (vi) −x+5/2, y−1/2, z.

(1b) bis(butylammonium)tetraiodoplumbate(II)

Crystal data

2(C4H12N)·I4Pb	F(000) = 1520
Mr = 863.08	Dx = 2.692 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4303 reflections
a = 8.8764 (1) Å	θ = 2.7–28.0°
b = 8.6925 (1) Å	µ = 13.71 mm^−1
c = 27.6014 (5) Å	T = 293 K
V = 2129.67 (5) Å^3	Cube, orange
Z = 4	0.15 × 0.14 × 0.08 mm

Data collection

Bruker APEX II CCD area detector diffractometer	1981 independent reflections
Radiation source: fine-focus sealed tube	1541 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
ω scans	θmax = 25.5°, θmin = 2.7°
Absorption correction: integration Bruker XPREP (Bruker, 2004)	h = −10→10
Tmin = 0.160, Tmax = 0.359	k = −10→10
15579 measured reflections	l = −33→32

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0196P)^2 + 10.8314P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
1981 reflections	Δρmax = 0.82 e Å^−3
71 parameters	Δρmin = −1.15 e Å^−3
36 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00341 (14)

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9692 (19)	0.4748 (18)	0.8819 (5)	0.150 (5)
H1D	0.8679	0.5025	0.8918	0.18*
H1E	0.9871	0.3691	0.8916	0.18*
C2	0.9822 (18)	0.4879 (19)	0.8282 (5)	0.176 (6)
H2A	1.0827	0.4579	0.818	0.212*
H2B	0.9659	0.5938	0.8184	0.212*
C3	0.866 (2)	0.384 (2)	0.8039 (6)	0.210 (7)
H3A	0.8749	0.2808	0.8167	0.252*
H3B	0.7655	0.4215	0.8114	0.252*
C4	0.886 (3)	0.380 (3)	0.7509 (6)	0.283 (11)
H4A	0.8104	0.3143	0.7368	0.424*
H4B	0.9839	0.341	0.7433	0.424*
H4C	0.8751	0.4821	0.738	0.424*
N1	1.0761 (10)	0.5741 (11)	0.9059 (4)	0.094 (3)
H1A	1.0594	0.5726	0.9377	0.141*
H1B	1.0657	0.6697	0.8949	0.141*
H1C	1.1692	0.5412	0.8999	0.141*
I1	1.03349 (8)	0.98557 (8)	0.88455 (3)	0.0782 (3)
I2	0.69648 (7)	1.19465 (7)	0.99571 (3)	0.0711 (3)
Pb1	1	1	1	0.04801 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.139 (11)	0.157 (13)	0.155 (9)	−0.035 (9)	−0.010 (10)	−0.033 (10)
C2	0.174 (13)	0.206 (14)	0.149 (8)	−0.008 (11)	−0.032 (10)	−0.044 (11)
C3	0.199 (15)	0.258 (17)	0.172 (11)	−0.028 (13)	−0.041 (12)	−0.062 (13)
C4	0.29 (3)	0.39 (3)	0.166 (12)	−0.04 (3)	−0.051 (17)	−0.08 (2)
N1	0.074 (6)	0.095 (7)	0.113 (7)	0.010 (5)	−0.005 (5)	−0.004 (5)
I1	0.0784 (5)	0.0804 (5)	0.0756 (5)	0.0008 (4)	−0.0086 (3)	0.0035 (4)
I2	0.0482 (3)	0.0474 (3)	0.1176 (6)	0.0195 (3)	−0.0124 (3)	−0.0075 (4)
Pb1	0.0338 (2)	0.0347 (2)	0.0755 (3)	0.00014 (16)	−0.00003 (19)	0.0008 (2)

Geometric parameters (Å, º)

C1—N1	1.443 (16)	C4—H4C	0.96
C1—C2	1.493 (9)	N1—H1A	0.89
C1—H1D	0.97	N1—H1B	0.89
C1—H1E	0.97	N1—H1C	0.89
C2—C3	1.526 (9)	I1—Pb1	3.2029 (7)
C2—H2A	0.97	I2—Pb1^i	3.1781 (5)
C2—H2B	0.97	I2—Pb1	3.1836 (5)
C3—C4	1.475 (10)	Pb1—I2^ii	3.1781 (5)
C3—H3A	0.97	Pb1—I2^iii	3.1781 (5)
C3—H3B	0.97	Pb1—I2^iv	3.1836 (5)
C4—H4A	0.96	Pb1—I1^iv	3.2029 (7)
C4—H4B	0.96
N1—C1—C2	111.1 (12)	H4B—C4—H4C	109.5
N1—C1—H1D	109.4	C1—N1—H1A	109.5
C2—C1—H1D	109.4	C1—N1—H1B	109.5
N1—C1—H1E	109.4	H1A—N1—H1B	109.5
C2—C1—H1E	109.4	C1—N1—H1C	109.5
H1D—C1—H1E	108	H1A—N1—H1C	109.5
C1—C2—C3	109.8 (11)	H1B—N1—H1C	109.5
C1—C2—H2A	109.7	Pb1^i—I2—Pb1	155.08 (2)
C3—C2—H2A	109.7	I2^ii—Pb1—I2^iii	180
C1—C2—H2B	109.7	I2^ii—Pb1—I2	91.256 (4)
C3—C2—H2B	109.7	I2^iii—Pb1—I2	88.744 (4)
H2A—C2—H2B	108.2	I2^ii—Pb1—I2^iv	88.744 (4)
C4—C3—C2	111.7 (12)	I2^iii—Pb1—I2^iv	91.256 (4)
C4—C3—H3A	109.3	I2—Pb1—I2^iv	180
C2—C3—H3A	109.3	I2^ii—Pb1—I1	91.077 (18)
C4—C3—H3B	109.3	I2^iii—Pb1—I1	88.922 (18)
C2—C3—H3B	109.3	I2—Pb1—I1	93.576 (19)
H3A—C3—H3B	107.9	I2^iv—Pb1—I1	86.424 (19)
C3—C4—H4A	109.5	I2^ii—Pb1—I1^iv	88.923 (18)
C3—C4—H4B	109.5	I2^iii—Pb1—I1^iv	91.078 (18)
H4A—C4—H4B	109.5	I2—Pb1—I1^iv	86.424 (19)
C3—C4—H4C	109.5	I2^iv—Pb1—I1^iv	93.576 (19)
H4A—C4—H4C	109.5	I1—Pb1—I1^iv	180
N1—C1—C2—C3	−178.9 (15)	Pb1^i—I2—Pb1—I2^iii	172.39 (5)
C1—C2—C3—C4	−173.6 (19)	Pb1^i—I2—Pb1—I1	−98.77 (6)
Pb1^i—I2—Pb1—I2^ii	−7.61 (5)	Pb1^i—I2—Pb1—I1^iv	81.23 (6)

Symmetry codes: (i) x−1/2, −y+5/2, −z+2; (ii) x+1/2, −y+5/2, −z+2; (iii) −x+3/2, y−1/2, z; (iv) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2^iii	0.89	2.97	3.619 (9)	131
N1—H1B···I1	0.89	2.77	3.645 (9)	166
N1—H1C···I1^v	0.89	2.72	3.598 (9)	171

Symmetry codes: (iii) −x+3/2, y−1/2, z; (v) −x+5/2, y−1/2, z.

(2a) bis(pentylammonium)tetraiodoplumbate(II)

Crystal data

2(C5H14N)·I4Pb	F(000) = 792
Mr = 891.13	Dx = 2.671 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 843 reflections
a = 8.4716 (18) Å	θ = 3.4–28.3°
b = 9.007 (2) Å	µ = 13.18 mm^−1
c = 14.784 (3) Å	T = 173 K
β = 100.881 (4)°	Rectangular, yellow
V = 1107.8 (4) Å^3	0.58 × 0.32 × 0.11 mm
Z = 2

Data collection

Bruker APEX II CCD area detector diffractometer	2649 independent reflections
Radiation source: fine-focus sealed tube	2334 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.080
ω scans	θmax = 28°, θmin = 2.7°
Absorption correction: integration Bruker XPREP (Bruker, 2004)	h = −11→11
Tmin = 0.035, Tmax = 0.241	k = −11→11
7043 measured reflections	l = −13→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0375P)^2 + 8.7673P] where P = (Fo^2 + 2Fc^2)/3
2649 reflections	(Δ/σ)max = 0.001
79 parameters	Δρmax = 1.50 e Å^−3
0 restraints	Δρmin = −2.67 e Å^−3

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9329 (13)	0.5152 (11)	0.7377 (8)	0.037 (2)
H1D	1.0511	0.5252	0.7453	0.045*
H1E	0.8834	0.5938	0.6947	0.045*
C2	0.8840 (14)	0.3669 (12)	0.6962 (7)	0.041 (2)
H2A	0.7683	0.3504	0.6957	0.05*
H2B	0.9454	0.2879	0.734	0.05*
C3	0.9160 (17)	0.3578 (13)	0.5954 (9)	0.053 (3)
H3A	0.8443	0.4293	0.5567	0.063*
H3B	1.0282	0.3889	0.5957	0.063*
C4	0.8908 (18)	0.2087 (14)	0.5526 (8)	0.052 (3)
H4A	0.7806	0.1744	0.555	0.063*
H4B	0.9674	0.1378	0.5885	0.063*
C5	0.9136 (16)	0.2087 (17)	0.4539 (8)	0.057 (3)
H5A	0.8956	0.1084	0.4284	0.086*
H5B	1.0233	0.2404	0.4513	0.086*
H5C	0.8366	0.2773	0.4178	0.086*
N1	0.8865 (11)	0.5381 (9)	0.8266 (6)	0.0353 (17)
H1A	0.9175	0.6304	0.848	0.053*
H1B	0.935	0.4687	0.8673	0.053*
H1C	0.7779	0.5296	0.8202	0.053*
I1	0.95279 (8)	0.92483 (6)	0.78682 (4)	0.03160 (16)
I2	0.68969 (6)	1.20798 (6)	0.95764 (4)	0.02885 (15)
Pb1	1	1	1	0.01954 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.040 (5)	0.032 (5)	0.042 (5)	0.000 (4)	0.014 (5)	−0.001 (4)
C2	0.043 (5)	0.034 (5)	0.046 (6)	0.007 (4)	0.006 (5)	−0.012 (5)
C3	0.060 (7)	0.040 (6)	0.061 (7)	0.001 (5)	0.020 (6)	−0.001 (6)
C4	0.068 (8)	0.048 (6)	0.040 (6)	−0.010 (6)	0.009 (6)	−0.007 (5)
C5	0.056 (7)	0.077 (9)	0.039 (6)	−0.003 (7)	0.011 (5)	−0.018 (6)
N1	0.043 (5)	0.029 (4)	0.032 (4)	0.005 (3)	0.003 (4)	−0.006 (3)
I1	0.0394 (3)	0.0272 (3)	0.0276 (3)	−0.0040 (2)	0.0048 (2)	−0.0025 (2)
I2	0.0226 (3)	0.0234 (3)	0.0406 (3)	0.00983 (19)	0.0060 (2)	0.0005 (2)
Pb1	0.01671 (19)	0.01495 (18)	0.0271 (2)	0.00023 (13)	0.00451 (15)	−0.00109 (15)

Geometric parameters (Å, º)

C1—N1	1.457 (13)	C5—H5A	0.98
C1—C2	1.496 (14)	C5—H5B	0.98
C1—H1D	0.99	C5—H5C	0.98
C1—H1E	0.99	N1—H1A	0.91
C2—C3	1.565 (16)	N1—H1B	0.91
C2—H2A	0.99	N1—H1C	0.91
C2—H2B	0.99	I1—Pb1	3.1743 (9)
C3—C4	1.483 (16)	I2—Pb1	3.1923 (7)
C3—H3A	0.99	I2—Pb1^i	3.2052 (7)
C3—H3B	0.99	Pb1—I1^ii	3.1743 (9)
C4—C5	1.508 (15)	Pb1—I2^ii	3.1923 (7)
C4—H4A	0.99	Pb1—I2^iii	3.2052 (7)
C4—H4B	0.99	Pb1—I2^iv	3.2052 (7)
N1—C1—C2	113.3 (9)	H5A—C5—H5B	109.5
N1—C1—H1D	108.9	C4—C5—H5C	109.5
C2—C1—H1D	108.9	H5A—C5—H5C	109.5
N1—C1—H1E	108.9	H5B—C5—H5C	109.5
C2—C1—H1E	108.9	C1—N1—H1A	109.5
H1D—C1—H1E	107.7	C1—N1—H1B	109.5
C1—C2—C3	110.7 (9)	H1A—N1—H1B	109.5
C1—C2—H2A	109.5	C1—N1—H1C	109.5
C3—C2—H2A	109.5	H1A—N1—H1C	109.5
C1—C2—H2B	109.5	H1B—N1—H1C	109.5
C3—C2—H2B	109.5	Pb1—I2—Pb1^i	150.22 (2)
H2A—C2—H2B	108.1	I1—Pb1—I1^ii	180
C4—C3—C2	114.6 (10)	I1—Pb1—I2	89.177 (16)
C4—C3—H3A	108.6	I1^ii—Pb1—I2	90.823 (16)
C2—C3—H3A	108.6	I1—Pb1—I2^ii	90.823 (16)
C4—C3—H3B	108.6	I1^ii—Pb1—I2^ii	89.177 (16)
C2—C3—H3B	108.6	I2—Pb1—I2^ii	180
H3A—C3—H3B	107.6	I1—Pb1—I2^iii	87.415 (17)
C3—C4—C5	112.2 (11)	I1^ii—Pb1—I2^iii	92.585 (17)
C3—C4—H4A	109.2	I2—Pb1—I2^iii	84.535 (17)
C5—C4—H4A	109.2	I2^ii—Pb1—I2^iii	95.465 (17)
C3—C4—H4B	109.2	I1—Pb1—I2^iv	92.585 (17)
C5—C4—H4B	109.2	I1^ii—Pb1—I2^iv	87.415 (17)
H4A—C4—H4B	107.9	I2—Pb1—I2^iv	95.465 (17)
C4—C5—H5A	109.5	I2^ii—Pb1—I2^iv	84.535 (17)
C4—C5—H5B	109.5	I2^iii—Pb1—I2^iv	180
N1—C1—C2—C3	172.2 (10)	Pb1^i—I2—Pb1—I1^ii	34.83 (4)
C1—C2—C3—C4	172.6 (11)	Pb1^i—I2—Pb1—I2^iii	−57.69 (5)
C2—C3—C4—C5	176.6 (11)	Pb1^i—I2—Pb1—I2^iv	122.31 (5)
Pb1^i—I2—Pb1—I1	−145.17 (4)

Symmetry codes: (i) −x+3/2, y+1/2, −z+2; (ii) −x+2, −y+2, −z+2; (iii) x+1/2, −y+5/2, z; (iv) −x+3/2, y−1/2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1	0.91	2.84	3.594 (9)	142
N1—H1B···I2^v	0.91	2.81	3.658 (9)	156
N1—H1C···I1^vi	0.91	2.74	3.625 (9)	166

Symmetry codes: (v) x+1/2, −y+3/2, z; (vi) x−1/2, −y+3/2, z.

(2b) bis(pentylammonium)tetraiodoplumbate(II)

Crystal data

2(C5H14N)·I4Pb	F(000) = 792
Mr = 891.13	Dx = 2.61 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 4406 reflections
a = 8.6716 (7) Å	θ = 2.5–30.8°
b = 8.9297 (6) Å	µ = 12.87 mm^−1
c = 14.8805 (13) Å	T = 293 K
β = 100.212 (2)°	Plate, orange
V = 1134.01 (15) Å^3	0.5 × 0.46 × 0.14 mm
Z = 2

Data collection

Bruker APEX II CCD area detector diffractometer	2734 independent reflections
Radiation source: fine-focus sealed tube	2259 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 28°, θmin = 1.4°
Absorption correction: integration Bruker XPREP (Bruker, 2004)	h = −10→11
Tmin = 0.020, Tmax = 0.179	k = −7→11
8718 measured reflections	l = −19→19

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0576P)^2 + 5.635P] where P = (Fo^2 + 2Fc^2)/3
2734 reflections	(Δ/σ)max = 0.001
79 parameters	Δρmax = 1.90 e Å^−3
46 restraints	Δρmin = −2.07 e Å^−3

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.939 (3)	0.5104 (17)	0.7438 (12)	0.127 (5)
H1D	1.0522	0.517	0.7507	0.152*
H1E	0.8951	0.5909	0.7035	0.152*
C2	0.888 (3)	0.3643 (18)	0.6987 (10)	0.133 (5)
H2A	0.7759	0.3518	0.6969	0.159*
H2B	0.9412	0.283	0.7347	0.159*
C3	0.921 (3)	0.355 (2)	0.6026 (10)	0.145 (6)
H3A	0.858	0.43	0.5657	0.174*
H3B	1.0303	0.3816	0.6043	0.174*
C4	0.892 (3)	0.207 (2)	0.5561 (10)	0.157 (7)
H4A	0.788	0.1718	0.5622	0.189*
H4B	0.9674	0.1347	0.586	0.189*
C5	0.902 (3)	0.215 (3)	0.4558 (9)	0.146 (8)
H5A	0.8853	0.1167	0.4292	0.22*
H5B	1.0046	0.2496	0.4494	0.22*
H5C	0.8244	0.2823	0.4253	0.22*
N1	0.8975 (18)	0.5338 (13)	0.8290 (8)	0.097 (4)
H1A	0.9285	0.6246	0.8493	0.145*
H1B	0.9434	0.465	0.8681	0.145*
H1C	0.7939	0.5267	0.824	0.145*
I1	0.95588 (11)	0.92510 (9)	0.78861 (5)	0.0753 (2)
I2	0.70034 (8)	1.21391 (8)	0.96155 (6)	0.0662 (2)
Pb1	1	1	1	0.04330 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.170 (14)	0.114 (11)	0.107 (9)	0.028 (9)	0.054 (10)	−0.006 (7)
C2	0.170 (13)	0.130 (10)	0.098 (8)	0.036 (10)	0.026 (9)	−0.021 (7)
C3	0.174 (14)	0.157 (12)	0.110 (9)	0.013 (11)	0.044 (10)	−0.027 (8)
C4	0.192 (16)	0.178 (14)	0.111 (9)	−0.004 (13)	0.051 (12)	−0.043 (9)
C5	0.159 (17)	0.183 (19)	0.093 (9)	−0.046 (15)	0.011 (11)	−0.030 (10)
N1	0.149 (11)	0.067 (6)	0.078 (6)	0.016 (7)	0.027 (7)	0.008 (5)
I1	0.1002 (6)	0.0647 (5)	0.0592 (4)	−0.0064 (4)	0.0094 (4)	−0.0039 (3)
I2	0.0552 (4)	0.0540 (4)	0.0922 (5)	0.0267 (3)	0.0212 (3)	0.0083 (3)
Pb1	0.0364 (2)	0.0325 (2)	0.0622 (3)	0.00046 (14)	0.01189 (18)	−0.00206 (18)

Geometric parameters (Å, º)

C1—N1	1.394 (19)	C5—H5A	0.96
C1—C2	1.499 (9)	C5—H5B	0.96
C1—H1D	0.97	C5—H5C	0.96
C1—H1E	0.97	N1—H1A	0.89
C2—C3	1.511 (9)	N1—H1B	0.89
C2—H2A	0.97	N1—H1C	0.89
C2—H2B	0.97	I1—Pb1	3.1720 (8)
C3—C4	1.498 (9)	I2—Pb1	3.1940 (6)
C3—H3A	0.97	I2—Pb1^i	3.1975 (6)
C3—H3B	0.97	Pb1—I1^ii	3.1720 (8)
C4—C5	1.513 (9)	Pb1—I2^ii	3.1940 (6)
C4—H4A	0.97	Pb1—I2^iii	3.1975 (6)
C4—H4B	0.97	Pb1—I2^iv	3.1975 (6)
N1—C1—C2	115.7 (14)	H5A—C5—H5B	109.5
N1—C1—H1D	108.4	C4—C5—H5C	109.5
C2—C1—H1D	108.4	H5A—C5—H5C	109.5
N1—C1—H1E	108.4	H5B—C5—H5C	109.5
C2—C1—H1E	108.4	C1—N1—H1A	109.5
H1D—C1—H1E	107.4	C1—N1—H1B	109.5
C1—C2—C3	112.2 (11)	H1A—N1—H1B	109.5
C1—C2—H2A	109.2	C1—N1—H1C	109.5
C3—C2—H2A	109.2	H1A—N1—H1C	109.5
C1—C2—H2B	109.2	H1B—N1—H1C	109.5
C3—C2—H2B	109.2	Pb1—I2—Pb1^i	153.68 (3)
H2A—C2—H2B	107.9	I1—Pb1—I1^ii	180
C4—C3—C2	116.0 (11)	I1—Pb1—I2^ii	90.16 (2)
C4—C3—H3A	108.3	I1^ii—Pb1—I2^ii	89.84 (2)
C2—C3—H3A	108.3	I1—Pb1—I2	89.84 (2)
C4—C3—H3B	108.3	I1^ii—Pb1—I2	90.16 (2)
C2—C3—H3B	108.3	I2^ii—Pb1—I2	180
H3A—C3—H3B	107.4	I1—Pb1—I2^iii	87.99 (2)
C3—C4—C5	112.3 (12)	I1^ii—Pb1—I2^iii	92.01 (2)
C3—C4—H4A	109.1	I2^ii—Pb1—I2^iii	93.399 (8)
C5—C4—H4A	109.1	I2—Pb1—I2^iii	86.601 (8)
C3—C4—H4B	109.1	I1—Pb1—I2^iv	92.01 (2)
C5—C4—H4B	109.1	I1^ii—Pb1—I2^iv	87.99 (2)
H4A—C4—H4B	107.9	I2^ii—Pb1—I2^iv	86.601 (8)
C4—C5—H5A	109.5	I2—Pb1—I2^iv	93.399 (8)
C4—C5—H5B	109.5	I2^iii—Pb1—I2^iv	180
N1—C1—C2—C3	173.6 (19)	Pb1^i—I2—Pb1—I1^ii	32.34 (6)
C1—C2—C3—C4	173 (2)	Pb1^i—I2—Pb1—I2^iii	−59.67 (7)
C2—C3—C4—C5	171 (2)	Pb1^i—I2—Pb1—I2^iv	120.33 (7)
Pb1^i—I2—Pb1—I1	−147.66 (6)

Symmetry codes: (i) −x+3/2, y+1/2, −z+2; (ii) −x+2, −y+2, −z+2; (iii) x+1/2, −y+5/2, z; (iv) −x+3/2, y−1/2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1	0.89	2.85	3.597 (12)	142
N1—H1B···I2^v	0.89	2.89	3.721 (13)	156
N1—H1C···I1^vi	0.89	2.92	3.787 (15)	166

Symmetry codes: (v) x+1/2, −y+3/2, z; (vi) x−1/2, −y+3/2, z.

(2c) bis(pentylammonium)tetraiodoplumbate(II)

Crystal data

2(C5H14N)·I4Pb	F(000) = 1584
Mr = 891.13	Dx = 2.512 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4614 reflections
a = 9.0078 (10) Å	θ = 2.6–28.9°
b = 8.731 (1) Å	µ = 12.39 mm^−1
c = 29.956 (4) Å	T = 333 K
V = 2356.0 (5) Å^3	Plate, red
Z = 4	0.5 × 0.45 × 0.14 mm

Data collection

Bruker APEX II CCD area detector diffractometer	2194 independent reflections
Radiation source: fine-focus sealed tube	1566 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ω scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: integration Bruker XPREP (Bruker, 2004)	h = −9→10
Tmin = 0.017, Tmax = 0.176	k = −6→10
11216 measured reflections	l = −31→36

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.124	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.284	H-atom parameters constrained
S = 1.32	w = 1/[σ^2(Fo^2) + (0.P)^2 + 291.1164P] where P = (Fo^2 + 2Fc^2)/3
2194 reflections	(Δ/σ)max = 0.003
79 parameters	Δρmax = 2.17 e Å^−3
48 restraints	Δρmin = −2.67 e Å^−3

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.973 (8)	0.468 (9)	0.894 (2)	0.27 (2)
H1D	0.8735	0.4994	0.9025	0.326*
H1E	0.9894	0.3654	0.9052	0.326*
C2	0.986 (7)	0.469 (11)	0.843 (2)	0.28 (2)
H2A	1.007	0.5721	0.8334	0.333*
H2B	1.069	0.4045	0.8348	0.333*
C3	0.847 (5)	0.412 (10)	0.820 (2)	0.29 (2)
H3A	0.7826	0.4984	0.814	0.342*
H3B	0.7941	0.3431	0.84	0.342*
C4	0.878 (9)	0.328 (6)	0.777 (3)	0.29 (3)
H4A	0.9555	0.2528	0.7816	0.347*
H4B	0.7896	0.2745	0.7672	0.347*
C5	0.927 (11)	0.435 (10)	0.739 (2)	0.30 (3)
H5A	0.9098	0.3869	0.7109	0.45*
H5B	1.0313	0.457	0.7423	0.45*
H5C	0.8718	0.5288	0.7409	0.45*
N1	1.080 (6)	0.572 (7)	0.914 (2)	0.25 (3)
H1A	1.0679	0.5735	0.9432	0.375*
H1B	1.0672	0.6654	0.9027	0.375*
H1C	1.1716	0.5395	0.9074	0.375*
I1	1.0425 (4)	0.9841 (4)	0.89404 (13)	0.1034 (12)
I2	0.7090 (3)	1.2066 (3)	0.99199 (13)	0.0927 (11)
Pb1	1	1	1	0.0610 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.15 (4)	0.20 (4)	0.46 (7)	−0.05 (3)	0.11 (4)	−0.03 (5)
C2	0.17 (4)	0.20 (4)	0.46 (7)	−0.05 (3)	0.10 (5)	−0.02 (5)
C3	0.18 (4)	0.21 (4)	0.47 (7)	−0.05 (3)	0.10 (5)	−0.03 (5)
C4	0.19 (4)	0.21 (5)	0.46 (7)	−0.05 (3)	0.09 (5)	−0.03 (5)
C5	0.22 (5)	0.21 (5)	0.46 (7)	−0.06 (5)	0.09 (5)	−0.02 (5)
N1	0.11 (4)	0.19 (5)	0.46 (7)	−0.02 (3)	0.11 (4)	−0.02 (5)
I1	0.099 (2)	0.104 (3)	0.108 (3)	0.019 (2)	−0.0040 (19)	0.009 (2)
I2	0.0608 (15)	0.0622 (16)	0.155 (3)	0.0314 (13)	−0.0187 (18)	−0.011 (2)
Pb1	0.0358 (8)	0.0403 (9)	0.1069 (17)	0.0003 (8)	0.0014 (10)	0.0057 (13)

Geometric parameters (Å, º)

C1—N1	1.449 (10)	C5—H5A	0.96
C1—C2	1.520 (10)	C5—H5B	0.96
C1—H1D	0.97	C5—H5C	0.96
C1—H1E	0.97	N1—H1A	0.89
C2—C3	1.518 (10)	N1—H1B	0.89
C2—H2A	0.97	N1—H1C	0.89
C2—H2B	0.97	I1—Pb1	3.200 (4)
C3—C4	1.520 (10)	I2—Pb1^i	3.188 (2)
C3—H3A	0.97	I2—Pb1	3.191 (2)
C3—H3B	0.97	Pb1—I2^ii	3.188 (2)
C4—C5	1.519 (10)	Pb1—I2^iii	3.188 (2)
C4—H4A	0.97	Pb1—I2^iv	3.191 (2)
C4—H4B	0.97	Pb1—I1^iv	3.200 (4)
N1—C1—C2	110.7 (16)	H5A—C5—H5B	109.5
N1—C1—H1D	109.5	C4—C5—H5C	109.5
C2—C1—H1D	109.5	H5A—C5—H5C	109.5
N1—C1—H1E	109.5	H5B—C5—H5C	109.5
C2—C1—H1E	109.5	C1—N1—H1A	109.5
H1D—C1—H1E	108.1	C1—N1—H1B	109.5
C3—C2—C1	113.2 (16)	H1A—N1—H1B	109.5
C3—C2—H2A	108.9	C1—N1—H1C	109.5
C1—C2—H2A	108.9	H1A—N1—H1C	109.5
C3—C2—H2B	108.9	H1B—N1—H1C	109.5
C1—C2—H2B	108.9	Pb1^i—I2—Pb1	159.01 (11)
H2A—C2—H2B	107.8	I2^ii—Pb1—I2^iii	180
C2—C3—C4	113.4 (16)	I2^ii—Pb1—I2^iv	92.095 (19)
C2—C3—H3A	108.9	I2^iii—Pb1—I2^iv	87.91 (2)
C4—C3—H3A	108.9	I2^ii—Pb1—I2	87.91 (2)
C2—C3—H3B	108.9	I2^iii—Pb1—I2	92.095 (19)
C4—C3—H3B	108.9	I2^iv—Pb1—I2	180.00 (14)
H3A—C3—H3B	107.7	I2^ii—Pb1—I1^iv	92.23 (10)
C5—C4—C3	113.1 (16)	I2^iii—Pb1—I1^iv	87.77 (10)
C5—C4—H4A	109	I2^iv—Pb1—I1^iv	92.76 (9)
C3—C4—H4A	109	I2—Pb1—I1^iv	87.24 (9)
C5—C4—H4B	109	I2^ii—Pb1—I1	87.77 (10)
C3—C4—H4B	109	I2^iii—Pb1—I1	92.23 (10)
H4A—C4—H4B	107.8	I2^iv—Pb1—I1	87.24 (9)
C4—C5—H5A	109.5	I2—Pb1—I1	92.76 (9)
C4—C5—H5B	109.5	I1^iv—Pb1—I1	180.0000 (10)
N1—C1—C2—C3	−159 (7)	Pb1^i—I2—Pb1—I2^iii	−19.9 (3)
C1—C2—C3—C4	−148 (7)	Pb1^i—I2—Pb1—I1^iv	67.8 (4)
C2—C3—C4—C5	−72 (8)	Pb1^i—I2—Pb1—I1	−112.2 (4)
Pb1^i—I2—Pb1—I2^ii	160.1 (3)

Symmetry codes: (i) x−1/2, −y+5/2, −z+2; (ii) −x+3/2, y−1/2, z; (iii) x+1/2, −y+5/2, −z+2; (iv) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2^ii	0.89	3.12	3.70 (5)	125
N1—H1B···I1	0.89	2.8	3.66 (7)	163
N1—H1C···I1^v	0.89	2.65	3.53 (5)	171

Symmetry codes: (ii) −x+3/2, y−1/2, z; (v) −x+5/2, y−1/2, z.

(3a) bis(hexylammonium)tetraiodoplumbate(II)

Crystal data

2(C6H16N)·I4Pb	F(000) = 824
Mr = 919.19	Dx = 2.489 Mg m^−3
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 866 reflections
a = 8.643 (4) Å	θ = 6.6–56.4°
b = 8.845 (4) Å	µ = 11.91 mm^−1
c = 16.052 (7) Å	T = 173 K
β = 91.985 (8)°	Plate, yellow
V = 1226.4 (10) Å^3	0.32 × 0.16 × 0.02 mm
Z = 2

Data collection

Bruker APEX II CCD area detector diffractometer	2984 independent reflections
Radiation source: fine-focus sealed tube	2563 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.092
ω scans	θmax = 28°, θmin = 1.3°
Absorption correction: integration Bruker XPREP (Bruker, 2004)	h = −11→11
Tmin = 0.147, Tmax = 0.784	k = −11→11
11777 measured reflections	l = −18→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.143	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 49.3157P] where P = (Fo^2 + 2Fc^2)/3
2984 reflections	(Δ/σ)max = 0.002
89 parameters	Δρmax = 4.93 e Å^−3
0 restraints	Δρmin = −2.77 e Å^−3

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9621 (18)	0.4637 (18)	0.8019 (11)	0.035 (4)
H1D	0.8616	0.4728	0.8293	0.041*
H1E	1.0015	0.3598	0.8115	0.041*
C2	0.939 (2)	0.490 (2)	0.7102 (11)	0.042 (4)
H2A	1.0403	0.4871	0.6836	0.05*
H2B	0.8946	0.5926	0.7011	0.05*
C3	0.831 (2)	0.3738 (18)	0.6686 (10)	0.035 (4)
H3A	0.8822	0.2735	0.6698	0.042*
H3B	0.735	0.366	0.7	0.042*
C4	0.791 (2)	0.417 (2)	0.5793 (11)	0.043 (4)
H4A	0.8874	0.4225	0.5479	0.051*
H4B	0.7427	0.5181	0.5783	0.051*
C5	0.681 (3)	0.305 (2)	0.5363 (12)	0.049 (5)
H5A	0.5848	0.2986	0.5677	0.059*
H5B	0.7295	0.2031	0.5374	0.059*
C6	0.640 (3)	0.347 (3)	0.4462 (13)	0.066 (7)
H6A	0.5689	0.2724	0.4217	0.098*
H6B	0.7349	0.3504	0.4142	0.098*
H6C	0.5911	0.4473	0.4447	0.098*
N1	1.0710 (16)	0.5717 (15)	0.8387 (10)	0.037 (3)
H1A	1.0832	0.5534	0.8943	0.056*
H1B	1.0342	0.6671	0.8306	0.056*
H1C	1.1639	0.5622	0.8142	0.056*
I1	0.97165 (12)	0.96748 (11)	0.80108 (6)	0.0293 (2)
I2	0.69394 (10)	1.19584 (10)	0.99643 (6)	0.0250 (2)
Pb1	1	1	1	0.01592 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.020 (7)	0.032 (8)	0.051 (10)	0.012 (6)	−0.007 (7)	−0.003 (7)
C2	0.057 (12)	0.036 (9)	0.032 (9)	−0.008 (8)	−0.006 (8)	0.008 (7)
C3	0.045 (9)	0.028 (8)	0.032 (8)	−0.004 (7)	−0.006 (7)	0.004 (6)
C4	0.056 (11)	0.042 (9)	0.030 (9)	0.009 (8)	−0.003 (8)	0.007 (7)
C5	0.065 (13)	0.046 (11)	0.035 (10)	−0.003 (9)	−0.009 (9)	−0.002 (8)
C6	0.093 (19)	0.065 (14)	0.036 (11)	0.012 (13)	−0.018 (11)	−0.012 (10)
N1	0.032 (7)	0.028 (7)	0.050 (9)	−0.004 (6)	−0.014 (6)	0.013 (6)
I1	0.0374 (5)	0.0256 (5)	0.0248 (5)	0.0015 (4)	0.0011 (4)	0.0039 (4)
I2	0.0176 (4)	0.0197 (4)	0.0376 (5)	0.0079 (3)	−0.0024 (3)	−0.0052 (3)
Pb1	0.0119 (3)	0.0118 (3)	0.0240 (4)	−0.0003 (2)	−0.0002 (2)	0.0001 (3)

Geometric parameters (Å, º)

C1—N1	1.45 (2)	C5—H5B	0.99
C1—C2	1.50 (2)	C6—H6A	0.98
C1—H1D	0.99	C6—H6B	0.98
C1—H1E	0.99	C6—H6C	0.98
C2—C3	1.53 (2)	N1—H1A	0.91
C2—H2A	0.99	N1—H1B	0.91
C2—H2B	0.99	N1—H1C	0.91
C3—C4	1.51 (2)	I1—Pb1	3.2069 (17)
C3—H3A	0.99	I2—Pb1	3.1608 (13)
C3—H3B	0.99	I2—Pb1^i	3.1712 (13)
C4—C5	1.52 (3)	Pb1—I2^ii	3.1608 (13)
C4—H4A	0.99	Pb1—I2^iii	3.1712 (14)
C4—H4B	0.99	Pb1—I2^iv	3.1712 (14)
C5—C6	1.53 (3)	Pb1—I1^ii	3.2069 (17)
C5—H5A	0.99
N1—C1—C2	111.1 (15)	H5A—C5—H5B	107.8
N1—C1—H1D	109.4	C5—C6—H6A	109.5
C2—C1—H1D	109.4	C5—C6—H6B	109.5
N1—C1—H1E	109.4	H6A—C6—H6B	109.5
C2—C1—H1E	109.4	C5—C6—H6C	109.5
H1D—C1—H1E	108	H6A—C6—H6C	109.5
C1—C2—C3	112.5 (14)	H6B—C6—H6C	109.5
C1—C2—H2A	109.1	C1—N1—H1A	109.5
C3—C2—H2A	109.1	C1—N1—H1B	109.5
C1—C2—H2B	109.1	H1A—N1—H1B	109.5
C3—C2—H2B	109.1	C1—N1—H1C	109.5
H2A—C2—H2B	107.8	H1A—N1—H1C	109.5
C4—C3—C2	111.2 (14)	H1B—N1—H1C	109.5
C4—C3—H3A	109.4	Pb1—I2—Pb1^i	155.11 (3)
C2—C3—H3A	109.4	I2^ii—Pb1—I2	180
C4—C3—H3B	109.4	I2^ii—Pb1—I2^iii	88.70 (3)
C2—C3—H3B	109.4	I2—Pb1—I2^iii	91.30 (3)
H3A—C3—H3B	108	I2^ii—Pb1—I2^iv	91.30 (3)
C3—C4—C5	112.7 (15)	I2—Pb1—I2^iv	88.70 (3)
C3—C4—H4A	109	I2^iii—Pb1—I2^iv	180
C5—C4—H4A	109	I2^ii—Pb1—I1	90.22 (3)
C3—C4—H4B	109	I2—Pb1—I1	89.78 (3)
C5—C4—H4B	109	I2^iii—Pb1—I1	85.39 (3)
H4A—C4—H4B	107.8	I2^iv—Pb1—I1	94.61 (3)
C4—C5—C6	112.9 (18)	I2^ii—Pb1—I1^ii	89.78 (3)
C4—C5—H5A	109	I2—Pb1—I1^ii	90.22 (3)
C6—C5—H5A	109	I2^iii—Pb1—I1^ii	94.61 (3)
C4—C5—H5B	109	I2^iv—Pb1—I1^ii	85.39 (3)
C6—C5—H5B	109	I1—Pb1—I1^ii	180
N1—C1—C2—C3	177.0 (15)	Pb1^i—I2—Pb1—I2^iii	174.29 (10)
C1—C2—C3—C4	171.6 (16)	Pb1^i—I2—Pb1—I2^iv	−5.71 (10)
C2—C3—C4—C5	−178.8 (17)	Pb1^i—I2—Pb1—I1	−100.32 (9)
C3—C4—C5—C6	180.0 (18)	Pb1^i—I2—Pb1—I1^ii	79.68 (9)

Symmetry codes: (i) −x+3/2, y+1/2, −z+2; (ii) −x+2, −y+2, −z+2; (iii) −x+3/2, y−1/2, −z+2; (iv) x+1/2, −y+5/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2^v	0.91	2.89	3.599 (13)	136
N1—H1B···I1	0.91	2.75	3.650 (13)	171
N1—H1C···I1^v	0.91	2.69	3.553 (15)	159

Symmetry code: (v) x+1/2, −y+3/2, z.

(3b) bis(hexylammonium)tetraiodoplumbate(II)

Crystal data

2(C6H16N)·I4Pb	F(000) = 1648
Mr = 919.19	Dx = 2.403 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5270 reflections
a = 8.9413 (2) Å	θ = 2.6–29.9°
b = 8.6874 (2) Å	µ = 11.50 mm^−1
c = 32.7027 (10) Å	T = 293 K
V = 2540.24 (11) Å^3	Plate, orange
Z = 4	0.46 × 0.28 × 0.05 mm

Data collection

Bruker APEX II CCD area detector diffractometer	3056 independent reflections
Radiation source: fine-focus sealed tube	2421 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 28°, θmin = 2.6°
Absorption correction: integration Bruker XPREP (Bruker, 2004)	h = −9→11
Tmin = 0.058, Tmax = 0.536	k = −10→11
12552 measured reflections	l = −42→43

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.081	H-atom parameters constrained
wR(F^2) = 0.168	w = 1/[σ^2(Fo^2) + (0.P)^2 + 101.7161P] where P = (Fo^2 + 2Fc^2)/3
S = 1.34	(Δ/σ)max < 0.001
3056 reflections	Δρmax = 1.65 e Å^−3
89 parameters	Δρmin = −1.69 e Å^−3
56 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00037 (4)

Special details

Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2004)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.970 (4)	0.463 (4)	0.9038 (6)	0.120 (8)
H1D	0.8689	0.4845	0.913	0.144*
H1E	0.9957	0.358	0.9111	0.144*
C2	0.985 (4)	0.489 (4)	0.8585 (6)	0.136 (8)
H2A	1.0882	0.4693	0.8508	0.163*
H2B	0.9647	0.5967	0.8528	0.163*
C3	0.883 (4)	0.391 (4)	0.8320 (6)	0.148 (8)
H3A	0.7796	0.4145	0.8379	0.177*
H3B	0.8999	0.2824	0.8379	0.177*
C4	0.917 (4)	0.423 (4)	0.7872 (6)	0.164 (9)
H4A	0.8935	0.5296	0.7813	0.197*
H4B	1.0236	0.409	0.7825	0.197*
C5	0.832 (4)	0.321 (4)	0.7578 (7)	0.177 (10)
H5A	0.7256	0.3351	0.762	0.213*
H5B	0.8561	0.2144	0.7632	0.213*
C6	0.871 (5)	0.360 (5)	0.7136 (7)	0.202 (15)
H6A	0.8147	0.294	0.6956	0.303*
H6B	0.9758	0.3435	0.7091	0.303*
H6C	0.8463	0.4652	0.7081	0.303*
N1	1.078 (2)	0.574 (2)	0.9216 (7)	0.086 (5)
H1A	1.0749	0.5688	0.9488	0.129*
H1B	1.055	0.6691	0.9136	0.129*
H1C	1.1703	0.5512	0.9131	0.129*
I1	1.03252 (17)	0.98288 (17)	0.90247 (5)	0.0689 (4)
I2	0.69807 (13)	1.19581 (14)	0.99628 (5)	0.0637 (4)
Pb1	1	1	1	0.0443 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.112 (16)	0.122 (17)	0.127 (12)	−0.016 (13)	−0.005 (15)	−0.027 (16)
C2	0.137 (17)	0.145 (18)	0.126 (12)	0.005 (15)	−0.008 (14)	−0.028 (15)
C3	0.149 (18)	0.164 (19)	0.130 (12)	0.012 (17)	−0.022 (15)	−0.035 (16)
C4	0.17 (2)	0.19 (2)	0.129 (12)	0.02 (2)	−0.022 (16)	−0.032 (17)
C5	0.18 (2)	0.22 (2)	0.132 (14)	0.02 (2)	−0.029 (18)	−0.041 (19)
C6	0.22 (3)	0.26 (4)	0.126 (13)	0.05 (3)	−0.03 (2)	−0.03 (2)
N1	0.057 (10)	0.082 (13)	0.120 (13)	0.016 (9)	−0.003 (10)	−0.003 (11)
I1	0.0759 (9)	0.0620 (8)	0.0687 (9)	0.0080 (8)	−0.0078 (7)	0.0020 (7)
I2	0.0451 (6)	0.0439 (6)	0.1019 (11)	0.0175 (5)	−0.0117 (7)	−0.0073 (7)
Pb1	0.0328 (4)	0.0322 (4)	0.0679 (6)	0.0001 (3)	−0.0003 (4)	0.0003 (5)

Geometric parameters (Å, º)

C1—N1	1.49 (3)	C5—H5B	0.97
C1—C2	1.504 (10)	C6—H6A	0.96
C1—H1D	0.97	C6—H6B	0.96
C1—H1E	0.97	C6—H6C	0.96
C2—C3	1.522 (10)	N1—H1A	0.89
C2—H2A	0.97	N1—H1B	0.89
C2—H2B	0.97	N1—H1C	0.89
C3—C4	1.525 (10)	I1—Pb1	3.2062 (15)
C3—H3A	0.97	I2—Pb1^i	3.1835 (11)
C3—H3B	0.97	I2—Pb1	3.1932 (11)
C4—C5	1.510 (10)	Pb1—I2^ii	3.1835 (11)
C4—H4A	0.97	Pb1—I2^iii	3.1835 (11)
C4—H4B	0.97	Pb1—I2^iv	3.1932 (11)
C5—C6	1.523 (10)	Pb1—I1^iv	3.2062 (15)
C5—H5A	0.97
N1—C1—C2	103 (2)	H5A—C5—H5B	108
N1—C1—H1D	111.1	C5—C6—H6A	109.5
C2—C1—H1D	111.1	C5—C6—H6B	109.5
N1—C1—H1E	111.1	H6A—C6—H6B	109.5
C2—C1—H1E	111.1	C5—C6—H6C	109.5
H1D—C1—H1E	109.1	H6A—C6—H6C	109.5
C1—C2—C3	114.9 (14)	H6B—C6—H6C	109.5
C1—C2—H2A	108.5	C1—N1—H1A	109.5
C3—C2—H2A	108.5	C1—N1—H1B	109.5
C1—C2—H2B	108.5	H1A—N1—H1B	109.5
C3—C2—H2B	108.5	C1—N1—H1C	109.5
H2A—C2—H2B	107.5	H1A—N1—H1C	109.5
C2—C3—C4	109.0 (13)	H1B—N1—H1C	109.5
C2—C3—H3A	109.9	Pb1^i—I2—Pb1	155.65 (5)
C4—C3—H3A	109.9	I2^ii—Pb1—I2^iii	180
C2—C3—H3B	109.9	I2^ii—Pb1—I2^iv	91.695 (9)
C4—C3—H3B	109.9	I2^iii—Pb1—I2^iv	88.305 (9)
H3A—C3—H3B	108.3	I2^ii—Pb1—I2	88.305 (9)
C5—C4—C3	113.8 (14)	I2^iii—Pb1—I2	91.695 (9)
C5—C4—H4A	108.8	I2^iv—Pb1—I2	180.0000 (10)
C3—C4—H4A	108.8	I2^ii—Pb1—I1^iv	91.50 (4)
C5—C4—H4B	108.8	I2^iii—Pb1—I1^iv	88.50 (4)
C3—C4—H4B	108.8	I2^iv—Pb1—I1^iv	93.64 (4)
H4A—C4—H4B	107.7	I2—Pb1—I1^iv	86.36 (4)
C4—C5—C6	111.2 (14)	I2^ii—Pb1—I1	88.50 (4)
C4—C5—H5A	109.4	I2^iii—Pb1—I1	91.50 (4)
C6—C5—H5A	109.4	I2^iv—Pb1—I1	86.36 (4)
C4—C5—H5B	109.4	I2—Pb1—I1	93.64 (4)
C6—C5—H5B	109.4	I1^iv—Pb1—I1	180.0000 (10)
N1—C1—C2—C3	−179 (3)	Pb1^i—I2—Pb1—I2^ii	171.92 (11)
C1—C2—C3—C4	−177 (3)	Pb1^i—I2—Pb1—I2^iii	−8.08 (11)
C2—C3—C4—C5	175 (3)	Pb1^i—I2—Pb1—I1^iv	80.32 (14)
C3—C4—C5—C6	180 (4)	Pb1^i—I2—Pb1—I1	−99.68 (14)

Symmetry codes: (i) x−1/2, −y+5/2, −z+2; (ii) −x+3/2, y−1/2, z; (iii) x+1/2, −y+5/2, −z+2; (iv) −x+2, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I2^ii	0.89	3.1	3.63 (2)	121
N1—H1B···I1	0.89	2.76	3.63 (2)	166
N1—H1C···I1^v	0.89	2.74	3.622 (18)	169

Symmetry codes: (ii) −x+3/2, y−1/2, z; (v) −x+5/2, y−1/2, z.