Structural diversity in hybrid organic–inorganic lead iodide materials

The structural chemistry of hybrid organic–inorganic lead iodide materials has become of increasing significance for energy applications since the discovery and development of perovskite solar cells based on methylammonium lead iodide. Seven new hybrid lead iodide compounds have been synthesized and structurally characterized using single-crystal X-ray diffraction. The lead iodide units in materials templated with bipyridyl, 1,2-bis(4-pyridyl)ethane, 1,2-di(4-pyridyl)ethylene and imidazole adopt one-dimensional chain structures, while crystallization from solutions containing piperazinium cations generates a salt containing isolated [PbI₆]⁴⁻ octahedral anions. Templating with 4-chlorobenzyl­ammonium lead iodide adopts the well known two-dimensional layered perovskite structure with vertex shared sheets of composition [PbI₄]²⁻ separated by double layers of organic cations. The relationships between the various structures determined, their compositions, stability and hydrogen bonding between the protonated amine and the iodide ions of the PbI₆ octahedra are described.

Computing details

For all structures, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014).

(shelx2)

Crystal data

C5.60H7.20Cl0.80I1.60N0.80Pb0.40	Z = 5
Mr = 400.00	F(000) = 888
Monoclinic, P21	Dx = 2.755 Mg m^−3
a = 8.5992 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9125 (3) Å	µ = 12.34 mm^−1
c = 15.8039 (6) Å	T = 150 K
β = 95.502 (3)°	Plate, orange
V = 1205.64 (7) Å^3

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	Rint = 0.029
Absorption correction: multi-scan	θmax = 29.2°, θmin = 3.3°
Tmin = 0.625, Tmax = 1.000	h = −9→11
5488 measured reflections	k = −11→10
4219 independent reflections	l = −20→13
3773 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.031	w = 1/[σ^2(Fo^2) + (0.0099P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.054	(Δ/σ)max = 0.001
S = 0.87	Δρmax = 1.50 e Å^−3
4219 reflections	Δρmin = −1.86 e Å^−3
211 parameters	Absolute structure: Refined as an inversion twin.
1 restraint	Absolute structure parameter: 0.114 (10)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	Uiso*/Ueq
Pb1	0.24730 (6)	0.84798 (12)	0.99932 (4)	0.01312 (9)
I1	0.44257 (10)	1.15242 (10)	1.00751 (6)	0.0195 (3)
I3	0.21991 (10)	0.87778 (12)	0.80009 (6)	0.0210 (3)
I2	0.26429 (10)	0.81183 (12)	1.20407 (6)	0.0186 (3)
I5	−0.05716 (10)	1.04131 (11)	1.01266 (6)	0.0209 (3)
Cl1	0.2958 (4)	0.7932 (4)	0.4586 (2)	0.0387 (9)
Cl2	−0.0300 (4)	0.9223 (4)	0.5821 (2)	0.0369 (9)
N2	0.6517 (15)	0.9286 (18)	0.8413 (8)	0.025 (3)
H2A	0.7076	0.9250	0.8931	0.037*
H2B	0.5514	0.8999	0.8464	0.037*
H2C	0.6525	1.0239	0.8207	0.037*
C10	−0.2603 (15)	0.868 (2)	0.2110 (9)	0.025 (4)
H10A	−0.3665	0.8238	0.2062	0.030*
H10B	−0.2665	0.9665	0.1823	0.030*
C11	−0.0976 (15)	0.994 (2)	0.3335 (10)	0.030 (4)
H11	−0.0579	1.0610	0.2939	0.036*
C12	0.7250 (15)	0.822 (3)	0.7801 (10)	0.030 (4)
H12A	0.8289	0.8603	0.7681	0.036*
H12B	0.7384	0.7214	0.8057	0.036*
C13	0.5460 (15)	0.6820 (19)	0.6750 (9)	0.023 (3)
H13	0.5648	0.5942	0.7085	0.028*
C14	0.6192 (13)	0.8146 (16)	0.7000 (8)	0.020 (3)
C15	−0.2044 (13)	0.8894 (15)	0.3039 (8)	0.020 (3)
C16	−0.1019 (13)	0.9107 (14)	0.4757 (7)	0.021 (3)
C17	−0.2646 (13)	0.7907 (14)	0.3637 (8)	0.026 (3)
H17	−0.3405	0.7173	0.3453	0.031*
C18	0.5916 (14)	0.9436 (14)	0.6490 (8)	0.022 (3)
H18	0.6431	1.0351	0.6648	0.026*
C19	0.4179 (13)	0.7998 (15)	0.5532 (7)	0.022 (3)
C20	−0.0444 (14)	1.0078 (15)	0.4183 (8)	0.026 (3)
H20	0.0302	1.0824	0.4368	0.032*
C21	−0.2110 (14)	0.8029 (15)	0.4497 (8)	0.025 (3)
H21	−0.2496	0.7371	0.4901	0.030*
C22	0.4462 (14)	0.6760 (15)	0.6018 (8)	0.021 (3)
H22	0.3965	0.5841	0.5852	0.026*
C26	0.4885 (14)	0.9368 (14)	0.5754 (8)	0.026 (3)
H26	0.4670	1.0234	0.5412	0.031*
N1	−0.1557 (13)	0.7690 (19)	0.1681 (8)	0.027 (4)
H1A	−0.0548	0.7970	0.1823	0.040*
H1B	−0.1783	0.7764	0.1108	0.040*
H1C	−0.1691	0.6724	0.1846	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.00994 (16)	0.01146 (17)	0.01755 (19)	−0.00016 (14)	−0.00079 (13)	0.00039 (14)
I1	0.0150 (4)	0.0160 (7)	0.0272 (6)	−0.0064 (5)	0.0015 (4)	−0.0041 (5)
I3	0.0209 (4)	0.0246 (8)	0.0165 (5)	−0.0007 (5)	−0.0025 (4)	−0.0023 (5)
I2	0.0188 (4)	0.0202 (7)	0.0160 (5)	0.0006 (5)	−0.0022 (4)	−0.0018 (5)
I5	0.0148 (4)	0.0187 (8)	0.0289 (6)	0.0097 (5)	0.0010 (4)	0.0032 (5)
Cl1	0.0382 (19)	0.048 (2)	0.027 (2)	0.0124 (18)	−0.0108 (15)	−0.0109 (17)
Cl2	0.0371 (19)	0.046 (2)	0.0254 (19)	0.0045 (17)	−0.0063 (15)	−0.0042 (17)
N2	0.034 (7)	0.020 (9)	0.018 (7)	−0.010 (6)	−0.005 (5)	0.004 (6)
C10	0.018 (6)	0.037 (11)	0.019 (7)	−0.006 (8)	−0.001 (5)	0.001 (8)
C11	0.019 (7)	0.033 (10)	0.037 (9)	−0.004 (7)	−0.005 (6)	0.008 (8)
C12	0.018 (7)	0.047 (12)	0.025 (8)	0.004 (8)	0.005 (6)	−0.003 (9)
C13	0.034 (8)	0.015 (8)	0.020 (8)	0.006 (7)	0.004 (6)	0.006 (6)
C14	0.009 (5)	0.026 (8)	0.025 (7)	0.005 (6)	−0.004 (5)	0.008 (6)
C15	0.013 (6)	0.024 (8)	0.021 (7)	0.003 (6)	−0.005 (5)	−0.003 (6)
C16	0.013 (5)	0.028 (7)	0.020 (7)	0.009 (6)	−0.006 (5)	−0.001 (6)
C17	0.017 (6)	0.019 (7)	0.039 (9)	0.001 (6)	−0.004 (6)	0.002 (6)
C18	0.031 (7)	0.021 (7)	0.015 (7)	−0.011 (6)	0.007 (5)	−0.011 (6)
C19	0.019 (6)	0.035 (8)	0.012 (6)	−0.004 (6)	0.003 (5)	−0.004 (6)
C20	0.024 (7)	0.019 (7)	0.036 (8)	−0.008 (7)	−0.003 (6)	−0.006 (7)
C21	0.029 (7)	0.028 (7)	0.020 (7)	0.009 (6)	0.004 (5)	0.010 (6)
C22	0.028 (7)	0.014 (6)	0.024 (7)	−0.002 (6)	0.010 (6)	−0.001 (6)
C26	0.031 (7)	0.017 (7)	0.029 (8)	0.000 (6)	0.001 (6)	0.000 (6)
N1	0.020 (6)	0.027 (10)	0.033 (8)	−0.001 (7)	0.000 (5)	−0.003 (7)

Geometric parameters (Å, º)

Pb1—I3	3.1461 (12)	C11—C15	1.36 (2)
Pb1—I5	3.1581 (11)	C11—C20	1.380 (19)
Pb1—I5^i	3.1812 (13)	C12—C14	1.488 (18)
Pb1—I1	3.1870 (13)	C13—C22	1.373 (18)
Pb1—I1^ii	3.1963 (11)	C13—C14	1.38 (2)
Pb1—I2	3.2411 (12)	C14—C18	1.410 (17)
I1—Pb1^iii	3.1964 (11)	C15—C17	1.423 (17)
I5—Pb1^iv	3.1812 (13)	C16—C21	1.378 (16)
Cl1—C19	1.743 (12)	C16—C20	1.379 (17)
Cl2—C16	1.737 (12)	C17—C21	1.396 (16)
N2—C12	1.53 (2)	C18—C26	1.395 (16)
C10—N1	1.47 (2)	C19—C22	1.354 (17)
C10—C15	1.513 (18)	C19—C26	1.393 (16)
I3—Pb1—I5	92.16 (3)	C22—C13—C14	120.4 (14)
I3—Pb1—I5^i	91.39 (4)	C13—C14—C18	119.2 (11)
I5—Pb1—I5^i	92.755 (17)	C13—C14—C12	120.6 (14)
I3—Pb1—I1	87.56 (4)	C18—C14—C12	120.2 (14)
I5—Pb1—I1	88.27 (4)	C11—C15—C17	118.2 (12)
I5^i—Pb1—I1	178.56 (4)	C11—C15—C10	124.2 (13)
I3—Pb1—I1^ii	89.71 (3)	C17—C15—C10	117.6 (13)
I5—Pb1—I1^ii	178.12 (4)	C21—C16—C20	121.2 (12)
I5^i—Pb1—I1^ii	87.43 (4)	C21—C16—Cl2	119.9 (10)
I1—Pb1—I1^ii	91.579 (16)	C20—C16—Cl2	118.8 (10)
I3—Pb1—I2	178.10 (4)	C21—C17—C15	119.4 (12)
I5—Pb1—I2	86.90 (3)	C26—C18—C14	120.0 (11)
I5^i—Pb1—I2	87.00 (4)	C22—C19—C26	121.4 (11)
I1—Pb1—I2	94.07 (3)	C22—C19—Cl1	121.3 (10)
I1^ii—Pb1—I2	91.24 (3)	C26—C19—Cl1	117.3 (10)
Pb1—I1—Pb1^iii	154.28 (4)	C16—C20—C11	118.5 (13)
Pb1—I5—Pb1^iv	152.80 (4)	C16—C21—C17	119.8 (12)
N1—C10—C15	111.9 (12)	C19—C22—C13	120.7 (13)
C15—C11—C20	122.9 (14)	C19—C26—C18	118.4 (11)
C14—C12—N2	108.1 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···I5^v	0.91	2.83	3.649 (13)	151
N2—H2B···I3	0.91	2.88	3.735 (13)	157
N2—H2C···I2^iii	0.91	2.70	3.578 (16)	162
C10—H10A···I2^vi	0.99	3.17	4.110 (13)	158
N1—H1A···I2^vii	0.91	2.74	3.622 (12)	165
N1—H1B···I1^viii	0.91	3.01	3.682 (13)	132
N1—H1B···I5^vii	0.91	3.06	3.611 (15)	121
N1—H1C···I3^viii	0.91	2.68	3.573 (17)	169

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

(shelx3)

Crystal data

C10H10I4N2Pb	Z = 4
Mr = 872.99	F(000) = 1512
Monoclinic, I2/a	Dx = 3.419 Mg m^−3
a = 7.7839 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.1821 (5) Å	µ = 17.21 mm^−1
c = 15.3644 (7) Å	T = 150 K
β = 90.434 (4)°	Block, black
V = 1696.06 (12) Å^3	0.3 × 0.2 × 0.1 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	Rint = 0.023
Absorption correction: multi-scan	θmax = 29.0°, θmin = 3.9°
Tmin = 0.792, Tmax = 1.000	h = −10→6
2612 measured reflections	k = −17→15
1652 independent reflections	l = −13→20
1440 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.054	w = 1/[σ^2(Fo^2) + (0.0156P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.004
1652 reflections	Δρmax = 0.80 e Å^−3
78 parameters	Δρmin = −1.08 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
N1	0.4173 (7)	0.4150 (4)	0.2922 (4)	0.0175 (13)
H1	0.4583	0.4144	0.2404	0.021*
C5	0.2874 (7)	0.4170 (4)	0.4560 (4)	0.0109 (14)
C6	0.2876 (8)	0.4990 (5)	0.4047 (4)	0.0166 (15)
H6	0.2438	0.5551	0.4265	0.020*
C3	0.4218 (8)	0.3350 (5)	0.3381 (5)	0.0194 (15)
H3	0.4687	0.2804	0.3146	0.023*
C1	0.3530 (8)	0.4956 (5)	0.3223 (5)	0.0201 (16)
H1A	0.3524	0.5492	0.2875	0.024*
C4	0.3558 (8)	0.3351 (5)	0.4208 (4)	0.0200 (16)
H4	0.3569	0.2799	0.4535	0.024*
Pb1	0.7500	0.09143 (3)	0.5000	0.01449 (10)
I2	0.41522 (5)	0.07270 (3)	0.37607 (3)	0.01553 (12)
I3	0.59764 (6)	0.25714 (3)	0.12524 (3)	0.01971 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.021 (3)	0.023 (3)	0.008 (3)	−0.002 (3)	0.006 (2)	0.002 (3)
C5	0.004 (3)	0.018 (3)	0.011 (4)	−0.003 (3)	−0.005 (3)	0.002 (3)
C6	0.017 (3)	0.017 (3)	0.016 (4)	0.003 (3)	−0.002 (3)	−0.003 (3)
C3	0.024 (3)	0.014 (3)	0.020 (4)	0.000 (3)	0.000 (3)	0.000 (3)
C1	0.022 (3)	0.020 (4)	0.019 (4)	0.004 (3)	−0.001 (3)	0.005 (3)
C4	0.024 (3)	0.015 (3)	0.021 (4)	−0.002 (3)	0.001 (3)	0.005 (3)
Pb1	0.01533 (17)	0.01623 (19)	0.0119 (2)	0.000	0.00130 (15)	0.000
I2	0.0171 (2)	0.0158 (2)	0.0137 (2)	−0.00084 (19)	−0.00030 (18)	0.00046 (18)
I3	0.0256 (2)	0.0183 (2)	0.0154 (3)	−0.0005 (2)	0.0055 (2)	0.00202 (19)

Geometric parameters (Å, º)

N1—C1	1.333 (8)	Pb1—I3^iii	3.1234 (5)
N1—C3	1.336 (8)	Pb1—I2	3.2267 (4)
C5—C4	1.389 (9)	Pb1—I2^iv	3.2267 (4)
C5—C6	1.405 (9)	Pb1—I2^v	3.2765 (5)
C5—C5^i	1.476 (12)	Pb1—I2^vi	3.2765 (5)
C6—C1	1.369 (9)	I2—Pb1^vi	3.2765 (5)
C3—C4	1.374 (9)	I3—Pb1^iii	3.1233 (5)
Pb1—I3^ii	3.1233 (5)
C1—N1—C3	123.6 (6)	I3^iii—Pb1—I2^iv	96.398 (12)
C4—C5—C6	118.1 (6)	I2—Pb1—I2^iv	170.55 (2)
C4—C5—C5^i	120.8 (4)	I3^ii—Pb1—I2^v	177.502 (13)
C6—C5—C5^i	121.1 (4)	I3^iii—Pb1—I2^v	88.735 (12)
C1—C6—C5	119.4 (6)	I2—Pb1—I2^v	85.261 (11)
N1—C3—C4	118.6 (7)	I2^iv—Pb1—I2^v	88.031 (12)
N1—C1—C6	119.6 (7)	I3^ii—Pb1—I2^vi	88.735 (12)
C3—C4—C5	120.6 (6)	I3^iii—Pb1—I2^vi	177.501 (13)
I3^ii—Pb1—I3^iii	93.124 (19)	I2—Pb1—I2^vi	88.031 (12)
I3^ii—Pb1—I2	96.397 (12)	I2^iv—Pb1—I2^vi	85.260 (11)
I3^iii—Pb1—I2	90.102 (12)	I2^v—Pb1—I2^vi	89.456 (18)
I3^ii—Pb1—I2^iv	90.103 (12)	Pb1—I2—Pb1^vi	91.969 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···I2^vii	0.86	3.04	3.666 (5)	132
N1—H1···I3	0.86	3.05	3.690 (6)	133
C6—H6···I3^vii	0.93	3.22	3.797 (7)	122
C3—H3···I2	0.93	3.12	3.765 (7)	128
C3—H3···I3	0.93	3.10	3.722 (7)	126
C1—H1A···I2^vii	0.93	3.13	3.718 (7)	123
C1—H1A···I3^vii	0.93	3.26	3.815 (7)	120
C4—H4···I2	0.93	3.20	3.813 (7)	125
C4—H4···I3^ii	0.93	3.27	3.877 (7)	125

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

(shelx4)

Crystal data

C7.47H11.73I3.20N1.07O1.07Pb1.07S1.07	F(000) = 5200
Mr = 794.79	Dx = 3.189 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 8.0519 (1) Å	µ = 16.95 mm^−1
b = 23.4398 (3) Å	T = 150 K
c = 32.8901 (5) Å	Needle, brown
V = 6207.51 (15) Å^3	0.5 × 0.2 × 0.1 mm
Z = 15

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	Rint = 0.033
Absorption correction: multi-scan	θmax = 29.5°, θmin = 3.3°
Tmin = 0.448, Tmax = 1.000	h = −10→6
15898 measured reflections	k = −31→18
7106 independent reflections	l = −30→41
5859 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0176P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.002
7106 reflections	Δρmax = 1.09 e Å^−3
257 parameters	Δρmin = −1.33 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
N1	0.0810 (7)	0.1010 (2)	0.1763 (2)	0.0215 (13)
C1	0.0759 (7)	0.1028 (2)	0.2601 (2)	0.0168 (14)
N2	0.0503 (6)	0.1085 (2)	0.38870 (19)	0.0253 (14)
H2	0.0413	0.1106	0.4147	0.030*
C9	0.1455 (7)	0.1472 (3)	0.2377 (2)	0.0216 (15)
H9	0.1917	0.1782	0.2512	0.026*
C8	0.0119 (8)	0.0573 (3)	0.1966 (2)	0.0250 (16)
H8	−0.0332	0.0268	0.1823	0.030*
C7	0.0072 (8)	0.0575 (3)	0.2380 (2)	0.0231 (16)
H7	−0.0421	0.0272	0.2517	0.028*
C6	−0.0078 (7)	0.0609 (3)	0.3278 (2)	0.0225 (16)
H6	−0.0552	0.0300	0.3143	0.027*
C3	0.1440 (8)	0.1481 (3)	0.3273 (2)	0.0232 (16)
H3	0.2016	0.1767	0.3137	0.028*
C2	0.0718 (7)	0.1037 (2)	0.3055 (2)	0.0168 (14)
C5	−0.0161 (8)	0.0641 (3)	0.3692 (2)	0.0230 (15)
H5	−0.0682	0.0352	0.3838	0.028*
C4	0.1301 (8)	0.1495 (3)	0.3688 (2)	0.0231 (16)
H4	0.1772	0.1795	0.3833	0.028*
C10	0.1468 (8)	0.1457 (3)	0.1964 (2)	0.0236 (16)
H10	0.1934	0.1757	0.1819	0.028*
S1	0.0345 (2)	0.12288 (8)	0.06681 (6)	0.0281 (4)
S2	0.1315 (2)	0.12153 (8)	0.49838 (6)	0.0302 (4)
O4	0.0003 (5)	0.1061 (2)	0.46691 (15)	0.0302 (12)
O3	0.1449 (5)	0.1009 (2)	0.10086 (16)	0.0308 (12)
C15	0.0856 (8)	0.0804 (3)	0.0239 (2)	0.0339 (19)
H15A	0.0407	0.0428	0.0274	0.051*
H15B	0.2042	0.0781	0.0213	0.051*
H15C	0.0396	0.0974	−0.0001	0.051*
C13	0.1324 (10)	0.1872 (3)	0.0509 (3)	0.045 (2)
H13A	0.0696	0.2040	0.0291	0.067*
H13B	0.2428	0.1790	0.0416	0.067*
H13C	0.1375	0.2134	0.0733	0.067*
C11	0.1698 (9)	0.0568 (3)	0.5247 (3)	0.043 (2)
H11A	0.2522	0.0631	0.5453	0.065*
H11B	0.2091	0.0285	0.5059	0.065*
H11C	0.0688	0.0437	0.5371	0.065*
H17	0.078 (7)	0.101 (3)	0.150 (2)	0.012 (17)*
Pb1	0.60139 (3)	0.35019 (2)	0.28752 (2)	0.01929 (7)
Pb2	0.10516 (3)	0.36302 (2)	0.36486 (2)	0.02104 (7)
I3	0.77799 (5)	0.43100 (2)	0.21751 (2)	0.02017 (10)
I4	0.43412 (5)	0.27565 (2)	0.21145 (2)	0.02108 (10)
I5	0.75896 (5)	0.42713 (2)	0.35423 (2)	0.02501 (11)
I6	0.43205 (5)	0.27496 (2)	0.35374 (2)	0.02439 (11)
I7	0.20837 (6)	0.46802 (2)	0.41361 (2)	0.03094 (12)
I8	0.00291 (6)	0.28885 (2)	0.43565 (2)	0.03636 (13)
C16	0.0225 (9)	0.1580 (3)	0.5368 (3)	0.042 (2)
H16A	−0.0079	0.1953	0.5273	0.063*
H16B	0.0919	0.1616	0.5604	0.063*
H16C	−0.0759	0.1370	0.5438	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.025 (3)	0.022 (3)	0.016 (4)	0.002 (2)	0.000 (3)	0.003 (3)
C1	0.015 (3)	0.015 (3)	0.020 (4)	0.006 (3)	−0.001 (3)	0.000 (3)
N2	0.029 (3)	0.028 (3)	0.019 (4)	−0.001 (3)	−0.001 (3)	−0.004 (3)
C9	0.022 (3)	0.023 (3)	0.020 (4)	−0.001 (3)	0.003 (3)	0.003 (3)
C8	0.030 (4)	0.021 (3)	0.023 (5)	−0.003 (3)	−0.003 (3)	−0.003 (3)
C7	0.028 (3)	0.019 (3)	0.022 (4)	0.004 (3)	0.000 (3)	0.005 (3)
C6	0.026 (3)	0.018 (3)	0.024 (4)	0.000 (3)	0.006 (3)	−0.001 (3)
C3	0.025 (3)	0.022 (3)	0.022 (5)	−0.003 (3)	−0.001 (3)	0.000 (3)
C2	0.015 (3)	0.015 (3)	0.020 (4)	0.004 (3)	0.000 (3)	0.000 (3)
C5	0.024 (3)	0.026 (3)	0.019 (4)	0.003 (3)	0.002 (3)	0.005 (3)
C4	0.030 (4)	0.022 (3)	0.017 (4)	−0.001 (3)	−0.003 (3)	−0.001 (3)
C10	0.027 (3)	0.020 (3)	0.024 (5)	0.003 (3)	0.001 (3)	0.002 (3)
S1	0.0284 (9)	0.0369 (10)	0.0188 (11)	0.0039 (8)	0.0023 (8)	−0.0017 (8)
S2	0.0255 (8)	0.0448 (11)	0.0202 (11)	−0.0044 (8)	0.0024 (8)	−0.0037 (9)
O4	0.032 (2)	0.044 (3)	0.014 (3)	−0.007 (2)	−0.002 (2)	−0.001 (2)
O3	0.032 (2)	0.042 (3)	0.018 (3)	0.008 (2)	−0.001 (2)	0.002 (2)
C15	0.037 (4)	0.039 (4)	0.026 (5)	−0.008 (4)	0.001 (4)	−0.005 (4)
C13	0.079 (6)	0.031 (4)	0.025 (5)	0.000 (4)	0.004 (5)	−0.001 (4)
C11	0.039 (4)	0.052 (5)	0.039 (6)	0.017 (4)	−0.003 (4)	0.007 (4)
Pb1	0.01597 (12)	0.02198 (13)	0.01991 (16)	0.00089 (10)	0.00010 (11)	0.00030 (11)
Pb2	0.02066 (12)	0.02386 (13)	0.01861 (16)	−0.00002 (11)	0.00050 (11)	−0.00057 (11)
I3	0.0187 (2)	0.0200 (2)	0.0218 (3)	0.00169 (17)	0.00147 (18)	0.00047 (18)
I4	0.0188 (2)	0.0195 (2)	0.0249 (3)	0.00164 (17)	−0.00082 (19)	−0.00022 (18)
I5	0.0231 (2)	0.0259 (2)	0.0259 (3)	0.00502 (19)	−0.0048 (2)	−0.0057 (2)
I6	0.0220 (2)	0.0254 (2)	0.0258 (3)	0.00013 (18)	0.0023 (2)	0.0042 (2)
I7	0.0335 (2)	0.0306 (2)	0.0288 (3)	−0.0056 (2)	−0.0018 (2)	−0.0063 (2)
I8	0.0468 (3)	0.0358 (3)	0.0265 (3)	−0.0067 (2)	0.0079 (2)	0.0037 (2)
C16	0.047 (5)	0.046 (5)	0.033 (6)	−0.003 (4)	0.010 (4)	−0.020 (4)

Geometric parameters (Å, º)

N1—C8	1.343 (8)	S2—O4	1.523 (5)
N1—C10	1.348 (8)	S2—C16	1.761 (7)
C1—C9	1.393 (8)	S2—C11	1.774 (8)
C1—C7	1.401 (9)	Pb1—I5	3.1107 (5)
C1—C2	1.494 (9)	Pb1—I6	3.1165 (5)
N2—C4	1.328 (8)	Pb1—I4^i	3.1987 (5)
N2—C5	1.335 (8)	Pb1—I3^ii	3.2242 (5)
C9—C10	1.359 (10)	Pb1—I3	3.3030 (5)
C8—C7	1.361 (10)	Pb1—I4	3.3356 (5)
C6—C5	1.365 (9)	Pb2—I8	3.0204 (6)
C6—C2	1.398 (9)	Pb2—I7	3.0526 (5)
C3—C4	1.371 (9)	Pb2—I5^iii	3.1860 (5)
C3—C2	1.390 (9)	Pb2—I6	3.3648 (5)
S1—O3	1.520 (5)	I3—Pb1^i	3.2242 (5)
S1—C15	1.775 (7)	I4—Pb1^ii	3.1987 (5)
S1—C13	1.781 (7)	I5—Pb2^iv	3.1860 (5)
C8—N1—C10	120.7 (7)	I6—Pb1—I4^i	92.861 (13)
C9—C1—C7	116.8 (7)	I5—Pb1—I3^ii	91.434 (12)
C9—C1—C2	121.8 (6)	I6—Pb1—I3^ii	90.853 (12)
C7—C1—C2	121.5 (6)	I4^i—Pb1—I3^ii	176.267 (14)
C4—N2—C5	121.4 (7)	I5—Pb1—I3	89.063 (14)
C10—C9—C1	120.8 (6)	I6—Pb1—I3	179.398 (14)
N1—C8—C7	120.5 (6)	I4^i—Pb1—I3	87.713 (12)
C8—C7—C1	120.7 (6)	I3^ii—Pb1—I3	88.571 (12)
C5—C6—C2	120.3 (6)	I5—Pb1—I4	175.893 (15)
C4—C3—C2	119.8 (6)	I6—Pb1—I4	92.929 (13)
C3—C2—C6	117.4 (7)	I4^i—Pb1—I4	93.441 (12)
C3—C2—C1	121.1 (6)	I3^ii—Pb1—I4	86.740 (12)
C6—C2—C1	121.5 (6)	I3—Pb1—I4	87.216 (13)
N2—C5—C6	120.2 (6)	I8—Pb2—I7	97.664 (16)
N2—C4—C3	120.9 (6)	I8—Pb2—I5^iii	96.755 (15)
N1—C10—C9	120.5 (6)	I7—Pb2—I5^iii	85.157 (13)
O3—S1—C15	105.0 (3)	I8—Pb2—I6	86.783 (14)
O3—S1—C13	104.2 (3)	I7—Pb2—I6	109.796 (14)
C15—S1—C13	98.0 (4)	I5^iii—Pb2—I6	164.113 (15)
O4—S2—C16	104.9 (3)	Pb1^i—I3—Pb1	92.671 (12)
O4—S2—C11	104.5 (3)	Pb1^ii—I4—Pb1	92.525 (12)
C16—S2—C11	98.7 (4)	Pb1—I5—Pb2^iv	99.251 (13)
I5—Pb1—I6	90.775 (15)	Pb1—I6—Pb2	94.077 (13)
I5—Pb1—I4^i	88.142 (12)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···S2	0.86	2.86	3.679 (7)	160
N2—H2···O4	0.86	1.75	2.604 (8)	171
C9—H9···I4	0.93	3.28	3.901 (6)	126
C9—H9···I4^ii	0.93	3.32	3.842 (6)	118
C8—H8···I3^v	0.93	3.20	3.833 (7)	127
C7—H7···I3^vi	0.93	3.26	3.731 (6)	114
C7—H7···I3^v	0.93	3.16	3.810 (7)	129
C6—H6···I5^v	0.93	3.20	3.831 (6)	127
C3—H3···I6	0.93	3.24	3.871 (6)	127
C5—H5···I5^v	0.93	3.12	3.790 (7)	131
C4—H4···I6	0.93	3.19	3.849 (6)	130
C10—H10···I4	0.93	3.19	3.857 (7)	130
C15—H15A···I7^vii	0.96	3.29	4.094 (7)	142
C15—H15B···O4^i	0.96	2.50	3.406 (8)	157
C13—H13A···I8^viii	0.96	3.13	3.970 (9)	148
C13—H13C···I6^ii	0.96	3.25	4.083 (8)	146
C11—H11A···I5^ix	0.96	3.31	4.063 (9)	137
N1—H17···S1	0.87 (7)	2.81 (7)	3.657 (7)	167 (5)
N1—H17···O3	0.87 (7)	1.70 (7)	2.534 (8)	160 (6)
C16—H16C···I7^ix	0.96	3.32	4.217 (8)	156

Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x−1/2, y, −z+1/2; (v) −x+1/2, y−1/2, z; (vi) −x+1, y−1/2, −z+1/2; (vii) −x, y−1/2, −z+1/2; (viii) x, −y+1/2, z−1/2; (ix) x−1/2, −y+1/2, −z+1.

(shelx)

Crystal data

C36H52I12N8O4Pb4	Z = 1
Mr = 3012.41	F(000) = 1320
Monoclinic, P21/c	Dx = 2.954 Mg m^−3
a = 11.8465 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 17.6887 (6) Å	µ = 15.42 mm^−1
c = 8.1762 (3) Å	T = 150 K
β = 98.798 (3)°	Needle, yellow
V = 1693.16 (10) Å^3	0.3 × 0.1 × 0.05 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	Rint = 0.050
Absorption correction: multi-scan	θmax = 29.3°, θmin = 3.4°
Tmin = 0.626, Tmax = 1.000	h = −15→16
7910 measured reflections	k = −23→24
3869 independent reflections	l = −6→11
3069 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.093	w = 1/[σ^2(Fo^2) + (0.033P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
3869 reflections	Δρmax = 2.47 e Å^−3
142 parameters	Δρmin = −2.47 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
O1	0.7444 (6)	0.8836 (3)	0.8081 (7)	0.0268 (14)
N1	0.6949 (7)	0.9469 (4)	0.5147 (9)	0.0259 (18)
H1	0.7235	0.9405	0.6169	0.031*
N2	0.7991 (7)	0.8377 (5)	1.0669 (9)	0.0268 (19)
C8	0.8088 (8)	0.8857 (6)	0.9448 (11)	0.026 (2)
C2	0.6046 (8)	0.9663 (5)	0.1902 (10)	0.021 (2)
C1	0.7046 (8)	1.0031 (5)	0.2600 (11)	0.022 (2)
H1A	0.7421	1.0351	0.1957	0.026*
C3	0.5525 (8)	0.9197 (5)	0.2896 (12)	0.029 (2)
H3	0.4859	0.8942	0.2464	0.034*
C4	0.5989 (9)	0.9106 (6)	0.4548 (12)	0.034 (3)
H4	0.5633	0.8794	0.5230	0.041*
C12	0.5561 (8)	0.9771 (5)	0.0094 (11)	0.026 (2)
H12A	0.5415	0.9281	−0.0429	0.031*
H12B	0.6113	1.0034	−0.0460	0.031*
C6	0.7474 (9)	0.9920 (6)	0.4235 (11)	0.029 (2)
H6	0.8141	1.0166	0.4701	0.034*
C11	0.8723 (9)	0.8458 (6)	1.2280 (12)	0.039 (3)
H11A	0.8537	0.8071	1.3018	0.059*
H11B	0.8602	0.8945	1.2738	0.059*
H11C	0.9509	0.8409	1.2138	0.059*
C10	0.7138 (9)	0.7766 (6)	1.0500 (13)	0.035 (3)
H10A	0.7203	0.7487	1.1518	0.053*
H10B	0.7269	0.7433	0.9621	0.053*
H10C	0.6386	0.7979	1.0252	0.053*
Pb1	1.20993 (3)	0.74905 (2)	0.94125 (4)	0.02022 (11)
I2	1.41004 (5)	0.79810 (3)	0.73216 (7)	0.02430 (16)
I3	1.19409 (5)	0.89297 (3)	1.17166 (7)	0.02501 (16)
I1	1.04403 (5)	0.84236 (3)	0.65055 (7)	0.02352 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.062 (4)	0.010	0.010	0.005 (3)	0.010	0.001 (3)
N1	0.031 (5)	0.022 (4)	0.024 (4)	0.000 (4)	0.003 (4)	0.005 (4)
N2	0.033 (5)	0.028 (5)	0.020 (4)	0.010 (4)	0.006 (3)	0.001 (4)
C8	0.032 (5)	0.022 (5)	0.026 (5)	0.008 (4)	0.012 (4)	−0.004 (4)
C2	0.027 (5)	0.018 (5)	0.018 (4)	0.001 (4)	0.003 (4)	0.001 (4)
C1	0.031 (5)	0.010 (4)	0.026 (5)	−0.004 (4)	0.007 (4)	0.004 (4)
C3	0.026 (5)	0.020 (5)	0.038 (6)	−0.007 (4)	−0.003 (4)	−0.003 (5)
C4	0.046 (7)	0.024 (6)	0.035 (6)	0.010 (5)	0.017 (5)	0.015 (5)
C12	0.028 (5)	0.025 (5)	0.024 (5)	0.006 (4)	−0.002 (4)	−0.006 (4)
C6	0.030 (5)	0.026 (5)	0.028 (5)	−0.004 (4)	−0.002 (4)	−0.002 (4)
C11	0.043 (7)	0.041 (7)	0.030 (5)	0.021 (5)	−0.008 (5)	0.002 (5)
C10	0.040 (6)	0.024 (5)	0.046 (6)	−0.002 (5)	0.017 (5)	0.000 (5)
Pb1	0.0239 (2)	0.01722 (19)	0.01980 (18)	−0.00033 (14)	0.00406 (14)	−0.00065 (15)
I2	0.0219 (3)	0.0247 (3)	0.0264 (3)	−0.0045 (3)	0.0042 (2)	−0.0008 (3)
I3	0.0373 (4)	0.0139 (3)	0.0247 (3)	−0.0012 (3)	0.0076 (3)	−0.0009 (3)
I1	0.0238 (3)	0.0216 (3)	0.0252 (3)	0.0016 (3)	0.0039 (2)	0.0014 (3)

Geometric parameters (Å, º)

O1—C8	1.254 (10)	C12—C12^i	1.543 (17)
N1—C6	1.313 (12)	Pb1—I3	3.1895 (7)
N1—C4	1.332 (13)	Pb1—I2^ii	3.2012 (6)
N2—C8	1.329 (12)	Pb1—I1^ii	3.2302 (7)
N2—C11	1.469 (11)	Pb1—I2	3.2457 (7)
N2—C10	1.472 (12)	Pb1—I1	3.2874 (6)
C2—C3	1.370 (13)	Pb1—I3^iii	3.3285 (7)
C2—C1	1.395 (12)	I2—Pb1^iii	3.2012 (6)
C2—C12	1.514 (11)	I3—Pb1^ii	3.3285 (7)
C1—C6	1.370 (12)	I1—Pb1^iii	3.2303 (7)
C3—C4	1.387 (12)
C6—N1—C4	122.5 (8)	I3—Pb1—I2	102.207 (18)
C8—N2—C11	120.3 (9)	I2^ii—Pb1—I2	86.760 (18)
C8—N2—C10	122.4 (8)	I1^ii—Pb1—I2	164.89 (2)
C11—N2—C10	117.2 (8)	I3—Pb1—I1	86.769 (17)
O1—C8—N2	122.7 (9)	I2^ii—Pb1—I1	163.93 (2)
C3—C2—C1	118.0 (8)	I1^ii—Pb1—I1	106.82 (2)
C3—C2—C12	121.1 (8)	I2—Pb1—I1	83.630 (17)
C1—C2—C12	120.8 (9)	I3—Pb1—I3^iii	172.36 (2)
C6—C1—C2	119.8 (9)	I2^ii—Pb1—I3^iii	104.816 (18)
C2—C3—C4	120.0 (9)	I1^ii—Pb1—I3^iii	89.758 (17)
N1—C4—C3	119.4 (9)	I2—Pb1—I3^iii	79.904 (17)
C2—C12—C12^i	110.8 (10)	I1—Pb1—I3^iii	86.170 (16)
N1—C6—C1	120.3 (9)	Pb1^iii—I2—Pb1	78.709 (15)
I3—Pb1—I2^ii	82.699 (17)	Pb1—I3—Pb1^ii	77.658 (13)
I3—Pb1—I1^ii	89.489 (18)	Pb1^iii—I1—Pb1	77.690 (14)
I2^ii—Pb1—I1^ii	85.261 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.84	2.631 (9)	151
C4—H4···I2^iv	0.93	3.04	3.957 (11)	169
C6—H6···I1^v	0.93	3.25	3.938 (10)	133
C11—H11C···I3	0.96	3.09	3.997 (12)	158
C10—H10C···I2^iv	0.96	3.33	4.122 (11)	141

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

(shelx5)

Crystal data

C10H18I3NO2PbS2	Z = 4
Mr = 836.26	F(000) = 1496
Monoclinic, P21/c	Dx = 2.685 Mg m^−3
a = 15.0068 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 16.9568 (15) Å	µ = 12.83 mm^−1
c = 8.1667 (5) Å	T = 150 K
β = 95.491 (9)°	Needle, yellow
V = 2068.6 (3) Å^3	0.4 × 0.1 × 0.05 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	Rint = 0.082
Absorption correction: multi-scan	θmax = 29.2°, θmin = 3.6°
Tmin = 0.623, Tmax = 1.000	h = −20→10
7724 measured reflections	k = −22→22
4632 independent reflections	l = −10→10
2814 reflections with I > 2σ(I)

Refinement

Refinement on F^2	15 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.089	H-atom parameters constrained
wR(F^2) = 0.197	w = 1/[σ^2(Fo^2) + (0.0447P)^2 + 4.461P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
4632 reflections	Δρmax = 2.87 e Å^−3
97 parameters	Δρmin = −2.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
O1	0.7258 (10)	0.3622 (9)	0.8140 (17)	0.030 (4)*
N1	0.6517 (11)	0.4260 (9)	0.058 (2)	0.026 (4)*
H4	0.6788	0.4124	−0.0260	0.032*
C1	0.5687 (12)	0.3939 (10)	0.070 (2)	0.014 (4)*
H1	0.5443	0.3575	−0.0071	0.017*
C5	0.6946 (17)	0.4764 (13)	0.164 (3)	0.047 (7)*
H5	0.7518	0.4950	0.1510	0.056*
C3	0.5644 (14)	0.4699 (11)	0.313 (2)	0.052 (8)*
C9	0.7042 (18)	0.2999 (16)	0.520 (3)	0.053 (8)*
H9A	0.6439	0.2824	0.5277	0.080*
H9B	0.7453	0.2596	0.5611	0.080*
H9C	0.7125	0.3104	0.4066	0.080*
C8	0.8383 (15)	0.4014 (14)	0.593 (3)	0.034 (6)*
H8A	0.8611	0.4482	0.6480	0.051*
H8B	0.8407	0.4073	0.4763	0.051*
H8C	0.8739	0.3569	0.6311	0.051*
C6	0.6483 (14)	0.4991 (14)	0.295 (3)	0.045 (7)*
H6	0.6743	0.5347	0.3714	0.054*
C2	0.5222 (19)	0.4173 (13)	0.201 (2)	0.059 (8)*
H2	0.4650	0.3985	0.2125	0.071*
O2	0.8423 (12)	0.3471 (11)	0.206 (2)	0.052 (5)*
C11	0.9507 (19)	0.3072 (18)	−0.011 (3)	0.061 (8)*
H11A	0.9069	0.2826	−0.0877	0.091*
H11B	0.9730	0.2693	0.0705	0.091*
H11C	0.9993	0.3264	−0.0679	0.091*
C10	0.994 (2)	0.418 (2)	0.220 (4)	0.092 (12)*
H10A	0.9789	0.4621	0.2849	0.137*
H10B	1.0418	0.4319	0.1556	0.137*
H10C	1.0131	0.3747	0.2920	0.137*
C7	0.5347 (13)	0.5027 (18)	0.454 (3)	0.077 (10)*
H7	0.5754	0.5402	0.4976	0.093*
Pb1	0.72734 (6)	0.74838 (5)	0.07495 (9)	0.0236 (2)
I2	0.74534 (10)	0.89757 (9)	0.31111 (16)	0.0280 (4)
I3	0.56824 (10)	0.70361 (9)	0.29857 (16)	0.0265 (4)
I4	0.85751 (10)	0.65370 (9)	0.34374 (17)	0.0299 (4)
S5	0.7241 (4)	0.3861 (4)	0.6353 (7)	0.0320 (14)*
S6	0.8996 (5)	0.3886 (4)	0.0890 (9)	0.0456 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.0346 (5)	0.0224 (5)	0.0141 (4)	0.0012 (4)	0.0038 (3)	−0.0003 (4)
I2	0.0446 (10)	0.0205 (8)	0.0197 (7)	−0.0018 (7)	0.0069 (7)	−0.0007 (6)
I3	0.0336 (9)	0.0298 (9)	0.0158 (6)	−0.0041 (7)	0.0003 (6)	−0.0015 (6)
I4	0.0339 (9)	0.0345 (9)	0.0218 (7)	0.0035 (7)	0.0049 (6)	0.0006 (7)

Geometric parameters (Å, º)

O1—S5	1.512 (15)	C10—S6	1.76 (3)
N1—C5	1.34 (3)	C7—C7^i	1.349 (10)
N1—C1	1.37 (2)	Pb1—I2	3.1768 (16)
C1—C2	1.388 (16)	Pb1—I4	3.2236 (17)
C5—C6	1.381 (17)	Pb1—I3^ii	3.2289 (16)
C3—C6	1.373 (16)	Pb1—I3	3.2320 (17)
C3—C7	1.387 (16)	Pb1—I4^ii	3.2930 (17)
C3—C2	1.388 (16)	Pb1—I2^ii	3.3094 (16)
C9—S5	1.75 (3)	I2—Pb1^iii	3.3093 (16)
C8—S5	1.80 (2)	I3—Pb1^iii	3.2289 (16)
O2—S6	1.520 (19)	I4—Pb1^iii	3.2930 (17)
C11—S6	1.81 (3)
C5—N1—C1	126 (2)	I3^ii—Pb1—I4^ii	84.93 (4)
N1—C1—C2	117.9 (19)	I3—Pb1—I4^ii	162.41 (5)
N1—C5—C6	116 (2)	I2—Pb1—I2^ii	169.50 (6)
C6—C3—C7	108.5 (18)	I4—Pb1—I2^ii	89.37 (4)
C6—C3—C2	122 (2)	I3^ii—Pb1—I2^ii	80.47 (4)
C7—C3—C2	130 (2)	I3—Pb1—I2^ii	107.64 (4)
C3—C6—C5	121 (2)	I4^ii—Pb1—I2^ii	85.06 (4)
C1—C2—C3	117 (2)	Pb1—I2—Pb1^iii	78.01 (3)
C7^i—C7—C3	140 (4)	Pb1^iii—I3—Pb1	78.40 (4)
I2—Pb1—I4	88.42 (4)	Pb1—I4—Pb1^iii	77.60 (4)
I2—Pb1—I3^ii	103.76 (5)	O1—S5—C9	106.5 (11)
I4—Pb1—I3^ii	163.93 (5)	O1—S5—C8	107.3 (10)
I2—Pb1—I3	82.44 (4)	C9—S5—C8	97.6 (12)
I4—Pb1—I3	86.02 (4)	O2—S6—C10	102.4 (14)
I3^ii—Pb1—I3	85.26 (4)	O2—S6—C11	102.7 (13)
I2—Pb1—I4^ii	85.75 (4)	C10—S6—C11	97.8 (16)
I4—Pb1—I4^ii	106.71 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H4···O1^iv	0.86	1.76	2.61 (2)	167
N1—H4···S5^iv	0.86	2.95	3.777 (19)	163
C1—H1···I3^v	0.93	2.97	3.850 (19)	158
C5—H5···S6	0.93	2.94	3.52 (2)	122
C9—H9B···O2^vi	0.96	2.54	3.50 (3)	172
C8—H8B···O2	0.96	2.43	3.29 (3)	149
C2—H2···I2^vii	0.93	3.14	4.02 (3)	158
C11—H11B···I4^viii	0.96	3.24	4.02 (3)	140
C11—H11C···I4^ix	0.96	3.28	4.20 (3)	161
C10—H10B···I2^viii	0.96	3.23	3.96 (4)	134

Symmetry codes: (iv) x, y, z−1; (v) −x+1, −y+1, −z; (vi) x, −y+1/2, z+1/2; (vii) −x+1, y−1/2, −z+1/2; (viii) −x+2, y−1/2, −z+1/2; (ix) −x+2, −y+1, −z.

(shelx6)

Crystal data

C3H5I3N2Pb	F(000) = 1668
Mr = 656.98	Dx = 3.894 Mg m^−3
Hexagonal, P63/m	Mo Kα radiation, λ = 0.71073 Å
a = 15.5643 (6) Å	µ = 23.26 mm^−1
c = 8.0123 (5) Å	T = 150 K
V = 1680.92 (17) Å^3	Needle, yellow
Z = 6	0.3 × 0.1 × 0.05 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	Rint = 0.034
Absorption correction: multi-scan	θmax = 28.7°, θmin = 3.7°
Tmin = 0.246, Tmax = 1.000	h = −3→17
3203 measured reflections	k = −13→16
1277 independent reflections	l = −9→6
977 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.096	H-atom parameters constrained
wR(F^2) = 0.225	w = 1/[σ^2(Fo^2) + (0.0564P)^2 + 177.1023P] where P = (Fo^2 + 2Fc^2)/3
S = 1.12	(Δ/σ)max < 0.001
1277 reflections	Δρmax = 5.09 e Å^−3
35 parameters	Δρmin = −10.07 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
C3	0.399 (4)	0.354 (4)	0.7500	0.069 (13)*
H3	0.4650	0.3691	0.7500	0.083*
N1	0.334 (3)	0.339 (3)	0.611 (8)	0.123 (16)*
H1	0.3457	0.3378	0.5069	0.148*
C1	0.262 (3)	0.330 (3)	0.670 (5)	0.086 (12)*
H1A	0.2086	0.3234	0.6071	0.103*
Pb1	0.0000	0.0000	0.5000	0.0370 (6)
Pb2	0.3333	0.6667	0.5034 (2)	0.0355 (5)
I3	0.1587 (2)	0.5134 (3)	0.7500	0.0687 (10)
I4	0.4986 (2)	0.1806 (2)	0.7500	0.0544 (8)
I5	−0.02512 (19)	0.14913 (18)	0.7500	0.0391 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pb1	0.0446 (9)	0.0446 (9)	0.0217 (13)	0.0223 (4)	0.000	0.000
Pb2	0.0432 (6)	0.0432 (6)	0.0203 (10)	0.0216 (3)	0.000	0.000
I3	0.0480 (17)	0.079 (2)	0.0389 (19)	0.0021 (15)	0.000	0.000
I4	0.0514 (16)	0.0445 (15)	0.0384 (17)	0.0023 (12)	0.000	0.000
I5	0.0516 (13)	0.0430 (13)	0.0303 (14)	0.0294 (12)	0.000	0.000

Geometric parameters (Å, º)

C3—N1	1.45 (6)	Pb2—I4^vii	3.225 (2)
C3—N1^i	1.45 (6)	Pb2—I4^viii	3.225 (2)
N1—C1	1.16 (5)	Pb2—I4^ii	3.225 (2)
C1—C1^i	1.28 (8)	Pb2—I3^ix	3.240 (3)
Pb1—I5^ii	3.2342 (18)	Pb2—I3^x	3.240 (3)
Pb1—I5^iii	3.2342 (18)	Pb2—I3	3.240 (3)
Pb1—I5^iv	3.2342 (18)	I3—Pb2^i	3.240 (3)
Pb1—I5^v	3.2342 (18)	I4—Pb2^xi	3.225 (2)
Pb1—I5^vi	3.2342 (18)	I4—Pb2^viii	3.225 (2)
Pb1—I5	3.2342 (18)	I5—Pb1^xii	3.2342 (18)
N1—C3—N1^i	100 (5)	I4^vii—Pb2—I4^viii	84.57 (5)
C1—N1—C3	105 (6)	I4^vii—Pb2—I4^ii	84.57 (5)
N1—C1—C1^i	114 (4)	I4^viii—Pb2—I4^ii	84.57 (5)
I5^ii—Pb1—I5^iii	180.0	I4^vii—Pb2—I3^ix	95.28 (7)
I5^ii—Pb1—I5^iv	85.68 (4)	I4^viii—Pb2—I3^ix	93.46 (7)
I5^iii—Pb1—I5^iv	94.32 (4)	I4^ii—Pb2—I3^ix	178.04 (8)
I5^ii—Pb1—I5^v	94.32 (4)	I4^vii—Pb2—I3^x	178.04 (8)
I5^iii—Pb1—I5^v	85.68 (4)	I4^viii—Pb2—I3^x	95.28 (8)
I5^iv—Pb1—I5^v	94.32 (4)	I4^ii—Pb2—I3^x	93.46 (7)
I5^ii—Pb1—I5^vi	85.68 (4)	I3^ix—Pb2—I3^x	86.68 (6)
I5^iii—Pb1—I5^vi	94.32 (4)	I4^vii—Pb2—I3	93.46 (7)
I5^iv—Pb1—I5^vi	85.68 (4)	I4^viii—Pb2—I3	178.04 (8)
I5^v—Pb1—I5^vi	180.0	I4^ii—Pb2—I3	95.28 (8)
I5^ii—Pb1—I5	94.32 (4)	I3^ix—Pb2—I3	86.68 (6)
I5^iii—Pb1—I5	85.68 (4)	I3^x—Pb2—I3	86.68 (6)
I5^iv—Pb1—I5	180.00 (9)	Pb2^i—I3—Pb2	75.16 (8)
I5^v—Pb1—I5	85.68 (4)	Pb2^xi—I4—Pb2^viii	78.04 (7)
I5^vi—Pb1—I5	94.32 (4)	Pb1—I5—Pb1^xii	76.54 (5)

Symmetry codes: (i) x, y, −z+3/2; (ii) x−y, x, −z+1; (iii) −x+y, −x, z; (iv) −x, −y, −z+1; (v) −y, x−y, z; (vi) y, −x+y, −z+1; (vii) y, −x+y+1, −z+1; (viii) −x+1, −y+1, −z+1; (ix) −x+y, −x+1, z; (x) −y+1, x−y+1, z; (xi) −x+1, −y+1, z+1/2; (xii) −x, −y, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···I4	0.93	3.23	3.73 (5)	116
C3—H3···I4^xiii	0.93	2.95	3.81 (5)	155
N1—H1···I3^vi	0.86	3.23	3.95 (6)	143

Symmetry codes: (vi) y, −x+y, −z+1; (xiii) −x+y+1, −x+1, z.

(shelx7)

Crystal data

C3.20H9.60I2.40N1.60Pb0.40	Z = 5
Mr = 457.96	F(000) = 1000
Monoclinic, P2/n	Dx = 3.381 Mg m^−3
a = 9.8058 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2603 (3) Å	µ = 15.73 mm^−1
c = 12.4081 (4) Å	T = 150 K
β = 93.553 (3)°	Columnar, yellow
V = 1124.55 (6) Å^3	0.4 × 0.3 × 0.1 mm

Data collection

SuperNova, Dual, Cu at zero, EosS2 diffractometer	Rint = 0.030
Absorption correction: multi-scan	θmax = 29.4°, θmin = 3.4°
Tmin = 0.923, Tmax = 1.000	h = −13→11
5870 measured reflections	k = −12→11
2624 independent reflections	l = −9→16
2339 reflections with I > 2σ(I)

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.049	w = 1/[σ^2(Fo^2) + (0.0115P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2624 reflections	Δρmax = 1.30 e Å^−3
87 parameters	Δρmin = −1.14 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq
N1	0.1190 (4)	0.6981 (5)	0.5305 (3)	0.0154 (10)
H5A	0.0977	0.6358	0.4775	0.018*
H5B	0.0512	0.6983	0.5749	0.018*
N2	0.3802 (4)	0.8006 (5)	0.4713 (4)	0.0166 (10)
H6A	0.4010	0.8627	0.5245	0.020*
H6B	0.4485	0.8007	0.4273	0.020*
C4	0.2530 (5)	0.8483 (6)	0.4108 (4)	0.0168 (12)
H4A	0.2335	0.7850	0.3495	0.020*
H4B	0.2650	0.9455	0.3837	0.020*
C2	0.2484 (5)	0.6501 (6)	0.5911 (4)	0.0164 (12)
H2A	0.2368	0.5531	0.6186	0.020*
H2B	0.2686	0.7138	0.6521	0.020*
C3	0.3651 (5)	0.6526 (6)	0.5174 (4)	0.0176 (12)
H3A	0.4491	0.6251	0.5576	0.021*
H3B	0.3480	0.5836	0.4594	0.021*
C1	0.1339 (5)	0.8456 (6)	0.4839 (5)	0.0194 (13)
H1A	0.1497	0.9152	0.5418	0.023*
H1B	0.0503	0.8722	0.4428	0.023*
Pb1	0.7500	0.71697 (3)	0.7500	0.01381 (8)
I2	0.48855 (3)	0.93880 (4)	0.73233 (3)	0.01518 (9)
I3	0.96757 (3)	0.45989 (4)	0.72953 (3)	0.01486 (9)
I4	0.74774 (3)	0.74899 (4)	0.49315 (3)	0.01744 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.011 (2)	0.023 (2)	0.013 (2)	−0.0023 (18)	0.0045 (17)	0.000 (2)
N2	0.012 (2)	0.021 (2)	0.017 (3)	−0.0056 (18)	0.0026 (18)	0.000 (2)
C4	0.015 (3)	0.020 (3)	0.015 (3)	−0.002 (2)	0.001 (2)	0.007 (3)
C2	0.017 (3)	0.021 (3)	0.012 (3)	−0.001 (2)	0.003 (2)	0.001 (2)
C3	0.017 (3)	0.020 (3)	0.017 (3)	0.005 (2)	0.008 (2)	0.007 (3)
C1	0.021 (3)	0.019 (3)	0.019 (3)	0.008 (2)	0.008 (2)	0.012 (3)
Pb1	0.01360 (14)	0.01519 (15)	0.01279 (15)	0.000	0.00200 (11)	0.000
I2	0.01478 (17)	0.01655 (18)	0.01430 (19)	−0.00069 (13)	0.00175 (13)	−0.00139 (15)
I3	0.01445 (17)	0.01582 (18)	0.01446 (19)	−0.00040 (13)	0.00217 (13)	−0.00147 (15)
I4	0.01396 (18)	0.0244 (2)	0.01408 (19)	−0.00220 (13)	0.00178 (13)	−0.00160 (16)

Geometric parameters (Å, º)

N1—C1	1.494 (6)	Pb1—I4^i	3.1995 (4)
N1—C2	1.501 (6)	Pb1—I4	3.1995 (4)
N2—C4	1.482 (6)	Pb1—I3^i	3.2172 (4)
N2—C3	1.496 (6)	Pb1—I3	3.2172 (4)
C4—C1	1.523 (7)	Pb1—I2	3.2819 (4)
C2—C3	1.509 (7)	Pb1—I2^i	3.2819 (4)
C1—N1—C2	111.4 (4)	I3^i—Pb1—I3	84.542 (14)
C4—N2—C3	111.5 (4)	I4^i—Pb1—I2	88.034 (9)
N2—C4—C1	110.2 (4)	I4—Pb1—I2	85.314 (9)
N1—C2—C3	109.9 (4)	I3^i—Pb1—I2	87.096 (8)
N2—C3—C2	110.0 (4)	I3—Pb1—I2	167.680 (10)
N1—C1—C4	110.0 (4)	I4^i—Pb1—I2^i	85.313 (9)
I4^i—Pb1—I4	169.365 (16)	I4—Pb1—I2^i	88.034 (10)
I4^i—Pb1—I3^i	87.343 (9)	I3^i—Pb1—I2^i	167.680 (10)
I4—Pb1—I3^i	100.574 (10)	I3—Pb1—I2^i	87.096 (8)
I4^i—Pb1—I3	100.575 (10)	I2—Pb1—I2^i	102.502 (14)
I4—Pb1—I3	87.343 (9)

Symmetry code: (i) −x+3/2, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H5A···I3^ii	0.89	2.75	3.596 (4)	158
N1—H5B···I2^iii	0.89	3.31	3.890 (4)	125
N1—H5B···I3^iv	0.89	3.07	3.691 (4)	129
N1—H5B···I4^iv	0.89	3.12	3.672 (4)	122
N2—H6A···I2	0.89	2.76	3.582 (4)	155
N2—H6B···I2^v	0.89	3.21	3.777 (4)	124
N2—H6B···I4	0.89	3.03	3.629 (4)	126
C4—H4A···I3^ii	0.97	3.12	3.923 (5)	141
C4—H4B···I2^v	0.97	3.08	3.744 (5)	127
C4—H4B···I4^v	0.97	3.22	3.915 (5)	130
C2—H2A···I3^iv	0.97	3.17	3.771 (5)	122
C2—H2A···I4^ii	0.97	3.13	3.842 (5)	132
C2—H2B···I2	0.97	3.12	3.906 (5)	139
C3—H3A···I3^i	0.97	3.12	3.885 (5)	137
C3—H3A···I4	0.97	3.29	3.886 (5)	122
C3—H3B···I3^vi	0.97	3.18	3.912 (6)	134
C3—H3B···I4^ii	0.97	3.28	3.880 (5)	122
C1—H1A···I2^iii	0.97	3.20	3.886 (6)	130
C1—H1A···I4^v	0.97	3.31	3.935 (5)	124
C1—H1B···I2^vii	0.97	3.17	3.900 (5)	133
C1—H1B···I4^iv	0.97	3.27	3.899 (5)	124

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