The structure-directing amine changes everything: structures and optical properties of two-dimensional thio­stannates

Two different two-dimensional thio­stannates (SnS) were synthesized using tris­(2-amino­ethyl)amine (tren) or 1-(2-amino­ethyl)piperidine (1AEP) as structure-directing agents. Both structures consist of negatively charged thio­stannate layers with charge stabilizing cations sandwiched in-between. The fundamental building units are Sn₃S₄ broken-cube clusters connected by double sulfur bridges to form polymeric (Sn₃S₇²⁻)_n honeycomb hexagonal layers. The compounds are members of the R-SnS-1 family of structures, where R indicates the type of cation. Despite consisting of identical structural units, the band gaps of the two semiconducting compounds were found to differ substantially at 2.96 eV (violet–blue light) and 3.21 eV (UV light) for tren–SnS-1 and 1AEP–SnS-1, respectively. Aiming to explain the observed differences in optical properties, the structures of the two thio­stannates were investigated in detail based on combined X-ray diffraction, solid-state ¹³C and ¹¹⁹Sn MAS NMR spectroscopy and scanning electron microscopy studies. The compound tren–SnS-1 has a hexagonal structure consisting of planar SnS layers with regular hexagonal pores and disordered cations, whereas 1AEP–SnS-1 has an orthorhombic unit cell with ordered cations, distorted hexagonal pores and non-planar SnS layers. In the formation of 1AEP–SnS-1, an intramolecular reaction of the structure-directing piperidine takes place to form an N-heterobicyclic cation through in situ C—H activation. Hirshfeld surface analysis was used to investigate the interaction between the SnS layers and cations in 1AEP–SnS-1 and revealed that the most nucleophilic part of the SnS sheets is one of the two crystallographically distinct double sulfur bridges.

Computing details

For all structures, data collection: APEX2 v2010.1-2 (Bruker AXS, 2005-2009); cell refinement: APEX2 v2010.1-2 (Bruker AXS, 2005-2009); data reduction: APEX2 v2010.1-2 (Bruker AXS, 2005-2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2014) for SnS_TAEA_300K, SnS_1AEP_300K; SHELXL2012 (Sheldrick, 2012) for SnS_1AEP_100K. For all structures, molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: ShelXle (Huebschle, 2011).

(SnS_TAEA_300K)

Crystal data

S28Sn12	Dx = 1.319 Mg m^−3
Mr = 2322.20	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P63/mmc	Cell parameters from 1297 reflections
a = 13.2748 (4) Å	θ = 2.8–26.6°
c = 19.1521 (7) Å	µ = 3.02 mm^−1
V = 2922.8 (2) Å^3	T = 298 K
Z = 1	Plate, pale green
F(000) = 1048	0.14 × 0.12 × 0.02 mm

Data collection

APEX2 charged-coupled device diffractometer	1297 independent reflections
Radiation source: fine-focus sealed tube	959 reflections with I > 4σ(I)
Detector resolution: 12.00 pixels mm^-1	Rint = 0.048
Narrow slices collected using φ– and ω–scans	θmax = 27.4°, θmin = 1.8°
Absorption correction: multi-scan SADABS (Sheldrick, 2004)	h = −16→17
Tmin = 0.657, Tmax = 0.769	k = −17→17
20714 measured reflections	l = −22→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F^2 > 2σ(F^2)] = 0.058	Secondary atom site location: difference Fourier map
wR(F^2) = 0.227	w = 1/[σ^2(Fo^2) + (0.1418P)^2 + 5.8926P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max < 0.001
1297 reflections	Δρmax = 1.54 e Å^−3
22 parameters	Δρmin = −1.16 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
Sn1	0.84744 (6)	0.42372 (3)	0.49152 (5)	0.0495 (4)
S1	0.6667	0.3333	0.5743 (3)	0.0445 (10)
S2	0.76919 (14)	0.23081 (14)	0.4409 (2)	0.0644 (10)
S3	0.9780 (3)	0.48899 (13)	0.58937 (18)	0.0653 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sn1	0.0313 (5)	0.0423 (5)	0.0711 (7)	0.0157 (2)	−0.0001 (3)	−0.00005 (15)
S1	0.0352 (13)	0.0352 (13)	0.063 (3)	0.0176 (6)	0.000	0.000
S2	0.0506 (12)	0.0506 (12)	0.090 (3)	0.0240 (13)	0.0128 (8)	−0.0128 (8)
S3	0.0348 (14)	0.0796 (18)	0.0665 (19)	0.0174 (7)	0.0017 (13)	0.0008 (6)

Geometric parameters (Å, º)

Sn1—S3	2.401 (3)	S1—Sn1^iii	2.614 (3)
Sn1—S2^i	2.433 (2)	S1—Sn1^i	2.614 (3)
Sn1—S2	2.433 (2)	S2—Sn1^iii	2.433 (2)
Sn1—S3^ii	2.535 (3)	S3—Sn1^ii	2.535 (3)
Sn1—S1	2.614 (3)
S3—Sn1—S2^i	122.85 (10)	S2—Sn1—S1	87.02 (8)
S3—Sn1—S2	122.85 (10)	S3^ii—Sn1—S1	179.68 (12)
S2^i—Sn1—S2	114.11 (19)	Sn1^iii—S1—Sn1^i	87.02 (13)
S3—Sn1—S3^ii	88.98 (11)	Sn1^iii—S1—Sn1	87.02 (13)
S2^i—Sn1—S3^ii	92.81 (8)	Sn1^i—S1—Sn1	87.02 (13)
S2—Sn1—S3^ii	92.81 (8)	Sn1—S2—Sn1^iii	95.44 (11)
S3—Sn1—S1	91.34 (12)	Sn1—S3—Sn1^ii	91.02 (11)
S2^i—Sn1—S1	87.02 (8)

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

(SnS_1AEP_300K)

Crystal data

S7Sn3·2(C7H13N2)	Dx = 2.064 Mg m^−3
Mr = 830.94	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P21212	Cell parameters from 9207 reflections
a = 13.2299 (2) Å	θ = 2.2–26.5°
b = 22.2673 (3) Å	µ = 3.34 mm^−1
c = 9.0772 (2) Å	T = 298 K
V = 2674.09 (8) Å^3	Plate, pale yellow
Z = 4	0.14 × 0.05 × 0.01 mm
F(000) = 1600

Data collection

Bruker X8 APEX-II diffractometer	9206 independent reflections
Radiation source: fine-focus sealed tube	6297 reflections with I > 4σ(I)
Detector resolution: 12.00 pixels mm^-1	Rint = 0.059
Narrow slices collected using φ– and ω–scans	θmax = 32.4°, θmin = 1.8°
Absorption correction: multi-scan SADABS (Sheldrick, 2004)	h = −19→19
Tmin = 0.709, Tmax = 0.833	k = −28→33
34528 measured reflections	l = −13→13

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)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0195P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max = 0.010
9206 reflections	Δρmax = 0.65 e Å^−3
264 parameters	Δρmin = −0.59 e Å^−3
281 restraints	Absolute structure: Flack x determined using 2184 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.015 (14)

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	Occ. (<1)
N1	0.4959 (6)	0.8051 (3)	0.0322 (8)	0.0722 (19)
C1	0.4851 (9)	0.7461 (4)	−0.0290 (12)	0.098 (3)
H1A	0.4771	0.7475	−0.1352	0.118*
H1B	0.4283	0.7249	0.0141	0.118*
N2	0.6324 (7)	0.7627 (4)	0.1101 (11)	0.115 (3)
H2	0.6884	0.7585	0.1571	0.138*
C2	0.5882 (10)	0.7171 (5)	0.0162 (13)	0.129 (4)
H2A	0.5780	0.6799	0.0695	0.155*
H2B	0.6302	0.7095	−0.0693	0.155*
C3	0.5775 (8)	0.8106 (4)	0.1147 (11)	0.078 (2)
C4A	0.5869 (15)	0.8658 (7)	0.213 (3)	0.095 (6)	0.652 (16)
H4A1	0.6087	0.8530	0.3097	0.114*	0.652 (16)
H4A2	0.6392	0.8916	0.1726	0.114*	0.652 (16)
C5A	0.4938 (14)	0.9010 (8)	0.228 (2)	0.109 (5)	0.652 (16)
H5A1	0.4520	0.8821	0.3028	0.130*	0.652 (16)
H5A2	0.5115	0.9407	0.2636	0.130*	0.652 (16)
C6A	0.4373 (13)	0.9072 (6)	0.102 (2)	0.093 (5)	0.652 (16)
H6A1	0.4711	0.9357	0.0380	0.111*	0.652 (16)
H6A2	0.3724	0.9243	0.1284	0.111*	0.652 (16)
C4B	0.619 (3)	0.8663 (12)	0.180 (6)	0.095 (6)	0.348 (16)
H4B1	0.6204	0.8630	0.2865	0.114*	0.348 (16)
H4B2	0.6879	0.8726	0.1457	0.114*	0.348 (16)
C5B	0.556 (3)	0.9165 (13)	0.136 (5)	0.109 (5)	0.348 (16)
H5B1	0.5299	0.9346	0.2256	0.130*	0.348 (16)
H5B2	0.5999	0.9461	0.0904	0.130*	0.348 (16)
C6B	0.476 (2)	0.9081 (11)	0.044 (4)	0.093 (5)	0.348 (16)
H6B1	0.4994	0.9216	−0.0516	0.111*	0.348 (16)
H6B2	0.4257	0.9368	0.0757	0.111*	0.348 (16)
C7	0.4184 (7)	0.8500 (4)	0.0145 (12)	0.094 (3)
H7A	0.3542	0.8331	0.0448	0.112*
H7B	0.4132	0.8602	−0.0891	0.112*
N3	0.7370 (5)	0.4937 (3)	0.2142 (7)	0.0534 (16)
N4	0.7017 (6)	0.3994 (3)	0.1989 (9)	0.081 (2)
H4	0.7067	0.3615	0.2156	0.097*
C8	0.6652 (6)	0.4906 (4)	0.0919 (10)	0.075 (3)
H8A	0.6961	0.5034	0.0003	0.090*
H8B	0.6059	0.5150	0.1110	0.090*
C9	0.6390 (7)	0.4249 (4)	0.0880 (11)	0.083 (3)
H9A	0.5681	0.4186	0.1103	0.100*
H9B	0.6538	0.4077	−0.0077	0.100*
C10	0.7511 (6)	0.4408 (3)	0.2727 (10)	0.057 (2)
C11	0.8169 (7)	0.4314 (3)	0.4005 (10)	0.073 (2)
H11A	0.8809	0.4148	0.3677	0.088*
H11B	0.7858	0.4024	0.4663	0.088*
C12	0.8358 (7)	0.4887 (4)	0.4826 (12)	0.098 (3)
H12A	0.8929	0.4834	0.5484	0.117*
H12B	0.7771	0.4984	0.5420	0.117*
C13	0.8574 (7)	0.5400 (3)	0.3782 (13)	0.084 (3)
H13A	0.8699	0.5763	0.4344	0.101*
H13B	0.9176	0.5311	0.3215	0.101*
C14	0.7699 (6)	0.5502 (3)	0.2751 (11)	0.066 (2)
H14A	0.7145	0.5689	0.3280	0.079*
H14B	0.7903	0.5769	0.1962	0.079*
Sn1	0.51901 (3)	0.57757 (2)	0.60991 (5)	0.02833 (10)
Sn2	0.68488 (3)	0.70336 (2)	0.54081 (5)	0.02972 (10)
Sn3	0.41812 (3)	0.72367 (2)	0.51938 (5)	0.02900 (10)
S1	0.54279 (10)	0.65305 (6)	0.38499 (19)	0.0290 (3)
S2	0.68038 (12)	0.61583 (6)	0.7006 (2)	0.0375 (4)
S3	0.56405 (11)	0.78330 (6)	0.5913 (2)	0.0399 (4)
S4	0.37631 (12)	0.63966 (7)	0.6815 (2)	0.0374 (4)
S5	0.5000	0.5000	0.4239 (3)	0.0399 (6)
S6	0.5000	0.5000	0.8029 (3)	0.0394 (6)
S7	0.79943 (11)	0.70743 (7)	0.33640 (19)	0.0357 (4)
S8	0.81953 (12)	0.75633 (6)	0.69730 (19)	0.0365 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.080 (4)	0.072 (4)	0.064 (5)	0.002 (3)	−0.016 (4)	0.005 (4)
C1	0.150 (8)	0.083 (5)	0.061 (6)	−0.002 (5)	0.001 (6)	−0.005 (5)
N2	0.124 (7)	0.127 (6)	0.094 (7)	0.041 (5)	−0.014 (6)	0.009 (5)
C2	0.206 (11)	0.113 (7)	0.069 (8)	0.052 (7)	−0.001 (8)	0.001 (6)
C3	0.082 (6)	0.086 (5)	0.066 (6)	0.015 (4)	−0.023 (5)	0.015 (4)
C4A	0.075 (11)	0.103 (6)	0.105 (12)	0.000 (6)	−0.026 (10)	−0.015 (6)
C5A	0.092 (10)	0.099 (8)	0.135 (12)	0.001 (6)	−0.022 (8)	−0.015 (7)
C6A	0.077 (10)	0.077 (5)	0.124 (13)	0.005 (6)	−0.003 (9)	−0.008 (6)
C4B	0.075 (11)	0.103 (6)	0.105 (12)	0.000 (6)	−0.026 (10)	−0.015 (6)
C5B	0.092 (10)	0.099 (8)	0.135 (12)	0.001 (6)	−0.022 (8)	−0.015 (7)
C6B	0.077 (10)	0.077 (5)	0.124 (13)	0.005 (6)	−0.003 (9)	−0.008 (6)
C7	0.086 (6)	0.077 (5)	0.118 (9)	0.008 (4)	−0.039 (6)	0.002 (5)
N3	0.053 (4)	0.043 (3)	0.064 (4)	−0.001 (3)	0.002 (3)	0.008 (3)
N4	0.099 (6)	0.044 (3)	0.099 (6)	−0.005 (4)	−0.016 (5)	0.003 (3)
C8	0.078 (6)	0.072 (5)	0.074 (6)	−0.006 (4)	−0.013 (5)	0.017 (4)
C9	0.101 (7)	0.075 (5)	0.073 (7)	−0.004 (5)	−0.008 (5)	0.001 (5)
C10	0.064 (5)	0.041 (4)	0.066 (5)	0.001 (3)	0.009 (4)	0.002 (3)
C11	0.077 (6)	0.055 (4)	0.087 (6)	0.005 (4)	−0.010 (5)	0.013 (4)
C12	0.108 (8)	0.072 (5)	0.113 (8)	0.006 (5)	−0.027 (6)	−0.001 (5)
C13	0.071 (5)	0.052 (4)	0.129 (8)	0.006 (4)	−0.027 (6)	−0.007 (5)
C14	0.056 (5)	0.041 (4)	0.101 (7)	−0.002 (3)	0.002 (4)	0.003 (4)
Sn1	0.02426 (19)	0.01737 (17)	0.0434 (3)	−0.00179 (15)	0.00070 (19)	−0.00065 (18)
Sn2	0.02006 (18)	0.02319 (18)	0.0459 (3)	−0.00340 (14)	0.00378 (19)	−0.00003 (18)
Sn3	0.01949 (17)	0.02222 (17)	0.0453 (3)	0.00194 (14)	−0.00037 (18)	0.00194 (18)
S1	0.0232 (7)	0.0240 (7)	0.0398 (9)	−0.0009 (5)	0.0021 (7)	−0.0014 (7)
S2	0.0291 (8)	0.0323 (8)	0.0512 (12)	−0.0060 (6)	−0.0091 (8)	0.0063 (7)
S3	0.0259 (8)	0.0248 (8)	0.0690 (12)	−0.0025 (6)	0.0021 (8)	−0.0079 (8)
S4	0.0296 (8)	0.0294 (8)	0.0532 (12)	0.0037 (6)	0.0121 (8)	0.0065 (7)
S5	0.0555 (16)	0.0252 (10)	0.0389 (16)	−0.0056 (9)	0.000	0.000
S6	0.0555 (16)	0.0240 (10)	0.0388 (15)	−0.0063 (10)	0.000	0.000
S7	0.0270 (8)	0.0359 (8)	0.0442 (11)	−0.0102 (6)	0.0054 (7)	−0.0080 (7)
S8	0.0317 (8)	0.0372 (8)	0.0405 (10)	−0.0109 (7)	−0.0005 (8)	−0.0007 (7)

Geometric parameters (Å, º)

N1—C3	1.319 (11)	N4—H4	0.8600
N1—C1	1.432 (10)	C8—C9	1.505 (10)
N1—C7	1.441 (10)	C8—H8A	0.9700
C1—C2	1.564 (14)	C8—H8B	0.9700
C1—H1A	0.9700	C9—H9A	0.9700
C1—H1B	0.9700	C9—H9B	0.9700
N2—C3	1.290 (11)	C10—C11	1.465 (12)
N2—C2	1.449 (13)	C11—C12	1.500 (11)
N2—H2	0.8600	C11—H11A	0.9700
C2—H2A	0.9700	C11—H11B	0.9700
C2—H2B	0.9700	C12—C13	1.511 (12)
C3—C4B	1.48 (2)	C12—H12A	0.9700
C3—C4A	1.522 (15)	C12—H12B	0.9700
C4A—C5A	1.467 (18)	C13—C14	1.506 (11)
C4A—H4A1	0.9700	C13—H13A	0.9700
C4A—H4A2	0.9700	C13—H13B	0.9700
C5A—C6A	1.375 (18)	C14—H14A	0.9700
C5A—H5A1	0.9700	C14—H14B	0.9700
C5A—H5A2	0.9700	Sn1—S5	2.4282 (17)
C6A—C7	1.521 (14)	Sn1—S4	2.4286 (15)
C6A—H6A1	0.9700	Sn1—S2	2.4417 (16)
C6A—H6A2	0.9700	Sn1—S6	2.4731 (18)
C4B—C5B	1.45 (2)	Sn1—S1	2.6631 (16)
C4B—H4B1	0.9700	Sn2—S7	2.3974 (16)
C4B—H4B2	0.9700	Sn2—S2	2.4303 (16)
C5B—C6B	1.36 (2)	Sn2—S3	2.4359 (14)
C5B—H5B1	0.9700	Sn2—S8	2.5655 (16)
C5B—H5B2	0.9700	Sn2—S1	2.6057 (15)
C6B—C7	1.53 (2)	Sn3—S8^i	2.4018 (17)
C6B—H6B1	0.9700	Sn3—S3	2.4325 (14)
C6B—H6B2	0.9700	Sn3—S4	2.4436 (16)
C7—H7A	0.9700	Sn3—S7^i	2.5561 (15)
C7—H7B	0.9700	Sn3—S1	2.5848 (14)
N3—C10	1.305 (9)	S5—Sn1^ii	2.4282 (17)
N3—C14	1.442 (9)	S6—Sn1^ii	2.4731 (18)
N3—C8	1.463 (9)	S7—Sn3^iii	2.5560 (15)
N4—C10	1.313 (10)	S8—Sn3^iii	2.4018 (17)
N4—C9	1.422 (11)
C3—N1—C1	112.8 (8)	C9—C8—H8B	111.3
C3—N1—C7	125.5 (8)	H8A—C8—H8B	109.2
C1—N1—C7	121.5 (8)	N4—C9—C8	103.6 (7)
N1—C1—C2	100.9 (8)	N4—C9—H9A	111.0
N1—C1—H1A	111.6	C8—C9—H9A	111.0
C2—C1—H1A	111.6	N4—C9—H9B	111.0
N1—C1—H1B	111.6	C8—C9—H9B	111.0
C2—C1—H1B	111.6	H9A—C9—H9B	109.0
H1A—C1—H1B	109.4	N3—C10—N4	110.8 (8)
C3—N2—C2	111.7 (10)	N3—C10—C11	122.4 (8)
C3—N2—H2	124.1	N4—C10—C11	126.8 (7)
C2—N2—H2	124.1	C10—C11—C12	111.8 (7)
N2—C2—C1	102.5 (8)	C10—C11—H11A	109.3
N2—C2—H2A	111.3	C12—C11—H11A	109.3
C1—C2—H2A	111.3	C10—C11—H11B	109.3
N2—C2—H2B	111.3	C12—C11—H11B	109.3
C1—C2—H2B	111.3	H11A—C11—H11B	107.9
H2A—C2—H2B	109.2	C11—C12—C13	111.3 (9)
N2—C3—N1	111.5 (9)	C11—C12—H12A	109.4
N2—C3—C4B	119.6 (15)	C13—C12—H12A	109.4
N1—C3—C4B	127.6 (14)	C11—C12—H12B	109.4
N2—C3—C4A	129.7 (11)	C13—C12—H12B	109.4
N1—C3—C4A	118.3 (10)	H12A—C12—H12B	108.0
C5A—C4A—C3	114.7 (13)	C14—C13—C12	111.0 (7)
C5A—C4A—H4A1	108.6	C14—C13—H13A	109.4
C3—C4A—H4A1	108.6	C12—C13—H13A	109.4
C5A—C4A—H4A2	108.6	C14—C13—H13B	109.4
C3—C4A—H4A2	108.6	C12—C13—H13B	109.4
H4A1—C4A—H4A2	107.6	H13A—C13—H13B	108.0
C6A—C5A—C4A	115.5 (17)	N3—C14—C13	109.8 (6)
C6A—C5A—H5A1	108.4	N3—C14—H14A	109.7
C4A—C5A—H5A1	108.4	C13—C14—H14A	109.7
C6A—C5A—H5A2	108.4	N3—C14—H14B	109.7
C4A—C5A—H5A2	108.4	C13—C14—H14B	109.7
H5A1—C5A—H5A2	107.5	H14A—C14—H14B	108.2
C5A—C6A—C7	116.1 (13)	S5—Sn1—S4	120.70 (5)
C5A—C6A—H6A1	108.3	S5—Sn1—S2	124.98 (5)
C7—C6A—H6A1	108.3	S4—Sn1—S2	113.00 (6)
C5A—C6A—H6A2	108.3	S5—Sn1—S6	89.15 (6)
C7—C6A—H6A2	108.3	S4—Sn1—S6	97.41 (5)
H6A1—C6A—H6A2	107.4	S2—Sn1—S6	95.38 (5)
C5B—C4B—C3	109 (2)	S5—Sn1—S1	85.88 (5)
C5B—C4B—H4B1	109.9	S4—Sn1—S1	86.43 (5)
C3—C4B—H4B1	109.9	S2—Sn1—S1	86.27 (5)
C5B—C4B—H4B2	109.9	S6—Sn1—S1	174.82 (5)
C3—C4B—H4B2	110.0	S7—Sn2—S2	120.51 (6)
H4B1—C4B—H4B2	108.3	S7—Sn2—S3	122.20 (6)
C6B—C5B—C4B	121 (3)	S2—Sn2—S3	117.24 (6)
C6B—C5B—H5B1	107.2	S7—Sn2—S8	88.41 (5)
C4B—C5B—H5B1	107.2	S2—Sn2—S8	93.16 (5)
C6B—C5B—H5B2	107.2	S3—Sn2—S8	90.89 (5)
C4B—C5B—H5B2	107.2	S7—Sn2—S1	92.99 (5)
H5B1—C5B—H5B2	106.8	S2—Sn2—S1	87.79 (5)
C5B—C6B—C7	128 (2)	S3—Sn2—S1	86.72 (5)
C5B—C6B—H6B1	105.3	S8—Sn2—S1	177.61 (5)
C7—C6B—H6B1	105.3	S8^i—Sn3—S3	123.34 (6)
C5B—C6B—H6B2	105.3	S8^i—Sn3—S4	120.81 (6)
C7—C6B—H6B2	105.3	S3—Sn3—S4	115.85 (6)
H6B1—C6B—H6B2	106.0	S8^i—Sn3—S7^i	88.54 (5)
N1—C7—C6A	114.0 (9)	S3—Sn3—S7^i	91.29 (5)
N1—C7—C6B	102.2 (13)	S4—Sn3—S7^i	90.69 (5)
N1—C7—H7A	108.8	S8^i—Sn3—S1	94.18 (5)
C6A—C7—H7A	108.8	S3—Sn3—S1	87.26 (5)
N1—C7—H7B	108.8	S4—Sn3—S1	87.88 (5)
C6A—C7—H7B	108.8	S7^i—Sn3—S1	177.28 (6)
H7A—C7—H7B	107.7	Sn3—S1—Sn2	86.71 (5)
C10—N3—C14	126.1 (7)	Sn3—S1—Sn1	86.95 (5)
C10—N3—C8	111.0 (7)	Sn2—S1—Sn1	86.59 (5)
C14—N3—C8	121.8 (6)	Sn2—S2—Sn1	95.74 (6)
C10—N4—C9	111.9 (7)	Sn3—S3—Sn2	94.10 (5)
C10—N4—H4	124.1	Sn1—S4—Sn3	95.66 (6)
C9—N4—H4	124.1	Sn1—S5—Sn1^ii	91.91 (8)
N3—C8—C9	102.3 (7)	Sn1^ii—S6—Sn1	89.78 (8)
N3—C8—H8A	111.3	Sn2—S7—Sn3^iii	90.84 (6)
C9—C8—H8A	111.3	Sn3^iii—S8—Sn2	90.51 (6)
N3—C8—H8B	111.3

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

(SnS_1AEP_100K)

Crystal data

S7Sn3·2(C7H13N2)	Dx = 2.111 Mg m^−3
Mr = 830.94	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P21212	Cell parameters from 3438 reflections
a = 13.1724 (5) Å	θ = 2.4–22.5°
b = 22.2035 (11) Å	µ = 3.41 mm^−1
c = 8.9383 (5) Å	T = 100 K
V = 2614.2 (2) Å^3	Plate, pale yellow
Z = 4	0.1 × 0.08 × 0.04 mm
F(000) = 1600

Data collection

Bruker X8 APEX-II diffractometer	3438 independent reflections
Radiation source: fine-focus sealed tube	3072 reflections with I > 4σ(I)
Detector resolution: 12.00 pixels mm^-1	Rint = 0.033
Narrow slices collected using φ– and ω–scans	θmax = 23.6°, θmin = 2.3°
Absorption correction: multi-scan SADABS (Sheldrick, 2004)	h = −14→12
Tmin = 0.668, Tmax = 0.742	k = −24→22
9968 measured reflections	l = −8→9

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)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.045	w = 1/[σ^2(Fo^2) + (0.0122P)^2 + 2.9445P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max = 0.001
3438 reflections	Δρmax = 0.69 e Å^−3
277 parameters	Δρmin = −0.57 e Å^−3
281 restraints	Absolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.49 (4)

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	Occ. (<1)
N1	0.5028 (6)	0.1934 (4)	0.9676 (10)	0.030 (2)
C1	0.5065 (8)	0.2547 (5)	1.0262 (14)	0.041 (3)
H1A	0.5606	0.2785	0.9770	0.049*
H1B	0.5180	0.2548	1.1356	0.049*
N2	0.3650 (7)	0.2328 (5)	0.8820 (12)	0.052 (3)
H2	0.3098	0.2363	0.8272	0.062*
C2	0.4016 (8)	0.2793 (5)	0.9877 (14)	0.049 (3)
H2A	0.3577	0.2820	1.0774	0.059*
H2B	0.4059	0.3194	0.9395	0.059*
C3	0.4243 (8)	0.1864 (5)	0.8805 (13)	0.033 (3)
C4A	0.4124 (13)	0.1309 (7)	0.790 (3)	0.042 (5)	0.797 (16)
H4A1	0.3866	0.1418	0.6894	0.050*	0.797 (16)
H4A2	0.3615	0.1044	0.8379	0.050*	0.797 (16)
C5A	0.5124 (11)	0.0961 (7)	0.7724 (18)	0.047 (4)	0.797 (16)
H5A1	0.4994	0.0558	0.7291	0.056*	0.797 (16)
H5A2	0.5591	0.1181	0.7051	0.056*	0.797 (16)
C6A	0.5588 (16)	0.0900 (8)	0.926 (3)	0.049 (5)	0.797 (16)
H6A1	0.5106	0.0691	0.9935	0.059*	0.797 (16)
H6A2	0.6214	0.0654	0.9201	0.059*	0.797 (16)
C4B	0.381 (6)	0.1317 (18)	0.813 (12)	0.06 (2)	0.203 (16)
H4A	0.3862	0.1336	0.7023	0.070*	0.203 (16)
H4B	0.3085	0.1276	0.8403	0.070*	0.203 (16)
C5B	0.442 (4)	0.079 (2)	0.874 (7)	0.047 (4)	0.203 (16)
H5B1	0.4121	0.0647	0.9687	0.056*	0.203 (16)
H5B2	0.4401	0.0450	0.8012	0.056*	0.203 (16)
C6B	0.551 (5)	0.097 (3)	0.900 (13)	0.051 (16)	0.203 (16)
H6A	0.5847	0.0617	0.9444	0.061*	0.203 (16)
H6B	0.5811	0.1026	0.7991	0.061*	0.203 (16)
C7	0.5836 (8)	0.1498 (4)	0.9891 (14)	0.037 (3)
H7A	0.5972	0.1455	1.0975	0.045*
H7B	0.6463	0.1650	0.9411	0.045*
N3	0.2653 (6)	0.5058 (4)	0.7886 (10)	0.022 (2)
N4	0.2991 (6)	0.6017 (4)	0.8023 (10)	0.029 (2)
H4	0.2933	0.6405	0.7836	0.035*
C8	0.3383 (7)	0.5093 (4)	0.9097 (12)	0.028 (3)
H8A	0.3989	0.4844	0.8883	0.033*
H8B	0.3078	0.4959	1.0053	0.033*
C9	0.3654 (8)	0.5757 (5)	0.9153 (13)	0.032 (3)
H9A	0.3514	0.5930	1.0153	0.038*
H9B	0.4377	0.5823	0.8901	0.038*
C10	0.2494 (7)	0.5594 (5)	0.7327 (13)	0.022 (2)
C11	0.1834 (8)	0.5691 (4)	0.5992 (12)	0.031 (3)
H11A	0.2158	0.5990	0.5322	0.037*
H11B	0.1174	0.5859	0.6321	0.037*
C12	0.1654 (8)	0.5119 (4)	0.5145 (13)	0.037 (3)
H12A	0.2262	0.5022	0.4540	0.044*
H12B	0.1075	0.5175	0.4452	0.044*
C13	0.1427 (7)	0.4598 (5)	0.6210 (15)	0.035 (3)
H13A	0.0812	0.4691	0.6802	0.042*
H13B	0.1294	0.4228	0.5624	0.042*
C14	0.2301 (7)	0.4493 (5)	0.7240 (13)	0.026 (3)
H14A	0.2092	0.4216	0.8051	0.031*
H14B	0.2864	0.4300	0.6682	0.031*
Sn1	0.48102 (5)	0.42253 (3)	0.39345 (8)	0.01265 (18)
Sn2	0.31383 (4)	0.29720 (3)	0.45948 (8)	0.01426 (18)
Sn3	0.58038 (4)	0.27612 (3)	0.48343 (8)	0.01373 (18)
S1	0.45610 (16)	0.34667 (11)	0.6189 (3)	0.0141 (6)
S2	0.31869 (19)	0.38528 (11)	0.3000 (3)	0.0177 (6)
S3	0.43403 (17)	0.21644 (11)	0.4097 (3)	0.0195 (6)
S4	0.62457 (17)	0.36000 (12)	0.3209 (3)	0.0173 (7)
S5	0.5000	0.5000	0.5830 (4)	0.0174 (9)
S6	0.5000	0.5000	0.1980 (4)	0.0184 (9)
S7	0.19764 (17)	0.29314 (11)	0.6649 (3)	0.0174 (6)
S8	0.17992 (18)	0.24462 (11)	0.2978 (3)	0.0183 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.034 (4)	0.026 (4)	0.030 (5)	0.001 (3)	−0.004 (4)	0.005 (4)
C1	0.059 (6)	0.034 (5)	0.031 (7)	−0.001 (5)	−0.001 (6)	−0.001 (5)
N2	0.052 (6)	0.052 (6)	0.051 (7)	0.019 (5)	−0.007 (5)	−0.002 (5)
C2	0.070 (7)	0.050 (6)	0.028 (7)	0.023 (5)	0.002 (6)	0.006 (5)
C3	0.037 (6)	0.035 (5)	0.028 (6)	0.010 (4)	−0.008 (5)	0.004 (4)
C4A	0.036 (9)	0.043 (7)	0.047 (10)	0.005 (6)	−0.017 (8)	−0.006 (7)
C5A	0.042 (8)	0.039 (7)	0.058 (9)	0.010 (6)	−0.020 (6)	−0.013 (6)
C6A	0.045 (9)	0.036 (8)	0.066 (11)	0.013 (6)	−0.024 (8)	−0.003 (6)
C4B	0.05 (2)	0.044 (9)	0.08 (4)	0.015 (9)	−0.03 (3)	−0.013 (10)
C5B	0.042 (8)	0.039 (7)	0.058 (9)	0.010 (6)	−0.020 (6)	−0.013 (6)
C6B	0.044 (12)	0.039 (14)	0.07 (4)	0.013 (9)	−0.024 (12)	−0.01 (2)
C7	0.038 (5)	0.036 (5)	0.038 (7)	0.005 (4)	−0.009 (5)	0.004 (5)
N3	0.021 (5)	0.012 (4)	0.033 (5)	0.002 (3)	−0.001 (4)	−0.004 (4)
N4	0.037 (5)	0.018 (4)	0.033 (6)	−0.002 (4)	−0.009 (4)	−0.002 (4)
C8	0.027 (6)	0.024 (5)	0.033 (6)	−0.002 (4)	−0.001 (5)	0.000 (5)
C9	0.037 (6)	0.026 (5)	0.032 (7)	−0.005 (5)	−0.007 (5)	0.003 (5)
C10	0.019 (5)	0.020 (5)	0.027 (6)	0.003 (4)	0.005 (4)	−0.005 (4)
C11	0.025 (6)	0.026 (5)	0.041 (6)	0.001 (5)	−0.007 (5)	−0.001 (5)
C12	0.038 (6)	0.025 (5)	0.047 (7)	0.001 (5)	−0.016 (6)	−0.003 (5)
C13	0.031 (6)	0.018 (6)	0.057 (8)	0.002 (5)	−0.016 (5)	−0.004 (5)
C14	0.022 (5)	0.018 (5)	0.039 (7)	−0.004 (4)	0.001 (5)	0.000 (5)
Sn1	0.0102 (3)	0.0082 (4)	0.0195 (4)	−0.0008 (3)	0.0004 (3)	0.0000 (3)
Sn2	0.0101 (3)	0.0108 (4)	0.0219 (4)	−0.0015 (3)	0.0016 (3)	−0.0003 (3)
Sn3	0.0094 (3)	0.0098 (4)	0.0219 (5)	0.0010 (3)	0.0002 (3)	0.0010 (3)
S1	0.0092 (13)	0.0123 (14)	0.0209 (15)	0.0005 (10)	0.0017 (12)	−0.0011 (13)
S2	0.0133 (14)	0.0151 (15)	0.0248 (18)	−0.0034 (12)	−0.0035 (13)	0.0027 (13)
S3	0.0123 (13)	0.0138 (16)	0.0323 (17)	0.0003 (11)	0.0028 (12)	−0.0031 (13)
S4	0.0122 (14)	0.0132 (16)	0.0265 (18)	0.0024 (12)	0.0052 (12)	0.0035 (13)
S5	0.022 (2)	0.011 (2)	0.019 (2)	−0.0032 (16)	0.000	0.000
S6	0.022 (2)	0.013 (2)	0.021 (2)	−0.0029 (17)	0.000	0.000
S7	0.0153 (13)	0.0140 (15)	0.0230 (16)	−0.0043 (13)	0.0020 (12)	−0.0051 (12)
S8	0.0140 (13)	0.0179 (16)	0.0228 (17)	−0.0042 (12)	0.0001 (13)	−0.0005 (12)

Geometric parameters (Å, º)

N1—C3	1.304 (12)	N4—H4	0.8800
N1—C7	1.452 (12)	C8—C9	1.518 (13)
N1—C1	1.459 (12)	C8—H8A	0.9900
C1—C2	1.525 (13)	C8—H8B	0.9900
C1—H1A	0.9900	C9—H9A	0.9900
C1—H1B	0.9900	C9—H9B	0.9900
N2—C3	1.293 (13)	C10—C11	1.491 (14)
N2—C2	1.481 (14)	C11—C12	1.498 (13)
N2—H2	0.8800	C11—H11A	0.9900
C2—H2A	0.9900	C11—H11B	0.9900
C2—H2B	0.9900	C12—C13	1.529 (15)
C3—C4B	1.47 (3)	C12—H12A	0.9900
C3—C4A	1.484 (16)	C12—H12B	0.9900
C4A—C5A	1.536 (19)	C13—C14	1.492 (14)
C4A—H4A1	0.9900	C13—H13A	0.9900
C4A—H4A2	0.9900	C13—H13B	0.9900
C5A—C6A	1.51 (3)	C14—H14A	0.9900
C5A—H5A1	0.9900	C14—H14B	0.9900
C5A—H5A2	0.9900	Sn1—S5	2.427 (3)
C6A—C7	1.476 (16)	Sn1—S4	2.434 (2)
C6A—H6A1	0.9900	Sn1—S2	2.440 (3)
C6A—H6A2	0.9900	Sn1—S6	2.464 (3)
C4B—C5B	1.53 (3)	Sn1—S1	2.647 (3)
C4B—H4A	0.9900	Sn2—S7	2.392 (3)
C4B—H4B	0.9900	Sn2—S2	2.421 (3)
C5B—C6B	1.50 (4)	Sn2—S3	2.433 (2)
C5B—H5B1	0.9900	Sn2—S8	2.562 (3)
C5B—H5B2	0.9900	Sn2—S1	2.598 (2)
C6B—C7	1.48 (3)	Sn3—S8^i	2.399 (3)
C6B—H6A	0.9900	Sn3—S3	2.430 (2)
C6B—H6B	0.9900	Sn3—S4	2.433 (3)
C7—H7A	0.9900	Sn3—S7^i	2.551 (2)
C7—H7B	0.9900	Sn3—S1	2.569 (2)
N3—C10	1.308 (13)	S5—Sn1^ii	2.427 (3)
N3—C8	1.450 (12)	S6—Sn1^ii	2.464 (3)
N3—C14	1.457 (12)	S7—Sn3^iii	2.551 (2)
N4—C10	1.302 (13)	S8—Sn3^iii	2.399 (3)
N4—C9	1.455 (13)
C3—N1—C7	125.5 (9)	C9—C8—H8B	111.1
C3—N1—C1	110.6 (9)	H8A—C8—H8B	109.0
C7—N1—C1	123.5 (9)	N4—C9—C8	102.8 (8)
N1—C1—C2	102.9 (9)	N4—C9—H9A	111.2
N1—C1—H1A	111.2	C8—C9—H9A	111.2
C2—C1—H1A	111.2	N4—C9—H9B	111.2
N1—C1—H1B	111.2	C8—C9—H9B	111.2
C2—C1—H1B	111.2	H9A—C9—H9B	109.1
H1A—C1—H1B	109.1	N4—C10—N3	113.1 (10)
C3—N2—C2	111.5 (10)	N4—C10—C11	124.8 (10)
C3—N2—H2	124.3	N3—C10—C11	122.0 (10)
C2—N2—H2	124.3	C10—C11—C12	112.0 (9)
N2—C2—C1	100.9 (9)	C10—C11—H11A	109.2
N2—C2—H2A	111.6	C12—C11—H11A	109.2
C1—C2—H2A	111.6	C10—C11—H11B	109.2
N2—C2—H2B	111.6	C12—C11—H11B	109.2
C1—C2—H2B	111.6	H11A—C11—H11B	107.9
H2A—C2—H2B	109.4	C11—C12—C13	111.0 (10)
N2—C3—N1	112.2 (10)	C11—C12—H12A	109.4
N2—C3—C4B	115 (2)	C13—C12—H12A	109.4
N1—C3—C4B	131 (2)	C11—C12—H12B	109.4
N2—C3—C4A	127.1 (12)	C13—C12—H12B	109.4
N1—C3—C4A	120.6 (11)	H12A—C12—H12B	108.0
C3—C4A—C5A	112.5 (11)	C14—C13—C12	110.6 (9)
C3—C4A—H4A1	109.1	C14—C13—H13A	109.5
C5A—C4A—H4A1	109.1	C12—C13—H13A	109.5
C3—C4A—H4A2	109.1	C14—C13—H13B	109.5
C5A—C4A—H4A2	109.1	C12—C13—H13B	109.5
H4A1—C4A—H4A2	107.8	H13A—C13—H13B	108.1
C6A—C5A—C4A	107.4 (17)	N3—C14—C13	110.8 (8)
C6A—C5A—H5A1	110.2	N3—C14—H14A	109.5
C4A—C5A—H5A1	110.2	C13—C14—H14A	109.5
C6A—C5A—H5A2	110.2	N3—C14—H14B	109.5
C4A—C5A—H5A2	110.2	C13—C14—H14B	109.5
H5A1—C5A—H5A2	108.5	H14A—C14—H14B	108.1
C7—C6A—C5A	110.8 (17)	S5—Sn1—S4	120.68 (7)
C7—C6A—H6A1	109.5	S5—Sn1—S2	124.72 (7)
C5A—C6A—H6A1	109.5	S4—Sn1—S2	113.33 (9)
C7—C6A—H6A2	109.5	S5—Sn1—S6	89.41 (8)
C5A—C6A—H6A2	109.5	S4—Sn1—S6	97.49 (8)
H6A1—C6A—H6A2	108.1	S2—Sn1—S6	94.75 (7)
C3—C4B—C5B	106 (3)	S5—Sn1—S1	86.12 (8)
C3—C4B—H4A	110.4	S4—Sn1—S1	86.35 (8)
C5B—C4B—H4A	110.4	S2—Sn1—S1	86.35 (8)
C3—C4B—H4B	110.4	S6—Sn1—S1	175.18 (8)
C5B—C4B—H4B	110.4	S7—Sn2—S2	119.96 (9)
H4A—C4B—H4B	108.6	S7—Sn2—S3	121.94 (9)
C6B—C5B—C4B	110 (4)	S2—Sn2—S3	118.05 (9)
C6B—C5B—H5B1	109.6	S7—Sn2—S8	88.59 (8)
C4B—C5B—H5B1	109.6	S2—Sn2—S8	93.10 (9)
C6B—C5B—H5B2	109.6	S3—Sn2—S8	90.51 (8)
C4B—C5B—H5B2	109.6	S7—Sn2—S1	93.23 (8)
H5B1—C5B—H5B2	108.1	S2—Sn2—S1	87.85 (9)
C7—C6B—C5B	125 (5)	S3—Sn2—S1	86.71 (8)
C7—C6B—H6A	106.0	S8—Sn2—S1	177.19 (8)
C5B—C6B—H6A	106.0	S8^i—Sn3—S3	123.37 (9)
C7—C6B—H6B	106.0	S8^i—Sn3—S4	120.20 (9)
C5B—C6B—H6B	106.0	S3—Sn3—S4	116.43 (9)
H6A—C6B—H6B	106.3	S8^i—Sn3—S7^i	88.69 (8)
N1—C7—C6A	112.8 (10)	S3—Sn3—S7^i	90.60 (8)
N1—C7—C6B	104 (2)	S4—Sn3—S7^i	90.35 (9)
N1—C7—H7A	109.0	S8^i—Sn3—S1	94.65 (8)
C6A—C7—H7A	109.0	S3—Sn3—S1	87.41 (8)
N1—C7—H7B	109.0	S4—Sn3—S1	88.12 (9)
C6A—C7—H7B	109.0	S7^i—Sn3—S1	176.66 (9)
H7A—C7—H7B	107.8	Sn3—S1—Sn2	86.75 (8)
C10—N3—C8	110.0 (8)	Sn3—S1—Sn1	87.14 (8)
C10—N3—C14	125.6 (9)	Sn2—S1—Sn1	86.61 (8)
C8—N3—C14	123.6 (8)	Sn2—S2—Sn1	95.47 (9)
C10—N4—C9	110.4 (9)	Sn3—S3—Sn2	93.71 (9)
C10—N4—H4	124.8	Sn3—S4—Sn1	95.26 (9)
C9—N4—H4	124.8	Sn1—S5—Sn1^ii	91.47 (13)
N3—C8—C9	103.5 (8)	Sn1^ii—S6—Sn1	89.71 (13)
N3—C8—H8A	111.1	Sn2—S7—Sn3^iii	90.63 (8)
C9—C8—H8A	111.1	Sn3^iii—S8—Sn2	90.22 (9)
N3—C8—H8B	111.1

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