Thiostannate

Sulfidostannates, or thiostannates are chemical compounds containing anions composed of tin linked with sulfur. They can be considered as stannates with sulfur substituting for oxygen. Related compounds include the thiosilicates, and thiogermanates, and by varying the chalcogen: selenostannates, and tellurostannates. Oxothiostannates have oxygen in addition to sulfur.^[1] Thiostannates can be classed as chalcogenidometalates, thiometallates, chalcogenidotetrelates, thiotetrelates, and chalcogenidostannates. Tin is almost always in the +4 oxidation state in thiostannates, although a couple of mixed sulfides in the +2 state are known,

Some thiostannate minerals are known. In nature the tin can be partly replaced by arsenic, germanium, antimony or indium. Many thiostannate minerals contain copper, silver or lead. In the field of mineralogy, these compound can be termed sulfostannates or sulphostannates.

Different cluster anions are known: [SnS₄]^4–, [SnS₃]^2–, [Sn₂S₅]^2–, [Sn₂S₆]^4–, [Sn₂S₇]^6–, [Sn₂S₈]^2–, [Sn₃S₇]^2–, [Sn₄S₉]^2–, [Sn₅S₁₂]^4–, or [Sn₄S₁₀]^4–.^[2]

The number of sulfur atoms coordinated around the tin atom is most commonly four. However there are also complexes with five or six sulfur atoms surrounding the tin. The behaviour for selenium and tellurium differs as only five selenium or four tellurium atoms can bind to a tin atom. The smaller germanium atom can only accommodate four sulfur atoms. For lead it is hard for it to be in the +4 oxidation state. The SnS_n polyhedrons can be standalone in strongly alkaline conditions, or at higher concentrations or less alkaline can condense together. Polyhedra shapes are tetrahedron for four, trigonal bipyramid for five, and octahedron for six sulfur atoms. The polyhedra can be connected at a vertex (corner), or at an edge. Where connected at an edge, four membered rings of -SnSSnS- with internal angles close to 90°.^[3] [Sn₂S₇]^6– is corner bridged. Tetrahedra linked by at the corner by a disulfur bridge are unknown.^[3]

Sn₁₀O₄S₂₀^8- is a supertetrahedron made from 1, 3 and 6 tin atoms connected by oxygen on the interior and sulfur on the surface.^[3]

For anions with formula Sn_xS_y the condensation ratio c is given by x⁄y. It can vary from 1⁄4 to just below ⁠1/2⁠.^[3]

Synthesis

The first human production of a thiostannate heated tin oxide with sodium carbonate and sulfur:^[4]

2SnO₂ + 2Na₂CO₃ + 9S → 2Na₂SnS₃ + 2CO₂ + 3SO₂

Transition metal complexes may be prepared by crystallisation from the ligand solvent.^[4]

Copper(II) is normally reduced by sulfide S^2- in thiostannates to copper(I).^[5]

Anions

formula	name	coordination	dimensionality	description
[SnS4]4−		4	0	tetrahedra
[Sn2S6]4−	bis(μ-sulfido)-tetrathiolato-di-tin	4	0	edge shared
[Sn3S9]6−	1,3,5,2,4,6-trithiatristanninane-2,2,4,4,6,6-hexakis(thiolate)	4	0	6 membered ring
[Sn4S10]4-		4	0	tetrameric adamantane-like : tetrahedron of tetrahedra, 6 bridging sulfur, 4 terminal sulfur

Reactions

Some hydrates are unstable, where water reacts with the sulfide to make hydrogen sulfide gas.

List

formula	system	space group	unit cell Å	volume	density	comment
Li4SnS4	orthorhombic	Pnma	a=13.812 b=7.962 c=6.370				[6]
[Li8(H2O)29][Sn10O4S20]·2H2O	triclinic	P1	a = 11.232, b = 13.097, c = 23.735, α = 102.73°, β = 90.43°, γ = 93.44°, Z = 2	3399		oxothiostannate	[7]
(NH4)4Sn2S6·3H2O	orthorhombic	P41212	a =8.56294 b =8.56294 c= 22.7703				[8]
(NH4)6Sn3S9·1.3H2O	monoclinic	C2	a 16.9872 b 10.54777 c 21.0871 β 108.0389°	3592.6	2.154	colourless	[9]
[(CH3)3NH]2Sn3S7							[3]
[(CH3)4N]2Sn3S7·H2O							[3]
[(CH3)4N]4Sn4S10							[8]
[(CH3CH2)4N]2Sn3S7							[3]
[(CH3CH2CH2)4N]2Sn4S9							[3]
[(CH3CH2CH2CH2)4N]2Sn4S9							[3]
[(CH3CH2CH2)4N][(CH3)3NH]Sn4S9							[3]
(C12H25NH3)4Sn2S6 ·2H2O							[3]
[dabcoH]2Sn3S7							[3]
(Et4N)2Sn(S4)3							[3]
(Et4N)2Sn(S4)2(S6)							[3]
((CH3C(NH2)2)8Sn2S6SnS4	monoclinic	C 1 2/m 1	a=23.7739 b=16.0647 c=11.8936 β=99.029 Z=4	4486.1	1.702	colourless	[9]
((CH3)2NH2)(NH4)SnS3 dimethylammonium ammonium	orthorhombic	P212121	a=5.9393 b=12.1816 c=12.4709 Z=4	902.26	2.054	colourless	[9]
(DBNH)2Sn3S6 DBN=1,5-diazabicyclo[4.3.0]non-7-ene						Sn(II) and Sn(IV)	[10]
(1AEP)2Sn3S7 1AEP = 1-(2-aminoethyl) piperidine	orthorhombic	P212121	a=13.2299 b= 22.2673 c=9.0772 Z=4	2674.1		pale yellow	[11]
SnS2·en	monoclinic	C2/c	a 15.317 b 10.443 c 12.754, β 93.62°				[12]
[enH]4[Sn2S6]·en	triclinic	P1	a 9.8770 b 9.9340 c 15.4230, α 72.630° β 86.220° γ 81.380°				[12]
Na2SnS3		R3m	a=3.834 c=19.876 Z=2	253	3.43		[4][13]
Na4SnS4	tetragonal	P421c	a=7.837 c=6.950	427	2.64		[13]
Na4Sn2S6							[3]
Na4Sn2S6·14H2O	triclinic	P1	a=10.114 b=7.027 c=9.801 α=108.30 β=92.18 γ=91.11 Z=1	663	1.95		[2]
Na4SnS4·14H2O	monoclinic	C2/c	a=8.622 b=23.534 c=11.347 β=110.53 Z=4	2156	1.82		[13]
Na4Sn3S8							[3]
Na5[SnS4]Cl·13H2O	monoclinic	P21/m	a=8.4335 b=11.4958 c=11.5609 β=91.066 Z=2	1120.63	1.872		[2]
Na4Sn2S6·5H2O							[3]
Na6Sn2S7		C2/c	a=9.395 b=10.719 c=15.671 β=109.97 Z=4	1483	2.69		[13]
Mg2SnS4	orthorhombic	Pnma	a=12.93 b=7.52 c=6.16 Z=4	599	3.28		[13]
Na2MgSnS4		R3m	a 3.7496 b 3.7496 c 19.9130				[14]
(Ph4P)2Sn(S4)3							[3]
K2SnS3 ·2H2O							[3]
K2SnS3·2H2O	orthorhombic	Pnma	a=6.429 b=15.621 c=10.569 Z=4	1061	2.06		[13]
K2Sn2S5							[3]
K2Sn3S7 ·H2O							[3]
[K4(H2O)4][SnS4]							[15]
Ca2SnS4	orthorhombic	Pnma	a=13.74 b=8.23 c=6.44 Z=4	728	2.99		[13]
[H2tepa][VIII(tepa)(μ-Sn2Q6)]2	orthorhombic	Abm2	a =7.7486 b =40.410 c =16.745				[16]
Mn2SnS4	tetragonal	I41/a	a=7.408 c=10.41 Z=8	571	4.15		[13]
[Mn(en)3]2[Sn2S6]	monoclinic	C2/c	a=15.138 b=10.6533 c=23.586 β=118.42 Z=4	3345.2	1.787	colourless	[5][17]
[Mn(en)3]2Sn2S6·2H2O	monoclinic	P21/c	a=10.129, b=15.746, c=11.524, β=102.36° Z=2	1795.5	1.732		[18]
[Mn(en)2]2(μ-en)[Sn2S6]	triclinic		a=9.0017 b=9.7735 c=10.8421 α=60.38° β=67.23° γ=70.25°	752.38			[16]
[Mn(dien)2]2Sn2S6	monoclinic	P21/c	a=12.48 12, b= 9.3760, c=17.7617, β=121.752°, Z=2,	1767.5	1.789		[18]
[Mn(tren)]2Sn2S6	triclinic	P1	a 7.653 b 8.088 c 12.200, α 97.27° β 104.06° γ 108.80° Z=1	676.0	2.044	yellow	[5][19]
[Mn(tren)(H2O)][Mn(baen)]3Mn4Sn6S20∙9H2O	orthorhombic	P213	a =21.404 b =21.404 c= 21.404			super tetrahedron	[20]
{Mn(tepa)}2(μ-Sn2S6)	tetragonal	I41/a	a=25.977 c=10.041 Z=8	6775	1.800	yellow	[19]
{[Mn(trien)]2[SnS4]}							[5]
{[Mn(C6H18N4)]2SnS4}·4H2O	monoclinic	P21/c	a 10.8446 b 20.974 c 13.2746 β 113.487°				[21]
{[Mn(phen)2]2(μ2-Sn2S6)}	monoclinic	P21/n	a =10.8230 b=9.8940 c=24.811 β=91.356°				[22]
{[Mn(phen)2]2(μ2-Sn2S6)}·phen	triclinic	P1	a=10.0642 b=10.6249 c=13.693, α=71.700° β=81.458° γ=84.346°				[22]
{[Mn(phen)2]2[Sn2S6]}·phen·H2O phen = 1,10-phenanthroline	triclinic	P1	a=11.3203 b=12.1436 c=12.7586, α=113.200° β=90.908° γ=110.974°				[5][22]
[Mn(phen)]2(SnS4)·H2O	monoclinic	C2/m	a=16.146 b=19.262 c=9.938 β=124.970 Z=4	2532.6	1.928	red chain	[23]
{[Mn(phen)2]2[μ-η2-η2-SnS4]2[Mn(phen)]2}·H2O	triclinic	P1	a=10.8703 b=12.5183 c=14.9644, α=103.381° β=108.390° γ=101.636°				[22]
{[Mn(2,2′-bipy)2]2[Sn2S6]}							[24]
(1,4-dabH)2MnSnS4 1,4-dab = 1,4-diaminobutane	orthorhombic	Fdd2	a = 22.812, b = 24.789, c = 6.4153, Z = 8	3627.8			[25]
Li4MnSn2Se7	monoclinic	Cc	a=18.126 b=7.2209 c=10.740 β=93.43 Z=4	1403.2	4.132	orange	[26]
Fe2SnS4	tetragonal	I41/a	a=7.308 c=10.338 Z=4	552	4.32		[13]
{[Fe(tepa)]2[Sn2S6]}	tetragonal	I41/a					[5][27]
{[Fe(1,2-dach)2][Sn2S6]}·2(1,2-dachH)							[5]
{[Fe(phen)2]2[Sn2S6]}·phen·H2O							[5]
[Co(en)3]2[Sn2S6]	orthorhombic	Pbca	a=15.640 b=11.564 c=18.742 Z=4	2289.7	1.779	yellow	[5][17]
[Co(dien)2]2[Sn2S6]							[5]
[Co2(cyclam)2Sn2S6]·2H2O							[28]
[Co(tren)]2Sn2S6	monoclinic	C2/c	a=12.228 b=9.7528 c=23.285 β=102.90	2706.8			[5][16]
{[Co(cyclam)]2[Sn2S6]}n·2nH2O cyclam = 1,4,8,11-tetraazacyclotetradecane							[5]
{[Co(tepa)]2[Sn2S6]} tepa=tetraethylenepentamine	tetragonal	I41/a	a=25.742 c=9.898	6558			[5][27][16]
{[Co(phen)2]2[Sn2S6]}·phen·H2O							[5]
[Co(2-(aminomethyl)pyridine)3]2Sn2S6·10H2O (2amp)	monoclinic	P21/c	a=10.1443 b=14.6124 c=18.8842 β=90.601° Z=2	2799.1	1.633	yellow	[29]
[Co(trans-1,2-diaminocyclohexane)3]2Sn2S6·8H2O (dach)	monoclinic	P21/n	a=12.6521 b=11.7187 c=20.4386 β=91.262° Z=2	3029.6	1.509	red	[29]
Ni6SnS2 Butianite	tetragonal	I4/mmm	a = 3.650, c = 18.141 Z=2	241.7	7.62	opaque	[30]
[Ni(en)3]2[Sn2S6]							[5]
[Ni(dap)3]2[Sn2S6]·2H2O dap=1,2-diaminopropane	triclinic	P1	a=9.9046 b=10.527 c=11.319 α =72.13° β =85.19° γ =63.63°	1004.5			[5][16]
[Ni(1,2-dach)3]2[Sn2S6]·4H2O 1,2-dach = 1,2-diaminocyclohexane							[5]
[Ni(dien)2]2[Sn2S6]							[5]
{[Ni(cyclen)]6[Sn6S12O2(OH)6]}·2(ClO4)·19H2O cyclen = 1,4,7,10-tetraazacyclododecane							[31]
[Ni(cyclen)(H2O)2]4[Sn10S20O4]·~13H2O							[31]
{[Ni(cyclen)]6[Sn6S12O2(OH)6]}·2(ClO4)·19H2O	monoclinic	C2/c	a=25.7223 b=15.6522 c=29.070 β=105.879 Z=4	11257	1.863	oxothiostannate	[32]
[Ni(2amp)3]2[Sn2S6]·9.5H2O 2amp = 2-(aminomethyl)pyridine	monoclinic	P21/n	a=18.7021 b=14.6141 c=20.2591 β=97.696 Z=4	5487.2	1.655	purple	[4]
[Ni(aepa)2]2[Sn2S6] aepa=N-2-aminoethyl-1,3-propandiamine							[5]
[Ni(tren)]2Sn2S6	monoclinic	C2/c	a=23.371 b=8.231 c=14.274 β =107.230 Z=4	2622.6	2.127		[5][33]
[Ni(tren)2]2[Sn2S6]·8H2O	orthorhombic	P42/n	a=26.1885 b=26.1885 c=11.1122				[5][34]
[Ni(tren)(2amp)]2[Sn2S6]	triclinic	P1	a =10.2878 b =11.1100 c =11.4206, α =84.740° β =84.395° γ =79.093°				[5][34]
[Ni(tren)(2amp)]2[Sn2S6]·10H2O	monoclinic	P21/n	a =12.1933 b =13.4025 c =14.8920 β= 103.090°				[35]
[Ni(tren)(en)]2[Sn2S6]·2H2O	monoclinic	P21/n	a 12.7041 b 9.8000 c 15.3989, β 108.843°				[35]
[Ni(tren)(en)]2[Sn2S6]·6H2O	monoclinic	P21/n	a 12.5580 b 9.7089 c 16.0359, β 91.827°				[35]
[Ni(tren)(1,2-dach)]2[Sn2S6]·3H2O	triclinic	P1	a 9.8121 b 10.0080 c 12.422, α 86.38° β 79.65° γ 65.72°				[35]
[Ni(tren)(1,2-dach)]2[Sn2S6]·4H2O	monoclinic	P21/n	a 10.7119 b 19.0797 c 11.1005, β 104.803°				[35]
{[Ni(cyclam)]2[Sn2S6]}·2H2O							[5]
{[Ni(tepa)]2[Sn2S6]}	monoclinic	P21/n					[5][27]
{[Ni(phen)2]2[Sn2S6]}·2,2′-bipy	monoclinic	P21/n	a=10.5715 b=9.9086 c=24.9960 β=92.800 Z=2	2615.17	1.809	deep red	[5][36]
{[Ni(phen)2]2Sn2S6}·4,4′-bipy·½H2O 4,4′-bipy = 4,4′-bipyridine	monoclinic	C2/c	a=18.3431 b=19.4475 c=15.0835 β=95.556 Z=4	5355.4	1.789	dark red-brown	[36]
{[Ni(phen)2]2[Sn2S6]}·phen·H2O							[24]
[Ni(L1)][Ni(L1)Sn2S6]n·2H2O L1 = 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane	monoclinic	P21/c					[37]
[Ni(L2)]2[Sn2S6]·4H2O L2 = 1,8-diethyl-1,3,6,8,10,13-hexaazacyclotetradecane	triclinic	P1					[37]
[Ni(tren)(ma)(H2O)]2[Sn2S6]·4H2O ma = methylamine	monoclinic	P21/n	a=11.1715 b=10.5384 c=15.8594 Z=2	1827.45	1.835		[33]
[Ni(tren)(1,2-dap)]2[Sn2S6]·2H2O	monoclinic	P21/n	a=12.9264 b=10.1627 c=15.6585 Z=2	1889.8	1.799		[33]
[Ni(tren)(1,2-dap)]2[Sn2S6]·4H2O	monoclinic	C2/c	a =14.3925 b=15.1550 c=18.9307, β=99.108°				[35]
[Ni(2amp)3]2[Sn2S6]·9.5H2O 2amp = 2-(aminomethyl)pyridine	monoclinic	P21/n	a=18.7021 b=14.6141 c=20.2591 Z=4	5487.23	1.655	purple	[4]
Cu2SnS3 Mohite	monoclinic		a=23.10 b=6.25 c=6.25 β=101.0°		4.69	greenish grey	[13][38]
Cu3SnS4 Kuramite	tetragonal	I42m	a = 5.445, c = 10.75, Z = 2	318.72	4.56		[39]
Cu4SnS4	orthorhombic	Pnma	a=13.70 b=7.750 c=6.454 Z=4	685	4.96		[13]
Cu4SnS6 Erazoite	rhombohedral	R3m	a = 3.739, c = 32.941, Z = 2		4.53	black	[40]
Cu4Sn7S16	monoclinic		a=12.75 b=7.34 c=12.71 β=109.5 Z=2	1121	4.74		[13]
(DBUH)CuSnS3 DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene	monoclinic	P21/n	a=9.254 b=8.6190 c=18.135, β=92.80°				[41]
(1,4-dabH2)Cu2SnS4 1,4-dab = 1,4-diaminobutane	tetragonal	P42/n	a=14.539 c=11.478				[42]
(enH)6Cu40Sn15S60 en=ethylenediamine	cubic	Pn3n	a=25.260 Z=4	16119	2.727	black	[43]
(enH)3Cu7Sn4S12	trigonal	R3c	a=13.532 c=28.933 Z=6	4588	3.23	red	[43]
[H2en]2[Cu8Sn3S12]							[5]
(trenH3)Cu7Sn4S12 tren = tris(2-aminoethyl)amine)	trigonal	R3c	a=13.1059 c=29.347 Z=6	4365.4	3.317		[43]
[dienH2][Cu2Sn2S6]							[5]
[DBUH][CuSnS3] DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene							[5]
[1,4-dabH2][Cu2SnS4]							[5]
{[Cu(cyclam)]2[Sn2S6]}·2H2O cyclam=1,4,8,11-tetraazacyclotetradecane	triclinic	P1	a=9.0580 b=9.9419 c=10.2352, α=97.068° β=94.314° γ=101.514°				[5]
(DBNH)2Cu6Sn2S8 DBN=1,5-diazabicyclo[4.3.0]non-7-ene							[10]
[Co(2-(aminomethyl)pyridine)3]2 Sn2S6·10H2O	monoclinic	P21/c	a=10.1443 b=14.6124 c=18.8842 β=90.601° Z=2	2799.1	1.633	yellow; unstable	[44]
[Co(trans-1,2-diaminocyclohexane)3]2Sn2S6·8H2O	monoclinic	P21/n	a=12.6521 b=11.7187 c=20.4386 β=91.262° Z=2	3029.6	1.509	red	[44]
Na4Cu32Sn12S48·4H2O	cubic	Fm3c	a = 17.921 z = 13			black; absorption edge 2.0 eV	[45]
CuAlSnS4	cubic		a=10.28 Z=8	1074	4.17		[13]
K11Cu32Sn12S48·4H2O	cubic	Fm3c	a = 18.0559 z = 14.75			black; absorption edge 1.9 eV	[45]
Cu2MnSnS4	tetragonal		a=5.49 c=10.72 Z=2	323	4.41		[13]
Cu2FeSnS4 Stannite Ferrokësterite	tetragonal	I42m	a = 5.4432, c = 10.7299 Z=2	317.91		grey	[46]
Cu2FeSn3S8	tetragonal	I41/a	a=7.29 c=10.31 Z=2	548	4.82		[13]
Cu6Fe2SnS8 Mawsonite	Tetragonal	P4m2	a = 7.603, c = 5.358 Z=1	309	4.65	brownish orange	[47]
Cu6FeSn2S8 Chatkalite	Tetragonal	P4m2	a = 7.61, c = 5.373 Z=1	311.1	5.00		[48]
Cu2CoSnS4	Tetragonal	I42m	a=5.402 c=10.805 Z=2	315	4.56		[13]
Cu2NiSnS4			a=5.425 Z=1	160	4.49		[13]
Cu13VSn3S16 Nekrasovite	isometric		a=10.73	1,235		brown	[49]
[Zn(en)3]2[Sn2S6]	orthorhombic	Pbca	a=15.452 b=11.524 c=18.614 Z=4	3315.3	1.845	colourless	[5][17]
{Zn(tren)}2(μ-Sn2S6)	monoclinic	C2/c	a 12.214 b 9.726 c 23.209 β 102.732°	2689.3	2.107	light yellow	[19][50]
Cu2ZnSnS4 Kësterite	tetragonal	I4	a = 5.427, c = 10.871 Z=2	320.18	4.55	greenish black	[51]
Cu6+Cu22+(Fe2+,Zn)3Sn2S12 Stannoidite	orthorhombic		a = 10.76, b = 5.4, c = 16.09	934.9	4.68	brass	[52]
Cu3(V,Ge,Sn)S4 Ge-Sn-Sulvanite				361			[53]
SnGeS3 Stangersite	monoclinic	P21/b	a = 7.270, b = 10.197, c = 6.846 β = 105.34° Z=4	489	3.98	orange
Rb4SnS4							[3]
Rb4Sn2S6							[3]
Rb2Sn3S7·2H2O							[3]
Rb2Cu2SnS4	orthorhombic	Ibam	a=5.528 b=11.418 c=13.700 Z=4	865	4.185	band gap 2.08 eV	[54]
Rb2Cu2Sn2S6	monoclinic	C2/c	a=11.026 b=11.019 c=20.299 β=97.79 Z=8	2444	3.956	band gap 1.44 eV	[54]
Rb2ZnSn3S8							[55]
[Rb4(H2O)4][SnS4]							[15]
Sr3MnSn2S8	cubic	I43d	a = 14.2287 Z = 8	2880.7	3.743	dark green	[56]
Cu2SrSnS4	trigonal	P31	a = 6.29, c = 15.57 Z=3	534	4.31		[57][13]
Sr6Cu4Sn4S16	cubic	I43d	a=13.982	2734	4.295	yellow	[58]
Sr6Cu2FeSn4S16	cubic	I43d	a=14.1349			band gap 1.53 eV	[59]
SrSnS3	orthorhombic	Pnma	a=8.264 b=3.867 c=14.116 Z=4	451	4.45		[13]
[Y2(dien)4(μ-OH)2]Sn2S6	monoclinic	P21/n	a=11.854 b=11.449 c=13.803 β=97.978 Z=2	1855	1.888	light yellow	[60]
α-Ag8SnS6	cubic		a=21.43	9842			[13]
β-Ag8SnS6	cubic		a=10.85	1277			[13]
Ag8SnS6 Canfieldite	orthorhombic		a = 15.298, b = 7.548, c = 10.699 Z=4	1,235.4	6.311	metallic	[61]
Na3AgSnS4	monoclinic	P21/c	a 8.109 b 6.483 c 15.941, α 90° β 103.713			double chain	[62]
AgCrSnS4	cubic		a=10.74 Z=8	1239	4.92		[13]
Ag2MnSnS4 – Agmantinite	orthorhombic		a = 6.632, b = 6.922, c = 8.156 Z=2		4.574	orange	[63]
Ag2ZnSnS4 Pirquitasite	tetragonal	I4	a = 5.78, c = 10.82	361		black	[64]
Ag2(Fe2+,Zn)SnS4 Hocartite	tetragonal	I42m	a = 5.74, c = 10.96 Z=2	361	4.77	brownish grey	[65]
Ag1+(Fe2+0.5Sn4+1.5)S4 Toyohaite	tetragonal					grey	[66]
[enH][Cu2AgSnS4]	orthorhombic	Pnma	a=19.7256 b=7.8544 c= 6.5083 Z=4	1008.3	3.577	red	[67]
Ag2SrSnS4	orthorhombic		a=7.127 b=8.117 c=6.854 Z=2	397	5.02		[13]
Sr6Ag4Sn4S16	cubic	I43d	a=14.2219 Z=4	2876.6	4.491	yellow	[58]
Sr6Ag2FeSn4S16	cubic	I43d	a=14.2766			band gap 1.87 eV	[59]
[1,4-dabH2][Ag2SnS4] 1,4-dab = 1,4-diaminobutane	tetragonal	P42/n	a = 14.7847, c = 11.9087, Z = 8	2603.1			[5][68]
[H2en][Ag2SnS4]							[5]
[CH3NH3]2Ag4SnIV2SnIIS8	orthorhombic	Pnma	a =19.378 b =7.390 c =13.683 Z=4	1959	3.756	Orange Sn(II)	[69]
[CH3NH3]6Ag12Sn6S21	monoclinic	P21/c	a =18.8646 b =19.9115 c =14.3125 β 100.117°				[70]
[(Me)2NH2]3[Ag5Sn4Se12]	tetragonal	P421m	a=13.998 c=8.685 Z=2	1701.9	4.403	dark red	[71]
[enH][Cu2AgSnS4]							[5]
Cu2CdSnS4		I42m	a=5.402 c=10.86 Z=2	338	4.77		[13]
Ag2CdSnS4		Cmc21	a=4.111 b=7.038 c=6.685 Z=1	193	4.95		[13]
Cu2(Cd,Zn,Fe)SnS4 Černýite	tetragonal	I42m	a = 5.48, c = 10.828 Z=4	326	4.76	metallic	[72]
CuInSnS4			a=10.50 Z=8	1158	4.91		[13]
AgInSnS4			a=10.16 Z=8	1048	4.59		[13]
(Cu,Fe,Zn,Ag)3(Sn,In)S4 Petrukite	orthorhombic		a = 7.66, b = 6.43, c = 6.26	308		brown	[73]
(Cu,Zn,Fe)3(In,Sn)S4 Sakuraiite	isometric		a = 5.46 Z=1	162		greenish grey	[74]
Sn2S3	orthorhombic	Pnma	a=8.864 b=3.7471 c=14.020 Z=4	466	4.76		[13]
Cs4SnS4						0d	[3]
Cs2Sn3S7 ·0.5S8						2d	[3]
Cs4Sn5S12·2H2O						2d	[3]
[Cs4(H2O)3][SnS4]							[15]
Cs2Sn(S4)2(S6)							[3]
Cs8Sn10O4S20·13H2O							[3]
[Cs10(H2O)18][Mn4(μ4-S)(SnS4)4]							[15]
Cs2ZnSn3S8	monoclinic	P21/n	a 7.5366 b 17.6947 c 12.4976, β=94.830° Z=4	1660.7	3.775	layered, band gap 3. eV	[55]
[Ba2(H2O)11][SnS4]							[15]
Li2Ba6MnSn4S16	cubic	I43d	a=14.6080 Z=4	3117.3	4.007	light yellow	[42]
Ag2Ba6MnSn4S16	cubic	I43d	a=14.7064 Z=4	3180.7	4.349	yellow	[42]
Ag2BaSnS4	orthorhombic	I222	a =7.127 b =8.117 c =6.854 Z=2			black	[75]
Ba3Ag2Sn2S8							[76]
BaSnS2						Sn(II)	[77]
BaSn2S3						Sn(II)	[77]
BaSnS3	orthorhombic	Pnma	a=8.527 b=3.933 c=14.515 Z=4	487	4.8		[13]
BaSnS3	monoclinic	C2/c Cc	a=24.49 b=6.354 c=23.09 β=90.15 Z=28	3593	4.55		[13]
α-Ba2SnS4	monoclinic	P21/c	a=8.481 b=8.526 c=12.280 β=112.97 Z=4	818	4.24		[13]
β-Ba2SnS4	orthorhombic	Pnma	a=17.823 b=7.359 c=12.613	1654	4.18		[13]
Ba3Sn2S7	monoclinic	P21/c	a=11.073 b=6.771 c=18.703 β=100.77 Z=4	1378	4.21		[13]
K2BaSnS4		R3c	a 25.419 c 7.497			band gap 3.09 eV; SHG 0.5×AgGaS2	[78]
Ba6Cu2FeSn4S16	cubic	I43d	a=14.5260			band gap 1.2 eV	[59]
Ba6Cu2NiSn4S16	cubic	I43d	a=14.511			band gap 0.82 eV	[59]
Ba6Li2ZnSn4S16	cubic	I43d	a=14.5924				[79]
Ba6Ag2ZnSn4S16	cubic	I43d	a=14.6839				[79]
BaCdSnS4	orthorhombic	Fdd2	a=21.57 b=21.76 c=13.110 Z=32	6152	4.290	yellow	[80]
Ba3CdSn2S8	cubic	I43d	a=14.723				[81]
Ba6CdAg2Sn4S16	cubic	I43d	a=14.725				[81]
La2SnS5	orthorhombic	Pbam	a=11.22 b=7.915 c=3.97 Z=2	352	5.26		[13]
[La(dien)3]2[Sn2S6]Cl2						band gap 3.25 eV	[82]
La(peha)(μ–SnS4H) peha=pentaethylenehexamine	triclinic	P1	a 8.609 b 9.327 c 14.649, α 79.2° β 85.5° γ 63.74°				[83]
BaCeSn2S6	orthorhombic	Pmc21	a 4.0665 b 19.859 c 11.873				[84]
BaPrSn2S6	orthorhombic	Pmc21	a 4.0478 b 19.8914 c 11.9303				[84]
BaNdSn2S6	orthorhombic	Pmc21	a 4.0098 b 19.761 c 11.841				[84]
[Nd2(en)6(μ2-OH)2]Sn2S6	monoclinic	P21/n	a =10.176, b =11.387, c=15.018, β =97.869°				[85]
Nd(peha)(μ–SnS4H)	triclinic	P1	a 8.621 b 9.372 c 14.656, α 78.28° β 84.33° γ 63.32°				[83]
{Nd(tepa)(μ–OH)}2(μ–Sn2S6)]·H2O tepa=tetraethylenepentamine	monoclinic	C2/c	a=21.537 b=12.863 c=17.697 β=124.308°				[83]
[Nd(dien)3]2[(Sn2S6)Cl2] dien = diethylenetriamine	monoclinic	P21/n	a = 11.672, b = 15.119, c = 14.157, β = 96.213°, Z = 4	2483.6			[86]
[Nd(dien)3]2[(Sn2S6)(SH)2]	monoclinic	P21/n	a = 11.719, b = 15.217, c = 14.221, β = 95.775°, Z = 4	2523.1			[86]
(tetaH)2[Eu2(teta)2(tren)2(μ-Sn2S6)]Sn2S6	triclinic	P1	a=9.886 b=10.371 c=17.442 α=89.78 β=88.00 γ=85.14 Z=1	1780.8	1.898	light yellow	[60]
[Eu2(tepa)2(μ-OH)2(μ-Sn2S6)](tepa)0.5·H2O tepa = tetraethylene-pentamine	monoclinic	C2/c	a=19.803 b=14.998 c=17.800 β=126.57 Z=4	4246	1.970	colourless	[60]
[{Eu(en)3}2(μ-OH)2]Sn2S6	monoclinic	P21/n	a = 10.116, b = 11.379, c = 14.949, β = 98.209°, Z=2	1703.1			[87]
[{Eu(en)3}2(μ-OH)2]Sn2Se6	monoclinic	P21/n	a = 10.136, b = 11.771, c = 15.423, β = 99.322°, Z = 2	1815.8			[87]
[Eu(dien)3]2[(Sn2S6)(SH)2]	monoclinic	P21/n	a = 11.656, b = 15.168, c = 14.173, β = 95.682°, Z = 2	2493.4			[87]
(tetaH)2[Sm2(teta)2(tren)2(μ-Sn2S6)]Sn2S6	triclinic	P1	a=9.920 b=10.382 c=17.520 α=89.91 β=88.07 γ=85.23 Z=1	1797.1	1.877	light yellow	[60]
{Sm(tepa)(μ–OH)}2(μ–Sn2S6)]·H2O	monoclinic	C2/c	a 21.487 b 12.8199 c 17.716 β 124.675°				[83]
[Sm2(en)6(μ 2-OH)2]Sn2S6	monoclinic	P21/n	a 10.129 b 11.377 c 14.962, β 98.128°				[88]
[Sm(dien)3]2[(Sn2S6)Cl2]	monoclinic	P21/n	a 11.631 b 15.091 c 14.1420 β 96.202°				[88]
[Sm(dien)3]2[(Sn2S6)(SH)2]	monoclinic	P21/n	a 11.698 b 15.212 c 14.219, β 95.654°				[88]
[Sm(trien)(tren)(Cl)]2Sn2S6 · en	triclinic	P1	a 10.320 b 10.491 c 13.791, α 100.524° β 91.930° γ 119.083°				[88]
{Gd(tepa)(μ–OH)}2(μ–Sn2S6)]·H2O	monoclinic	C2/c	a 21.455 b 12.804 c 17.735 β 124.81°				[83]
[Gd2(en)6(μ2-OH)2]Sn2S6	monoclinic	P21/n	a =10.1053 b =11.357 c =14.924, β = 98.346°				[85]
[Gd(dien)3]2[(Sn2S6)Cl2] dien = diethylenetriamine	monoclinic	P21/n	a =11.662, b =15.168. c 14.185, β =95.696°				[85]
{Dy(tepa)(μ–OH)}2(μ–Sn2S6)]·H2O	monoclinic	C2/c	a 21.363 b 12.717 c 17.654 β 124.915°				[83]
[Hen]2[La(en)4(CuSn3S9)]⋅0.5 en							[89]
[Hen]2[Ce(en)4(CuSn3S9)]⋅0.5 en							[89]
[Hen]4[Nd(en)4]2[Cu6Sn6S20]⋅3 en							[89]
[enH]4[Sm(en)4]2[Cu6Sn6S20]·3en	monoclinic	C2/m	a 14.257 b 24.242 c 13.119 β 92.223°				[90]
[Hen]4[Gd(en)4]2[Cu6Sn6S20]⋅3 en							[89]
[enH]4[Ho(en)4]2[Cu6Sn6S20]·3en	monoclinic	C2/m	a 14.3859 b 24.361 c 13.175, β 93.526°				[90]
EuCu2SnS4	orthorhombic	Ama2	a=10.4793, b=10.3610, c=6.4015, Z=4				[91][92]
[Hen]4[Er(en)4]2[Cu6Sn6S20]⋅3 en							[89]
[Hen]4[Er(en)4]2[Ag6Sn6S20]·3en	monoclinic	C2/m	a 14.557 b 24.397 c 13.412 β 94.42°				[93]
[Hen]4[Tm(en)4]2[Ag6Sn6S20]·3en	monoclinic	C2/m	a 14.517 b 24.380 c 13.422 β 94.46°				[93]
[Hen]4[Yb(en)4]2[Ag6Sn6S20]·3en	monoclinic	C2/m	a 14.536 b 24.397 c 13.397, β 94.63°				[93]
Cu6SnWS8 Kiddcreekite	isometric	F43m	a = 10.8178 Z=4	1265.9	4.934	grey	[94]
PtSnS Bowlesite	orthorhombic	Pca21	a = 6.12 Å, b = 6.12 Å, c = 6.10 Å Z=4	228.47	10.06	metallic	[95]
(Pd,Pt)5(Cu,Fe)4SnTe2S2 Oulankaite	tetragonal		a = 9.044, c = 4.937 Z=2	403.8	10.27	metallic
K2Au2SnS4	triclinic	P1	a=8.212 b=11.019 c=7.314 α=97.82° β=111.72° γ=72.00° Z=2	483.2	4.941	band gap 2.75 eV	[96][54]
K2Au2Sn2S6	tetragonal	P4/mmc	a=7.968 c=19.200 Z=4	1219	4.914	band gap 2.30 eV	[96][54]
Cs2Au2SnS4	orthorhombic	Fddd	a = 6.143 b = 14.296 c = 24.578 Z = 4	2158.4			[96]
Ba[Au2SnS4]	orthorhombic	C2221	a=6.6387 b=11.0605 c=10.9676 Z=1	805.32	6.418	red; blue-green luminescent	[96]
K2Hg3Sn2S8							[97]
Cu2HgSnS4 Velikite	tetrahedral	I42m	a = 5.55, c = 10.91	336	5.450	dark grey	[98]
SrHgSnSe4							[99]
BaHgSnSe4	orthorhombic	Fdd2	a 22.441 b 22.760 c 13.579				[99]
EuHgSnS4		Ama2	a=10.3730 b=10.4380 c=6.5680			SHG 1.77×AgGaS2	[100]
Tl4SnS4						0d
Tl2SnS3						1d
Tl2Sn2S5						3d
Tl4Sn5S12						3d
PbSnS2 Teallite	orthorhombic	Pnma	a = 4.26, b = 11.41, c = 4.09	198.8	6.36	metallic
PbSnS3 Suredaite	orthorhombic	Pnma	a=8.738 b=3.792 c=14.052 Z=4	466	6.01	metallic	[13]
(Pb,Sn)12.5Sn5FeAs3S28 Coiraite	monoclinic		a = 5.84, b = 5.86, c = 17.32 β = 94.14° Z=4	591	5.92	dark grey	[101]
Fe2+(Pb,Sn2+)6Sn4+2Sb2S14 Franckeite	triclinic	P1	a = 46.9, b = 5.82, c = 17.3 α = 90°, β = 94.66°, γ = 90° Z=8	4701	5.90	black	[102]
Pb25.7Sn8.3Mn3.4Sb6.4S56.2 Ramosite	monoclinic		a = 5.82, b = 5.92, c = 17.65 β = 99.1°	600			[103]
Pb3Sn4FeSb2S14 Cylindrite	triclinic	P1			5.46	black	[104]
Pb6Sn3FeSb3S16 Potosíite	triclinic					grey
(Pb,Ag)4Sn4FeSb2S15 Incaite	monoclinic						[105]
Pb2Fe2Sn2Sb2S11 Plumbostannite						dark grey	[106]
Ba5Pb2Sn3S13	orthorhombic	Pnma					[107]
Pb2SnInBiS7 Abramovite	triclinic	P1	a = 23.4, b = 5.77, c = 5.83 α = 89.1°, β = 89.9°, γ = 91.5°	786.79		metallic	[108]
Pb8Sn7Cu3(Bi,Sb)3S28 Lévyclaudite	triclinic	P1			5.71	grey	[109]