Silicide carbide

Silicide carbides or carbide silicides are compounds containing anions composed of silicide (Si⁴⁻) and carbide (C⁴⁻) or clusters therof. They can be considered as mixed anion compounds or intermetallic compounds, as silicon could be considered as a semimetal.

Related compounds include the germanide carbides, phosphide silicides, boride carbides and nitride carbides. Other related compounds may contain more condensed anion combinations such as the carbidonitridosilicates with C(SiN₃)₄ with N bridging between two silicon atoms.[1]

Production

Silicide carbide compounds can be made by heating silicon, graphite, and metal together. It is important to exclude oxygen before and during the reaction.[2] The flux method involves a reaction in a molten metal. Gallium is suitable, because it dissolves carbon and silicon, but does not react with them.[3]

Properties

Silicide carbides are a kind of ceramic, yet they also have metallic properties. They are not as brittle as most ceramics, but are stiffer than metals. They have high melting temperatures.[4]

In air silicide carbide compounds are stable, and are hardly affected by water. The appearance is often metallic grey. When powdered the colour is dark grey.[5]

When ErFe₂SiC is dissolved in acid, mostly methane is produced, but the products include some hydrocarbons with two and three carbon atoms.[5]

The lanthanide contraction is evident with the cell sizes for rare earth element silicide carbides.[5]

List

formula	system	space group	unit cell Å	volume	density	comment	ref
Ti₃SiC₂	hexagonal	P6₃/mmc	a = 3.064 c = 17.65 Z=2	143.5	4.53	mp 2300°C	[6]
Ti₅Si₃C_x							[4]
Y₃Si₂C₂	orthorhombic	Cmmm	a=3.845 b=15.634 c=4.213	253.3		Pauli paramagnetic grey metallic air stable	[7]
Y₅Si₃C_1.8							[8]
Y_1.8C₂Si₈(B₁₂)₃	rhombohedral	R3m	a=10.101, c=16.441, Z=3	1452.7	1.551		[3]
YCr₂Si₂C	tetragonal	P4/mmm	a=3.998 c=5.289 Z=1			Pauli paramagnetic grey metallic	[9]
YCr₃Si₂C							[10]
YMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
YFe₂SiC	orthorhombic	Cmcm	Z=4	270		grey metallic air stable	[5]
YRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Ba₃Si₄C₂	tetragonal	I4/mcm	a = 8.7693 c = 12.3885			semiconductor; contains [Si₄]⁴⁻ and [C₂]²⁻	[12]
La₃Si₂C₂	orthorhombic	Cmmm	a=4.039,b=16.884, and c=4.506	307.3		grey metallic air stable	[7]
LaCr₂Si₂C	tetragonal	P4/mmm	a=4.037 c=5.347 Z=1				[9]
La₂Fe₂Si₂C	monoclinic	C2/m	Z=2				[13]
Ce₃Si₂C₂	orthorhombic	Cmmm	a=3.990 b=16.592 c= 4.434	293.5		grey metallic air stable ?ferromagnetic (T_C=10K	[7]
CeCr₂Si₂C	tetragonal	P4/mmm	a=4.020 c=5.284 Z=1			grey metallic	[9]
Ce₂Fe₂Si₂C	monoclinic	C2/m	Z=2				[13]
CeMo₂Si₂C							[14]
CeRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Pr₃Si₂C₂	orthorhombic	Cmmm	a=3.967 b=16.452 c=4.399	287.1		grey metallic air stable ferromagnetic T_C=25K	[7]
PrCr₂Si₂C	tetragonal	P4/mmm	a=4.022, c = 5.352 Z=1	86.58	6.00	grey metallic Si-Si pair bond 2.453 Å	[9]
PrMo₂Si₂C	tetragonal	P4/mmm	a=4.2139 c=5.4093 Z=1	96.1		metallic dark grey	[15]
PrRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Nd₃Si₂C₂	orthorhombic	Cmmm	a=3.949 b=16.303 c=4.375	281.7		grey metallic air stable ferromagnetic T_C=30K	[7]
NdCr₂Si₂C	tetragonal	P4/mmm	a=4.026 c=5.336 Z=1			grey metallic	[9]
NdRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Sm₃Si₂C₂	orthorhombic	Cmmm	a=3.913 b=16.073 c=4.316	271.4		grey metallic air stable antiferromagnetic T_N=19K	[7]
SmCr₂Si₂C	tetragonal	P4/mmm	a=4.011 c=5.321 Z=1			grey metallic	[9]
SmMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
SmFe₂SiC	orthorhombic	Cmcm	Z=4	278		grey metallic air stable	[5]
Sm₂Fe₂Si₂C	monoclinic	C2/m	Z=2				[13]
SmRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Gd₃Si₂C₂	orthorhombic	Cmmm	a=3.886 b=15.863 c=4.726			grey metallic air stable antiferromagnetic T_N=50K	[7]
GdCr₂Si₂C	tetragonal	P4/mmm	a=4.007 c=5.324 Z=1	263.6		grey metallic	[9]
GdCr₃Si₂C	hexagonal	P6/mmm					[10]
GdMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
GdFe₂SiC	orthorhombic	Cmcm	Z=4	273		grey metallic air stable	[5]
GdRu₂SiC	orthorhombic	Cmcm	a = 3.830, b = 11.069, c = 7.157 Z=4	303.4	8.745	silvery air stable	[11][16]
Tb₃Si₂C₂	orthorhombic	Cmmm	a=3.854 c=15.702 c=4.236	256.3		grey metallic air stable antiferromagnetic T_N=28K	[7]
Tb_1.8C₂Si₈(B₁₂)₃	rhombohedral	R3m	a=10.1171, c=16.397, Z=3	1453.4	1.583		[3]
TbCr₂Si₂C	tetragonal	P4/mmm	a=4.002 c=5.314 Z=1			grey metallic	[9]
TbCr₃Si₂C	hexagonal	P6/mmm					[10]
TbMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
TbFe₂SiC	orthorhombic	Cmcm	Z=4	270		grey metallic air stable	[5]
TbRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Dy₃Si₂C₂	orthorhombic	Cmmm	a=3.838 b=15.611 c=4.203	251.8		grey metallic air stable antiferromagnetic T_N=30K	[7]
DyCr₂Si₂C	tetragonal	P4/mmm	a=3.999 c=5.306 Z=1			grey metallic	[9]
DyCr₃Si₂C	hexagonal	P6/mmm					[10]
DyMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
Dy₂Fe₂Si₂C	monoclinic	C2/m				grey metallic air stable	[7]
DyFe₂SiC	orthorhombic	Cmcm	Z=4	269		grey metallic air stable	[17]
DyRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Ho₃Si₂C₂	orthorhombic	Cmmm	a=3.828 b=15.507 c=4.189	248.7		grey metallic air stable metamagnetic T_N=14K	[7]
HoCr₂Si₂C	tetragonal	P4/mmm	a=3.996 c=5.274 Z=1			grey metallic	[9]
HoCr₃Si₂C	hexagonal	P6/mmm					[10]
HoMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
HoFe₂SiC	orthorhombic	Cmcm	Z=4	267		grey metallic air stable	[5]
HoRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Er₃Si₂C₂	orthorhombic	Cmmm	a=3.811 b=15.420 c=4.172	245.2		grey metallic air stable metamagnetic	[7]
Er_1.8C₂Si₈(B₁₂)₃	rhombohedral	R3m	a=10.0994, c=16.354, Z=3	1444.6	1.619		[3]
ErCr₃Si₂C	hexagonal	P6/mmm					[10]
ErMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
ErFe₂SiC	orthorhombic	Cmcm	Z=4	265		grey metallic air stable	[5]
ErRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
Tm₃Si₂C₂	orthorhombic	Cmmm	a=3.796, b=15.328, c=4.145			grey metallic air stable metamagnetic	[7]
TmCr₃Si₂C	hexagonal	P6/mmm					[10]
TmMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
TmFe₂SiC	orthorhombic	Cmcm	Z=4	263		grey metallic air stable	[5]
Tm₂Fe₂Si₂C	monoclinic	C2/m	a = 10.497, b = 3.882, c = 6.646, β = 128.96°			antiferromagnetic at T_N = 2.7 K metallic	[17]
TmRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
LuCr₃Si₂C	hexagonal	P6/mmm					[10]
LuMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
LuFe₂SiC	orthorhombic	Cmcm	Z=4	261		grey metallic air stable	[5]
Lu₂Fe₂Si₂C	monoclinic	C2/m				Pauli paramagnetic metallic	[17]
YRe₂SiC	orthorhombic	Cmcm	Z=4			superconductor T_c ≈ 5.9 K	[11][18]
Y₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
La₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
CeRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Ce₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
PrRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
NdRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Nd₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
SmRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Sm₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
GdRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Gd₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
TbRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Tb₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
DyRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Dy₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
HoRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Ho₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
ErRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Er₂Re₂Si₂C	monoclinic	C2/m	Z=2				[13]
TmRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
YOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
LaOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
CeOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
PrOs₂SiC	orthorhombic	Cmcm	a=3.9602,b=11.058,c=7.172 Z=4				[11]
NdOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
SmOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
GdOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
TbOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
DyOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
HoOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
ErOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
TmOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
ThMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
ThFe₂SiC	orthorhombic	Cmcm	a = 3.8632, b = 10.806, c = 6.950 Z=4	290	8.79	grey metallic air stable	[5]
Th₂Fe₂Si₂C	monoclinic	C2/m	Z=2				[13]
ThFe₁₀SiC_2-x	tetragonal		a = 10.053 and c = 6.516				[17]
ThMo₂Si₂C	tetragonal	P4/mmm	a = 4.2296 c = 5.3571 Z=1	95.84		superconductor Tc=2.2K	[19]
ThRu₂SiC	orthorhombic	Cmcm	Z=4				[11]
ThRe₂SiC	orthorhombic	Cmcm	Z=4				[11]
Th₂Re₂Si₂C	monoclinic	C2/m	a=11.1782, b=4.1753, c=7.0293, β=128.721° Z=2				[13]
ThOs₂SiC	orthorhombic	Cmcm	Z=4				[11]
U₃Si₂C₂	tetrahedral	I4/mmm	a=3.5735 c=18.882 Z=2	241.1	10.94	C-Si bond 1.93 Å Spin glass freeze at 28K grey metallic air stable	[2][20]
U₂₀Si₁₆C₃	hexagonal	P6/mmm	a= 10.377, c= 8.005, Z= 1	746.5	11.67	grey metallic air stable	[2]
UCr₂Si₂C	tetragonal	P4/mmm	a =3.983 c =5.160 Z=1	81.84	8.32		[21]
UCr₃Si₂C	hexagonal	P6/mmm					[10]
UMn₂SiC	orthorhombic	Cmcm	Z=4				[11]
UFe₂SiC	orthorhombic	Cmcm	Z=4	268		grey metallic air stable	[5]
U₂MoSi₂C	tetragonal	P4/mbm	a = 6.67 c = 4.33				[22]
UOs₂SiC	orthorhombic	Cmcm	Z=4				[11]

References

Höppe, Henning A.; Kotzyba, Gunter; Pöttgen, Rainer; Schnick, Wolfgang (2001-11-23). "High-temperature synthesis, crystal structure, optical properties, and magnetism of the carbidonitridosilicates Ho2[Si4N6C] and Tb2[Si4N6C]". Journal of Materials Chemistry. 11 (12): 3300–3306. doi:10.1039/b106533p.
Pöttgen, Rainer; Kaczorowski, Dariusz; Jeitschko, Wolfgang (1993). "Crystal structure, magnetic susceptibility and electrical conductivity of the uranium silicide carbides U 3 Si 2 C 2 and U 20 Si 16 C 3". J. Mater. Chem. 3 (3): 253–258. doi:10.1039/JM9930300253. ISSN 0959-9428.
Salvador, James R.; Bilc, Daniel; Mahanti, S. D.; Kanatzidis, Mercouri G. (2002). "Gallium Flux Synthesis of Tb3−xC2Si8(B12)3: A Novel Quaternary Boron-Rich Phase Containing B12 Icosahedra". Angewandte Chemie International Edition. 41 (5): 844–846. doi:10.1002/1521-3773(20020301)41:5<844::AID-ANIE844>3.0.CO;2-R. ISSN 1521-3773. PMID 12491355.
Andrievski, R A (2017-03-31). "High-melting-point compounds: new approaches and new results". Physics-Uspekhi. 60 (3): 276–289. Bibcode:2017PhyU...60..276A. doi:10.3367/UFNe.2016.09.037972. ISSN 1063-7869. S2CID 126026240.
Witte, Anne M.; Jeitschko, Wolfgang (October 1994). "Carbides with Filled Re3B-Type Structure". Journal of Solid State Chemistry. 112 (2): 232–236. Bibcode:1994JSSCh.112..232W. doi:10.1006/jssc.1994.1297.
Nowotny, V (1971). "Strukturchemie einiger Verbindungen der Übergangsmetalle mit den elementen C, Si, Ge, Sn". Progress in Solid State Chemistry. 5: 27–70. doi:10.1016/0079-6786(71)90016-1.
Gerdes, Martin H.; Witte, Anne M.; Jeitschko, Wolfgang; Lang, Arne; Künnen, Bernd (July 1998). "Magnetic and Electrical Properties of a New Series of Rare Earth Silicide Carbides with the CompositionR3Si2C2(R=Y, La–Nd, Sm, Gd–Tm)". Journal of Solid State Chemistry. 138 (2): 201–206. Bibcode:1998JSSCh.138..201G. doi:10.1006/jssc.1998.7772.
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Pohlkamp, Marc W.; Jeitschko, Wolfgang (2001-11-01). "Preparation, Properties, and Crystal Structure of Quaternary Silicide Carbides RCr 2 Si 2 C (R = Y, La - Nd, Sm, Gd - Ho)". Zeitschrift für Naturforschung B. 56 (11): 1143–1148. doi:10.1515/znb-2001-1108. ISSN 1865-7117. S2CID 197329371.
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[1] Höppe, Henning A.; Kotzyba, Gunter; Pöttgen, Rainer; Schnick, Wolfgang (2001-11-23). "High-temperature synthesis, crystal structure, optical properties, and magnetism of the carbidonitridosilicates Ho2[Si4N6C] and Tb2[Si4N6C]". Journal of Materials Chemistry. 11 (12): 3300–3306. doi:10.1039/b106533p.

[:1-2] Pöttgen, Rainer; Kaczorowski, Dariusz; Jeitschko, Wolfgang (1993). "Crystal structure, magnetic susceptibility and electrical conductivity of the uranium silicide carbides U 3 Si 2 C 2 and U 20 Si 16 C 3". J. Mater. Chem. 3 (3): 253–258. doi:10.1039/JM9930300253. ISSN 0959-9428.

[:6-3] Salvador, James R.; Bilc, Daniel; Mahanti, S. D.; Kanatzidis, Mercouri G. (2002). "Gallium Flux Synthesis of Tb3−xC2Si8(B12)3: A Novel Quaternary Boron-Rich Phase Containing B12 Icosahedra". Angewandte Chemie International Edition. 41 (5): 844–846. doi:10.1002/1521-3773(20020301)41:5<844::AID-ANIE844>3.0.CO;2-R. ISSN 1521-3773. PMID 12491355.

[:7-4] Andrievski, R A (2017-03-31). "High-melting-point compounds: new approaches and new results". Physics-Uspekhi. 60 (3): 276–289. Bibcode:2017PhyU...60..276A. doi:10.3367/UFNe.2016.09.037972. ISSN 1063-7869. S2CID 126026240.

[:4-5] Witte, Anne M.; Jeitschko, Wolfgang (October 1994). "Carbides with Filled Re3B-Type Structure". Journal of Solid State Chemistry. 112 (2): 232–236. Bibcode:1994JSSCh.112..232W. doi:10.1006/jssc.1994.1297.

[6] Nowotny, V (1971). "Strukturchemie einiger Verbindungen der Übergangsmetalle mit den elementen C, Si, Ge, Sn". Progress in Solid State Chemistry. 5: 27–70. doi:10.1016/0079-6786(71)90016-1.

[:5-7] Gerdes, Martin H.; Witte, Anne M.; Jeitschko, Wolfgang; Lang, Arne; Künnen, Bernd (July 1998). "Magnetic and Electrical Properties of a New Series of Rare Earth Silicide Carbides with the CompositionR3Si2C2(R=Y, La–Nd, Sm, Gd–Tm)". Journal of Solid State Chemistry. 138 (2): 201–206. Bibcode:1998JSSCh.138..201G. doi:10.1006/jssc.1998.7772.

[8] Button, T.W.; McColm, I.J. (February 1984). "Reaction of carbon with lanthanide silicides IV: The Y5Si3-C system". Journal of the Less Common Metals. 97: 237–244. doi:10.1016/0022-5088(84)90028-6.

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