Carbide bromide

Class of chemical compounds

Carbide bromides are mixed anion compounds containing bromide and carbide anions. Many carbide bromides are cluster compounds, containing on, two or more carbon atoms in a core, surrounded by a layer of metal atoms, encased in a shell of bromide ions. These ions may be shared between clusters to form chains, double chains or layers.[1]

The great majority of these carbide bromide compounds contain rare earth elements. Since these elements have similar properties, similar structures can be made by substituting the elements. R2CBr2 forms a structure with layers of R6C clusters that contain one carbon atom. Each layer has bromide coating the top and bottom. Very similar is R2CBr2 which has layers of R6C2 clusters containing pairs of carbon atoms. This dicarbon is an ethenide (C24−), and contains a double bond. Layers have bromide on both sides, and so they are only weakly held together by van der Waals forces. If these layers are aligned with each other a 1T- form results with a small c measurement on the unit cell. In some compounds the layers are not quite aligned, but repeat after three layers giving a 3R form, with a larger c unit cell height. Where the layers align, the crystal system is trigonal. But if the layers never quite align at any height, a monoclinic crystal results. The C2 unit sits at an angle to the layers, and thus reduces symmetry compared to compounds with single carbon atoms in the cluster.[1]

In R2CBr there are layers of R6C that share bromide between layers.[1]

List

formula system space group unit cell volume density comment reference
Sc7CBr12 trigonal R3 a=13.628, c=9.203 4.33 [2]
Y2CBr2 trigonal R3m a=3.7545, c=29.125 4.90 bronze [2]
Y2C2Br2 monoclinic C12/m1 a=6.953, b=3.764, c=9.938, β=99.98 3.85 superconductor Tc=5.04K [2][3]
Y2C0.7Br2 trigonal P3m1 a=3.73 c=9.864 4.83 grey [2]
Y10Br18(C2)2 monoclinic P21/n a=9.729 b=16.323 c=13.229 β =121.131° Z=24 1798.3 black [4]
Na0.23Y2C2Br2 monoclinic C2/m a=7.061, b=3.724, c=10.464, β=92.96 4.43 copper red [5]
Zr6CBr14 orthorhombic Cmce a=14.69 b=13.229 c=11.991 [2]
NaZr6CBr14 orthorhombic Cmca a=14.6876, b=13.2266, c=11.9864 [5]
K4Zr6Br18C triclinic P1 a=10.114, b=10.283, c=10.374, α=118.54, β=99.98, γ=104.08, Z=1 [6]
RbZr6CBr14 orthorhombic Cmca a=14.719, b=13.287, c=12.043 [5]
Cs2Zr6Br10C trigonal R3c a=13.0862 c=35.823 Z=6 5312.8 [7]
CsZr6Br9C trigonal R3c a=13.1031 c=35.800 Z=6 5321.5 [7]
Cs3Zr6Br15C trigonal R3c a=13.116 c=35.980 Z=6 [7]
Cs4Zr6Br15C trigonal R3c a=13.098 c=35.756 Z=6 5312 [7]
La2C2Br monoclinic C12/c1 a=15.313, b=4.193, c=6.842, β=100.53,90 5.87 [8]
La3CBr5 monoclinic C12/c1 a=14.234, b=10.858, c=14.588, β =106.8 5.10 yellow [8]
La3C2Br3 orthorhombic C2221 a=11.533, b=17.0698, c=17.054 5.38 bronze [8]
La4C2Br5 orthorhombic Immm a = 3.9950, b = 8.277, c = 18.101 5.43 black [9]
La5C2Br9 orthorhombic Pnma a=11.309, b=9.9477, c=16.4911 5.15 red [2]
La5C6Br3 monoclinic C12/m1 a=22.809, b=3.9855, c=16.599, β=123.32 5.30 bronze [2]
La6C2Br9 monoclinic C2/c a=14,234 b=10.858 c=14.588 β=106.80 Z=4 2158.4 4.85 yellow insulator [10]
La10(C2)6Br6 monoclinic C2/m a = 22.809, b = 3.9855, c = 16.599, β = 123.32° Z=2 1260.9 5.301 bronze; air sensitive [11]
La3Br2C2B Pnma f =15.323, b = 3.973, c =11.567 black [12]
Ce2C2Br monoclinic C2/c a = 15.120, b = 4.179, c = 6.743, β = 101.09 ° [13]
Ce4CBr5 monoclinic C2/m a = 18.306, b = 3.9735, c = 8.378, β=104.91° [14]
Ce4C1.5Br5 monoclinic C2/m a = 18.996, b = 3.9310, c = 8.282, β = 106.74° [14]
Ce4C2Br5 orthorhombic Immm a = 3.9835, b = 8.186, c = 18.017 5.54 violet [9]
Ce4Br3C4 triclinic P 1 a = 4.227, b = 11.034, c = 11.268, α = 77.15°, β = 90.13° and γ = 84.42° [15]
Ce10(C2)6Br6 monoclinic C2/m a = 22.483, b = 3.9253, c = 16.375, β = 123.15° Z=2 1209.9 5.558 bronze; air sensitive [11]
Ce6Br3C3B2 monoclinic P21/m a = 8.602, b = 3.829, c = 10.220, β = 112.53 black [12]
Pr2CBr hexagonal P63/mmc a=3.8071, c=14.7787 6.69 black [2]
Pr2C2Br monoclinic C12/c1 a=15.054, b=4.139, c=6.713, β=101.08 6.24 [2]
Pr3CBr3 cubic I4131 a=11.61 5.73 [2]
Pr3CBr5 triclinic P1 a=7.571, b=9.004, c=9.062, α=108.57, β=97.77, γ=106.28 5.09 black [2]
Pr4C1.3Br5 monoclinic C2/m a = 18.467, b = 3.911, c = 8.258, β = 105.25° [14]
Pr4C1.5Br5 monoclinic C2/m a = 19.044, b = 3.9368, c = 8.254, β = 106.48° [14]
Pr5C2Br8 triclinic P1 a=9.096, b=12.185, c=16.688, α=79.57, β=89.86, γ=84.38 5.02 black [2]
Pr5C2Br9 monoclinic P21/n a = 10.069; b = 18.861; c = 10.459; β = 108.130° Z = 4 5.09 dark red [2]
Pr5C6Br3 monoclinic C12/m1 a=22.36, b=3.895, c=16.269, β=90,123.44 5,71 [2]
Pr6C2Br10 triclinic P1 a=7.571 b=9.004 c=9.062 α=108.57° β=97.77° γ=106.28° Z=1 544.8 5.09 black [16]
Pr7C3Br10 a=9.054, b=11.1265, c=13.352, α=79.641, β=72.57, γ=64.67 5.22 black [2]
Pr10C4Br15 triclinic P1 a=9.098 b=10.127 c=10.965 α=70.38° β=66.31° γ=70.84° Z=1 849.3 5.19 silver [16]
Pr10(C2)2Br16 triclinic P1 a = 9.096, b = 12.185, c = 16.688, α = 79.57°, β = 89.86°, γ = 84.38° metallic black [17]
Pr10(C2)6Br6 monoclinic C2/m a = 22.36, b = 3.895, c = 16.269, β = 123.44° Z=2 bronze; air sensitive [11]
Pr14C6Br20 triclinic P1 a=9.098 b=10.935 c=13.352 α=86.27° β=75.57° γ=66.88° Z=1 1157.8 5.23 black [16]
Pr6C2Cl5Br5 monoclinic C2/c a = 13.689(1) Å, b = 10.383(1) Å, c = 14.089(1) Å, β = 106.49(1)° yellow to green [18]
Gd2CBr hexagonal P63/mmc a=3.7858, c=14.209 7.65 dark grey [8]
Gd2Br2C trigonal P3m1 a=3.8209, c=9.824 black [19]
3s-Gd2C2Br2 monoclinic C2/m a = 7.066, b = 3.827, c = 9.967, β = 99.95° 5.69 black; contains C24− [20][21][22]
Gd2C2Br2 monoclinic C2/m a=7.025, b=3.8361, c=9.868, β =94.47 6.24 gold [8]
Gd4C2Br3 orthorhombic Pnma a = 10.844, b = 3.730, c = 20.361 6.58 bronze [23]
Gd10C4Br18 monoclinic P21/n a=9.7406 b=16.4817 c=11.8604 β =104.394° Z=24 contains C24− [4]
Gd10(C2)6Br6 monoclinic C2/m a = 21.507, b = 3.7193, c = 15.331, β = 123.34° Z=2 1024.5 6.254 bronze; air sensitive [11]
Gd4Br3C2B monoclinic P21/m a=9.547, b=3.693, c=l2.44,5, β=106.68 black [12]
K2[Gd10(C2)2]Br19 orthorhombic Pbcn a=12.751, b=23.17, c=14.423 5.01 black [24]
K2[Gd10(C2)2]Br20 orthorhombic Pbca a=1.2751, b=2.317, c=1.4423 4.70 black [24]
Rb2[Gd10(C2)2]Br19 orthorhombic Pbcn a=1.2737, b=2.325, c=1.4412 5.15 black [24]
Cs2[Gd10(C2)2]Br19 orthorhombic [24]
TbCBr monolinic C12/m1 a=7.015, b=3.801, c=9.948, β=100.05 6.28 [2]
Tb2CBr hexagonal P63/mmc a=3.6915, c=14.043 8.21 [2]
Tb2CBrH hexagonal P63mc a=3.7376, c=14.315 7.88 [5]
Tb4C2Br3 orthorhombic Pnma a = 10.743, b = 3.706, c = 20.194 7.31 bronze [23]
Tb10Br18(C2)2 monolinic P121/c1 a=9.7562 b=16.4254 c=13.3043 β =120.675° 1833.7 5.57 dark red [4][2]
Rb2[Tb10(C2)2]Br19 orthorhombic a=1.2664, b=2.3105, c=1.4303 black [24]
Dy10Br18(C2)2 monolinic P21/c a = 9.740 b = 16.340 c = 13.247 β = 120.869° Z = 2 1809.6 black [25]
Ho10Br18(C2)2 monolinic P21/n a=9.6838 b=16.2436 c=11.6374 β =104.427° Z=24 1772.8 [4]
[Er10(C2)2]Br18 monoclinic P21/n a = 9.718, b = 16.234, c = 11.638, β = 104.00°; Z = 2 5.89 black [26]
Lu2CBr2 trigonal R3m a= 3.6663, c=28.799 7.75 gold [2]
La0.9Lu0.1CBr monoclinic C2/m a=7.434, b=4.0568, c=10.046, β=93.7 5.15 [5]
W30C2(Cl,Br)68 triclinic P1 a = 12.003, b = 14.862, c = 15.792, α = 88.75°, β = 68.85°, γ = 71.19° Z=1 2472.9 6.35 black [27]
Th6CBr15 orthorhombic Cmce a=15.764, b=14.16, c=13.124 5.72 green [28]
Y0.8Th0.2CBr monoclinic C2/m a=7.061, b=3.776, c=9.983, β=100.36 5.31 [5]

References

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  2. ^ a b c d e f g h i j k l m n o p q r s Villars, Pierre; Cenzual, Karin; Gladyshevskii, Roman (2014-12-17). Handbook of Inorganic Substances 2015. Walter de Gruyter GmbH & Co KG. p. 341. ISBN 978-3-11-031174-7.
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  19. ^ Simon, Arndt (March 1985). "Empty, filled, and condensed metal clusters". Journal of Solid State Chemistry. 57 (1): 2–16. Bibcode:1985JSSCh..57....2S. doi:10.1016/S0022-4596(85)80055-4.
  20. ^ Miller, Gordon J.; Burdett, Jeremy K.; Schwarz, Christine; Simon, Arndt (November 1986). "Molecular interstitials: an analysis of the gadolinium carbide chloride, Gd2C2Cl2". Inorganic Chemistry. 25 (24): 4437–4444. doi:10.1021/ic00244a031. ISSN 0020-1669.
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  22. ^ Mattausch, Hj.; Kremer, R. K.; Eger, R.; Simon, A. (March 1992). "3s-Gd2C2Br2: Eine neue Stapelvariante". Zeitschrift für anorganische und allgemeine Chemie (in German). 609 (3): 7–11. doi:10.1002/zaac.19926090302. ISSN 0044-2313.
  23. ^ a b Bauhofer, Christine; Mattausch, Hansjürgen; Kremer, Reinhard K.; Simon, Arndt (September 1995). "Die Gadoliniumcarbidhalogenide Gd4C2X3 (X = Cl, Br)". Zeitschrift für anorganische und allgemeine Chemie (in German). 621 (9): 1501–1507. doi:10.1002/zaac.19956210911. ISSN 0044-2313.
  24. ^ a b c d e Ließ, Henning; Steffen, Frank; Meyer, Gerd (January 1997). "Quaternary chlorides and bromides with interstitially stabilized double octahedra, A2[Gd10(C2)2]Cl19 (A = Rb, Cs), A2[Gd10(C2)2]Br19 (A = K,Rb), Rb2[Tb10(C2)2]Br19, and K2[Gd10(C2)2]Br20". Journal of Alloys and Compounds. 246 (1–2): 242–247. doi:10.1016/S0925-8388(96)02476-0.
  25. ^ Daub, Kathrin; Meyer, Gerd (2008-01-15). "Octadecabromidobis(dicarbido)decadysprosium, [Dy 10 Br 18 (C 2 ) 2 ]". Acta Crystallographica E. 64 (1): i4. doi:10.1107/S1600536807066111. ISSN 1600-5368. PMC 2914882. PMID 21200454.
  26. ^ Uhrlandt, Stefan; Meyer, Gerd; Artelt, Holger M. (September 1994). "Cs[Er10(C2)2]I18 und [Er10(C2)2]Br18: zwei neue Beispiele für "reduzierte" Halogenide der Lanthanide mit isolierten [M10(C2)2]-Clustern". Zeitschrift für anorganische und allgemeine Chemie (in German). 620 (9): 1532–1536. doi:10.1002/zaac.19946200907. ISSN 0044-2313.
  27. ^ Ströbele, Markus; Meyer, H.-Jürgen (2010-07-05). "The Trigonal Prismatic Cluster Compound W 6 CCl 15 and a Carambolage of Tungsten Clusters in the Structure of the Heteroleptic Cluster Compound W 30 C 2 (Cl,Br) 68". Inorganic Chemistry. 49 (13): 5986–5991. doi:10.1021/ic100516t. ISSN 0020-1669. PMID 20521794.
  28. ^ Simon, Arndt; Böttcher, Fred; Cockcroft, Jeremy Karl (January 1991). "Th6Br15H7—Stabilization of a Th6Br12 Cluster by Seven Hydrogen Atoms". Angewandte Chemie International Edition in English. 30 (1): 101–102. doi:10.1002/anie.199101011. ISSN 0570-0833.
  • v
  • t
  • e
Salts and covalent derivatives of the bromide ion
HBr He
LiBr BeBr2 BBr3
+BO3 		CBr4
+C 		NBr3
BrN3
NH4Br
NOBr
+N 		Br2O
BrO2
Br2O3
Br2O5 		BrF
BrF3
BrF5 		Ne
NaBr MgBr2 AlBr
AlBr3 		SiBr4 PBr3
PBr5
PBr7
+P 		S2Br2
SBr2 		BrCl Ar
KBr CaBr2
 ScBr3 TiBr2
TiBr3
TiBr4 		VBr2
VBr3 		CrBr2
CrBr3 		MnBr2 FeBr2
FeBr3 		CoBr2 NiBr2
NiBr42− 		CuBr
CuBr2 		ZnBr2 GaBr3 GeBr2
GeBr4 		AsBr3
+As
+AsO3 		SeBr2
SeBr4 		Br2 Kr
RbBr SrBr2 YBr3 ZrBr3
ZrBr4 		NbBr5 MoBr2
MoBr3
MoBr4 		TcBr4 RuBr3 RhBr3 PdBr2 AgBr CdBr2 InBr
InBr3 		SnBr2
SnBr4 		SbBr3
+Sb
-Sb 		Te2Br
TeBr4
+Te 		IBr
IBr3 		XeBr2
CsBr BaBr2 * LuBr3 HfBr4 TaBr5 WBr5
WBr6 		ReBr3 OsBr3
OsBr4 		IrBr3
IrBr
4 		PtBr2
PtBr4 		AuBr
AuBr3 		Hg2Br2
HgBr2 		TlBr PbBr2 BiBr3 PoBr2
PoBr4 		AtBr Rn
FrBr RaBr2 ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* LaBr3 CeBr3 PrBr3 NdBr2
NdBr3 		PmBr3 SmBr2
SmBr3 		EuBr2
EuBr3 		GdBr3 TbBr3 DyBr3 HoBr3 ErBr3 TmBr2
TmBr3 		YbBr2
YbBr3
** AcBr3 ThBr4 PaBr4
PaBr5 		UBr4
UBr5 		NpBr3
NpBr4 		PuBr3 AmBr2
AmBr3 		CmBr3 BkBr3 CfBr3 EsBr2
EsBr3 		Fm Md No
  • v
  • t
  • e
Salts and covalent derivatives of the carbide ion
CH4
+H 		He
Li4C
Li2C2 		Be2C B4C
BnCm
+B 		C
C2
C4− 		CN−
(CN)2
+N 		CO
CO2
C3O2 		CF
CF4 		Ne
Na2C2 Mg2C Al4C3 SiC
+Si 		+P CS2
+S 		CCl4
+Cl 		Ar
K2C2 CaC
CaC2 		ScC
Sc3C4
Sc4C3
Sc15C19 		TiC VC Cr3C2 MnC2 Fe2C
Fe3C
Fe5C2 		CoC Ni2C CuC
CuC2 		Zn2C Ga +Ge +As CSe2 CBr4
+Br 		Kr
Rb2C2 SrC2 YC ZrC NbC MoC
Mo2C 		Tc Ru2C Rh2C PdC2 Ag2C2 CdC InC Sn Sb Te CI4
+I 		Xe
Cs2C2 BaC2 * LuC2 HfC TaC
TaC5 		WC Re2C Os2C Ir2C PtC Au2C2 Hg2C2 TlC ?PbC Bi Po At Rn
Fr Ra ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
 
* LaC2 CeC2 PrC2 NdC2 PmC2 SmC2 EuC2 GdC2 TbC2 DyC2 HoC2 ErC2 TmC2 YbC2
** Ac ThC
ThC2 		PaC UC NpC PuC
Pu2C3 		Am Cm Bk Cf Es Fm Md No