Carbide bromide explained

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 (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
Y2CBr2	trigonal	Rm	a=3.7545, c=29.125		4.90	bronze
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	Pm1	a=3.73 c=9.864		4.83	grey
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
NaZr6CBr14	orthorhombic	Cmca	a=14.6876, b=13.2266, c=11.9864
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
Cs2Zr6Br10C	trigonal	Rc	a=13.0862 c=35.823 Z=6	5312.8			^[7]
CsZr6Br9C	trigonal	Rc	a=13.1031 c=35.800 Z=6	5321.5
Cs3Zr6Br15C	trigonal	Rc	a=13.116 c=35.980 Z=6
Cs4Zr6Br15C	trigonal	Rc	a=13.098 c=35.756 Z=6	5312
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
La3C2Br3	orthorhombic	C2221	a=11.533, b=17.0698, c=17.054		5.38	bronze
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
La5C6Br3	monoclinic	C12/m1	a=22.809, b=3.9855, c=16.599, β=123.32		5.30	bronze
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°
Ce4C2Br5	orthorhombic	Immm	a = 3.9835, b = 8.186, c = 18.017		5.54	violet
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
Ce6Br3C3B2	monoclinic	P21/m	a = 8.602, b = 3.829, c = 10.220, β = 112.53			black
Pr2CBr	hexagonal	P63/mmc	a=3.8071, c=14.7787		6.69	black
Pr2C2Br	monoclinic	C12/c1	a=15.054, b=4.139, c=6.713, β=101.08		6.24
Pr3CBr3	cubic	I4131	a=11.61		5.73
Pr3CBr5	triclinic	P	a=7.571, b=9.004, c=9.062, α=108.57, β=97.77, γ=106.28		5.09	black
Pr4C1.3Br5	monoclinic	C2/m	a = 18.467, b = 3.911, c = 8.258, β = 105.25°
Pr4C1.5Br5	monoclinic	C2/m	a = 19.044, b = 3.9368, c = 8.254, β = 106.48°
Pr5C2Br8	triclinic	P	a=9.096, b=12.185, c=16.688, α=79.57, β=89.86, γ=84.38		5.02	black
Pr5C2Br9	monoclinic	P21/n	a = 10.069; b = 18.861; c = 10.459; β = 108.130° Z = 4		5.09	dark red
Pr5C6Br3	monoclinic	C12/m1	a=22.36, b=3.895, c=16.269, β=90,123.44		5,71
Pr6C2Br10	triclinic	P	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
Pr10C4Br15	triclinic	P	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
Pr10(C2)2Br16	triclinic	P	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
Pr14C6Br20	triclinic	P	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
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
Gd2Br2C	trigonal	Pm1	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 C2^4−	^[20] ^[21] ^[22]
Gd2C2Br2	monoclinic	C2/m	a=7.025, b=3.8361, c=9.868, β =94.47		6.24	gold
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 C2^4−
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
Gd4Br3C2B	monoclinic	P21/m	a=9.547, b=3.693, c=12.44,5, β=106.68			black
K2[Gd<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Br19	orthorhombic	Pbcn	a=12.751, b=23.17, c=14.423		5.01	black
K2[Gd<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Br20	orthorhombic	Pbca	a=1.2751, b=2.317, c=1.4423		4.70	black	^[24]
Rb2[Gd<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Br19	orthorhombic	Pbcn	a=1.2737, b=2.325, c=1.4412		5.15	black
Cs2[Gd<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Br19	orthorhombic
TbCBr	monolinic	C12/m1	a=7.015, b=3.801, c=9.948, β=100.05		6.28
Tb2CBr	hexagonal	P63/mmc	a=3.6915, c=14.043		8.21
Tb2CBrH	hexagonal	P63mc	a=3.7376, c=14.315		7.88
Tb4C2Br3	orthorhombic	Pnma	a = 10.743, b = 3.706, c = 20.194		7.31	bronze
Tb10Br18(C2)2	monolinic	P121/c1	a=9.7562 b=16.4254 c=13.3043 β =120.675°	1833.7	5.57	dark red
Rb2[Tb<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Br19	orthorhombic		a=1.2664, b=2.3105, c=1.4303			black
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
[Er<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Br18	monoclinic	P21/n	a = 9.718, b = 16.234, c = 11.638, β = 104.00°; Z = 2		5.89	black	^[26]
Lu2CBr2	trigonal	Rm	a= 3.6663, c=28.799		7.75	gold
La0.9Lu0.1CBr	monoclinic	C2/m	a=7.434, b=4.0568, c=10.046, β=93.7		5.15
W30C2(Cl,Br)68	triclinic	P	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

Notes and References

1. Book: Handbook on the physics and chemistry of rare earths . 1978 . North-Holland . Amsterdam . 9780444889669 . 221–225.
2. Book: Villars . Pierre . Handbook of Inorganic Substances 2015 . Cenzual . Karin . Gladyshevskii . Roman . 2014-12-17 . Walter de Gruyter GmbH & Co KG . 978-3-11-031174-7 . 341 . en.
3. Henn . R. W. . Schnelle . W. . Kremer . R. K. . Simon . A. . 1996-07-08 . Bulk Superconductivity at 10 K in the Layered Compounds Y 2 C 2 I 2 and Y 2 C 2 Br 2 . Physical Review Letters . en . 77 . 2 . 374–377 . 10.1103/PhysRevLett.77.374 . 10062435 . 1996PhRvL..77..374H . 0031-9007.
4. Compounds Comprising Lanthanide Clusters and Their Potential as Molecular Magnets: Synthesis, Structure and Magnetic Properties . 2016-06-13 . Thesis . en . Escobedo . Cruz.
5. Book: Villars . Pierre . Handbook of Inorganic Substances 2015 . Cenzual . Karin . Gladyshevskii . Roman . 2014-12-17 . Walter de Gruyter GmbH & Co KG . 978-3-11-031174-7 . 924 . en.
6. Qi . Ru-Yi . Corbett . John D . August 1998 . Comparative Zirconium Bromide Cluster Chemistry. A New Structure in K4Zr6Br18C . Journal of Solid State Chemistry . en . 139 . 1 . 85–92 . 10.1006/jssc.1998.7814. 1998JSSCh.139...85Q .
7. Qi . Ru-Yi . Corbett . John D. . March 1995 . Cs3Zr6Br15Z (Z = C, B): A Stuffed Rhombohedral Perovskite Structure of Linked Clusters . Inorganic Chemistry . en . 34 . 7 . 1657–1662 . 10.1021/ic00111a009 . 0020-1669.
8. Book: Villars . Pierre . Handbook of Inorganic Substances 2015 . Cenzual . Karin . Gladyshevskii . Roman . 2014-12-17 . Walter de Gruyter GmbH & Co KG . 978-3-11-031174-7 . 340 . en.
9. Mattausch . Hansjürgen . Schaloske . Manuel C. . Hoch . Constantin . Simon . Arndt . Halogenide der Seltenerdmetalle Ln4X5Z. Teil 2: Eine orthorhombische Verknüpfungsvarianteo-Ln4X5Z . Zeitschrift für anorganische und allgemeine Chemie . March 2008 . 634 . 3 . 498–502 . 10.1002/zaac.200700478.
10. Mattausch . Hansjürgen . Hoch . Constantin . Simon . Arndt . 2007-02-01 . La 6 C 2 Br 9 : La-Tetraederdoppel mit endohedralen C 4– -Ionen / La 6 C 2 Br 9 : La Bitetrahedral Clusters with Endohedral C 4− Ions . Zeitschrift für Naturforschung B . en . 62 . 2 . 143–147 . 10.1515/znb-2007-0201 . 98503059 . 1865-7117. free .
11. Mattausch . Hansjürgen . Kienle . Lorenz . Duppel . Viola . Hoch . Constantin . Simon . Arndt . September 2009 . Seltenerdethenidhalogenide Ln 2 n +6(C 2) n +4 X 2 n +2: Darstellung, Struktur, Verwachsung und Verzwilligung . Zeitschrift für anorganische und allgemeine Chemie . en . 635 . 11 . 1527–1535 . 10.1002/zaac.200900289.
12. Mattausch . Hansjürgen . Simon . Arndt . 1995-08-18 . Bromides of Rare Earth Metal Boride Carbides—A System of Building Blocks . Angewandte Chemie International Edition in English . en . 34 . 15 . 1633–1635 . 10.1002/anie.199516331 . 0570-0833.
13. Mattausch . Hansjürgen . Simon . Arndt . July 2011 . Variationen modulo 4-4+, 4+3-3+4-, 4-5+, 5-4+4-5+4-4+ bei Seltenerdcarbidhalogeniden . Zeitschrift für anorganische und allgemeine Chemie . en . 637 . 9 . 1093–1100 . 10.1002/zaac.201100055.
14. Mattausch . Hansjürgen . Schaloske . Manuel C. . Hoch . Constantin . Zheng . Chong . Simon . Arndt . March 2008 . Seltenerdhalogenide Ln4X5Z. Teil 1: C und/oder C2 in Ln4X5Z . Zeitschrift für anorganische und allgemeine Chemie . de . 634 . 3 . 491–497 . 10.1002/zaac.200700500. free .
15. Struktur, Verzwillingung und Eigenschaften von Ce4Br3C4. Zeitschrift für Anorganische und Allgemeine Chemie. 2000. 10.1002/(SICI)1521-3749(200002)626:2<518::AID-ZAAC518>3.0.CO;2-2. Mattausch. Hansjürgen. Oeckler. Oliver. Kremer. Reinhard K.. Simon. Arndt. 626. 2. 518–523.
16. Schaloske . Manuel Christian . Mattausch . Hansjürgen . Duppel . Viola . Kienle . Lorenz . Simon . Arndt . 2009-08-01 . The Starting Members of the Series Pr 4n+2 (C 2) n Br 5n+5 (n = 1, 2, 3) . Zeitschrift für Naturforschung B . en . 64 . 8 . 922–928 . 10.1515/znb-2009-0808 . 197260171 . 1865-7117. free .
17. Schaloske . Manuel Christian . Mattausch . Hansjürgen . Kienle . Lorenz . Simon . Arndt . October 2008 . Pr 10 (C 2) 2 Br 16 : Eine neue Struktur mit diskreten Pr 10 -Doppeloktaedern . Zeitschrift für anorganische und allgemeine Chemie . en . 634 . 12–13 . 2246–2254 . 10.1002/zaac.200800204.
18. Schaloske . Manuel C. . Mattausch . Hansjürgen . Kienle . Lorenz . Simon . Arndt . August 2008 . Pr6C2-Doppeltetraeder in Pr6C2Cl10 und Pr6C2Cl5Br5 . Zeitschrift für anorganische und allgemeine Chemie . 634 . 9 . 1493–1500 . 10.1002/zaac.200800026.
19. Simon . Arndt . March 1985 . Empty, filled, and condensed metal clusters . Journal of Solid State Chemistry . en . 57 . 1 . 2–16 . 10.1016/S0022-4596(85)80055-4. 1985JSSCh..57....2S .
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 . en . 25 . 24 . 4437–4444 . 10.1021/ic00244a031 . 0020-1669.
21. Book: Villars . Pierre . Handbook of Inorganic Substances 2015 . Cenzual . Karin . Gladyshevskii . Roman . 2014-12-17 . Walter de Gruyter GmbH & Co KG . 978-3-11-031174-7 . 353 . en.
22. Mattausch . Hj. . Kremer . R. K. . Eger . R. . Simon . A. . March 1992 . 3s-Gd2C2Br2: Eine neue Stapelvariante . Zeitschrift für anorganische und allgemeine Chemie . de . 609 . 3 . 7–11 . 10.1002/zaac.19926090302 . 0044-2313.
23. Bauhofer . Christine . Mattausch . Hansjürgen . Kremer . Reinhard K. . Simon . Arndt . September 1995 . Die Gadoliniumcarbidhalogenide Gd4C2X3 (X = Cl, Br) . Zeitschrift für anorganische und allgemeine Chemie . de . 621 . 9 . 1501–1507 . 10.1002/zaac.19956210911 . 0044-2313.
24. 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 . en . 246 . 1–2 . 242–247 . 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 . 10.1107/S1600536807066111 . 1600-5368 . 2914882 . 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 . de . 620 . 9 . 1532–1536 . 10.1002/zaac.19946200907 . 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 . en . 49 . 13 . 5986–5991 . 10.1021/ic100516t . 20521794 . 0020-1669.
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 . en . 30 . 1 . 101–102 . 10.1002/anie.199101011 . 0570-0833.