Carbide chloride explained

Carbide chlorides are mixed anion compounds containing chloride anions and anions consisting entirely of carbon. In these compounds there is no bond between chlorine and carbon. But there is a bond between a metal and carbon. Many of these compounds are cluster compounds, in which metal atoms encase a carbon core, with chlorine atoms surrounding the cluster. The chlorine may be shared between clusters to form polymers or layers. Most carbide chloride compounds contain rare earth elements. Some are known from group 4 elements. The hexatungsten carbon cluster can be oxidised and reduced, and so have different numbers of chlorine atoms included.

The carbide chlorides are a subset of the halide carbides, with related compounds including the carbide bromides, and carbide iodides. Cluster compounds similar to these carbides, may instead replace carbon with boron, hydrogen, nitrogen or phosphorus.

List

formula	system	space group	unit cell	volume	density	comment	reference
Ca3C3Cl2	orthorhombic	Cmcm	a=3.876, b=13.524, c=11.653		2.47	red	^[1]
Sc2CCl2		Pm1	a=3.39977 c=8.858		3.24	black	^[2]
Sc5CCl8	monoclinic	C12/m1	a=17.8 b=3.5259 c=12.052 β=130.11		2.99
Sc7C2Cl10	monoclinic	C12/m1	a=18.62 b=11.81 β=99.81		3.04	ruby red; moisture sensitive	^[3]
Ti6CCl14	orthorhombic	Cmce	a=12.4592 b=12.2458 c=10.9576		2.93	black
YCCl		C12/m1	a=6.82 b=3.713 c=9.327 β=94.75		3.85
Y2C0.7Cl2		Pm1	a=3.7022 c=9.195		3.91	silvery grey
Zr6CCl14	orthorhombic	Cmce	a=14.091 b=12.595 c=11.506		3.43	brown red	^[4]
KZr6CCl15	orthorhombic	Pnma	a=18.489 b=13.909 c=9.690 Z=4	2492		dark red; Zr6C clusters	^[5]
Rb4Zr6CCl18		C2/m	a=10.460 b=17.239 c=9.721 β=115.05 Z=2				^[6]
Rb[(Zr<sub>6</sub>C)Cl<sub>15</sub>]	orthorhombic	Pnma	a=18.484,b= 18.962,c=9.708 Z= 4	2505.4	3.12	dark red-brown	^[7]
Cs4[Sc<sub>6</sub>C]Cl13	tetragonal	I41/amd	a = 15.405, c = 10.179 Z=4			green black	^[8]
Cs[(Zr<sub>6</sub>C)Cl<sub>15</sub>]	orthorhombic	Pnma	a = 18.513 b = 13.916 c = 9.6383 Z=4	2483.1		dark red	^[9]
La2CCl		Rm	a=3.878 c=16.91		5.74	coppery red	^[10]
La2C2Cl	monoclinic	C12/c1	a=14.77 b=4.187 c=6.802 β=101.5		5.44	gold	^[11]
La3C3Cl2	monoclinic	C12/c1	a=7.771 b=12.962 c=6.91 β=104.3		5.16	gold
La4C2Cl5	orthorhombic	Immm	a=3.92 b=7.945 c=19.297		4.67	black
La4C5Cl2	monoclinic	C12/m1	a=22.57 b=3.91 c=1.019 β=95.69		5.07	gold
La5C2Cl9	triclinic	P	a=8.645 b=8.706 c=11.925 α=84.97° β=85.78° γ=61.31°		4.40	red
La6(C2)3Cl4	monoclinic	P21/c	a = 7.770, b = 12.962, c = 6.910 and β = 104.30° Z=2	674.4	5.158	gold; sheets of octahedra	^[12]
La8C8Cl5	monoclinic	P121/c1	a=7.756 b=16.951 c=6.878 β=104.2		5.24	gold
La8(C2)5Cl4	monoclinic	C2/m	a = 22.570, b = 3.9300, c = 10.190 β = 95.69° Z=2	899.4	5.071	gold
La11C11Cl7	monoclinic	P121/c1	a=7.77 b=47.038 c=6.901 β=104.28		5.19	gold
La14C14Cl9	monoclinic	P1C1	a=7.775 b=2.9963 c=6.895 β=104.21		5.19	gold
La20C20Cl13	monoclinic	P121/c1	a=7.762 b=42.941 c=6.903 β=104.26		5.18	black
La36C36Cl23	monoclinic	P121/c1	a=7.764 b=77.055 c=6.897 β=104.26		5.18	grey
K[La<sub>5</sub>(C<sub>2</sub>)]Cl10	monoclinic	P21/c	a=8.5632, b=15.074, 17.115 β=119.74 Z=4	1918.3	3.85	light red	^[13]
Ce2C2Cl	monoclinic	C12/c1	a=14.573, b=4.129, c=6.696, β=101.37		5.71	gold
Ce2(C2)2Cl	monoclinic	C2/c	a = 14.573, b = 4.129, c = 6.696, β = 101.37 °				^[14]
Ce3CCl5	monoclinic	C12/c1	a=13.899, b=8.71, c=15.765, β=98.22		4.29	orange
Ce4CCl8	monoclinic	P1C1	a=13.538, b=10.487, c=22.845, β=126.31		4.35	black	^[15]
Ce5C2Cl9	triclinic	P	a=8.57, b=8.627, c=11.869, α=84.8, β=85.5, γ=61.29			red
Ce6Cl10C2	monoclinic	C12/c1	a= 13.899,b= 8.710,c= 15.765,β= 98.22° Z=4	1888.9			^[16]
Ce8C8Cl5	monoclinic	P121/c1	a=7.669, b=16.784, c=6.798, β=104.05		5.46	gold
Ce18(C2)9Cl11	triclinic	P	a = 6.771, b = 7.657, c = 18.98,α = 88.90 °, β = 80.32 °, γ = 76.09 °
Ce26(C2)13Cl16	monoclinic	P21/c	a = 7.664, b = 54.25, c = 6.796, β = 103.98 °
K[Ce<sub>5</sub>(C<sub>2</sub>)]Cl10	monoclinic	P21/c	a=8.4739, b=15.017, c=1639 β=119.76 Z=4	1871.2	3.97	red
Pr3CCl5	monoclinic	C12/c1	a=13.867 b=8.638 c=15.69 β=97.67		4.37	yellow
Pr4C2Cl5	orthorhombic	Immm	a=3.848 b=7.759 c=17.01		5.00	black
Pr5C2Cl9	triclinic	P	a=8.526 b=8.592 c=11.821 α=84.77 β=85.42 γ=61.26		4.61	brown red
Pr6C2Cl10	monoclinic	C2/c	a = 13.687, b = 8.638, c = 15.690, β = 97.67°			yellow to green	^[17]
Pr8C8Cl5	monoclinic	C121/c1	a=7.617 b=16.689 c=6.769 β=103.94		5.57	gold
Pr11C11Cl7	monoclinic	P121/c1	a=7.612 b=6.127 c=6.761 β=103.92		5.56	gold
Pr14C14Cl9	monoclinic	P1c1	a=7.611 b=29.392 c=6.764 β=103.9		5.56	gold
KCl10	hexagonal	P63/m	a=8.426 c=14.894 Z=2	915.9		dark red	^[18]
RbCl10	hexagonal	P63/m	a=8.4499, c=14.976 Z=2	926	4.19	red; trigonal bipyrmamid of Pr containing a C2 unit	^[19]
Rb[Nd<sub>5</sub>(C<sub>2</sub>)]Cl10	hexagonal		a=08.398, c=14.88		4.33	dark red
Gd2C2Cl		Pm	a=3.6902, c=20.308
Gd2C2Cl2	monoclinic	Pm1	a=3.7633, c=9.4593		5.69	black; contains C2^4−
Gd3CCl3	cubic	I4132	a=10.734		6.34
Gd4C2Cl3	orthorhombic	Pnma	a=10.596, b=3.684, c=19.627		6.58	bronze	^[20]
Gd5C2Cl9	monoclinic	P121/c1	a=9.182, b=16.12, c=12.886, β=119.86		4.54	black
Gd5C6Cl3	monoclinic	C12/m1	2.1507,0.37193,1.5331,90,123.34		6.25	bronze
Gd6C3Cl5	monoclinic	C12/m1	a=16.688,b=3.6969,c=12.824, β=128.26		6.18	grey
Gd10C4Cl17	triclinic	P	a=8.498, b=9.174, c=11.462, α=104.56, β=95.98, γ=111.35		4.70	black; contains C2^4−
Gd10C4Cl18	triclinic	P	a = 8.498, b = 9.174, c = 11.462, α = 104.56°, β = 95.98°, γ = 111.35°, Z = 1			contains C2^4−	^[21]
[Gd<sub>4</sub>(C<sub>2</sub>)](Cl, I)6	tetragonal	P4/mbm	a = 13.475, c = 12.125, Z = 2			black	^[22]
Rb2[Gd<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Cl19	orthorhombic		a=1.2228, b=2.2347, c=1.3896		4.31	black	^[23]
Cs2[Gd<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Cl19	orthorhombic		a=1.2344, b=2.2434, c=1.3924		4.41	black
Cs3[Tb<sub>10</sub>(C<sub>2</sub>)<sub>2</sub>]Cl21	monoclinic	C2/c	Z = 4; a = 23.187; b = 12.458; c = 15.02; β = 98.13°			black	^[24]
Lu2CCl2		Rm	a=3.6017, c=27.16		7.07	brown
Lu2CCl2		Pm1	a= 3.5972, c=9.0925		7.05
Cs2Lu[Lu<sub>6</sub>C]Cl18		R	a = 9.817, c = 27.232, Z = 3				^[25]
Hf6CCl14	orthorhombic	Cmce	a=13.938, b=12.498, c=11.399		5.28
W2CCl8	orthorhombic	Pbca	a=11.96 b=12.156 c=10.9576		2.83	black
W6CCl15	monoclinic	C121/c1	a=9.8831 b=11.8945 c=17.867 β =107.883		5.47	black
W6CCl16	orthorhombic	Pnma	a=16.637 b=12.958 c=9.797		5.29	black
W6CCl18		P2c	a=8.923 c=17.503		4.82	black
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		black	^[26]
Li[W<sub>6</sub>CCl<sub>18</sub>]	hexagonal	P63/m	a = 8.8648, c = 17.490 Z=2	1188.2		black	^[27] ^[28]
(Bu4N)[W<sub>6</sub>CCl<sub>18</sub>]							^[29]
(Me4N)2[W<sub>6</sub>CCl<sub>18</sub>]
(Bu4N)2[W<sub>6</sub>CCl<sub>18</sub>]
(Bu4N)3[W<sub>6</sub>CCl<sub>18</sub>]
Na[W<sub>6</sub>CCl<sub>18</sub>]	hexagonal	P63/m	a=8.9592 c=17.5226 Z=2	1188.2
Ca[W<sub>6</sub>CCl<sub>18</sub>]	hexagonal	P63/m	a=8.9384 c=17.6526 Z=2	1220.4
Cu[W<sub>6</sub>CCl<sub>18</sub>]	triclinic	P	a=8.89 b=8.929 c=17.669 α=81.85 β=80.78 γ=60.39 Z=2	1200.7	5.025	black	^[30]
Cu(C2H6OS)6[W<sub>6</sub>CCl<sub>18</sub>]	monoclinic	C2/c	a=17.333 b=16.011 c=18.082 β=94.61 Z=4	5001.7	3.035	dark brown
Cu(C2H6OS)4[W<sub>6</sub>CCl<sub>18</sub>]2	triclinic	P	a=9.47 b=12.630 c=13.634 α=104.69° β=90.16° γ=92.99° Z=1	1575.2	4.095	dark violet
Ag[W<sub>6</sub>CCl<sub>18</sub>]	hexagonal	P63/m	a=8.874 c=17.58 Z=2	1199
Cs[W<sub>6</sub>CCl<sub>18</sub>]·CH3OH	orthorhombic	P212121	a = 9.6957, b =  14.046, c = 20.238 Z=4		4.623	black; W in trigonal prism around C

Notes and References

1. 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 . 352 . en.
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 . 354 . en.
3. Hwu . Shiou-Jyh . Corbett . John D. . John Corbett (chemist) . Kenneth Poeppelmeier . Poeppelmeier . Kenneth R. . March 1985 . Interstitial atoms in metal-metal bonded arrays: The synthesis and characterization of heptascandium decachlorodicarbide, Sc7Cl10C2, and comparison with the interstitial-free Sc7Cl10 . Journal of Solid State Chemistry . en . 57 . 1 . 43–58 . 10.1016/S0022-4596(85)80059-1.
4. 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.
5. Ziebarth . Robin P. . Corbett . John D. . August 1987 . Cation distributions within a cluster framework. Synthesis and structure of the carbon- and boron-centered zirconium cluster compounds KZr6Cl15C and CsKZr6Cl15B . Journal of the American Chemical Society . en . 109 . 16 . 4844–4850 . 10.1021/ja00250a015 . 0002-7863.
6. Zhang . Jie . Ziebarth . Robin P. . Corbett . John D. . February 1992 . Two novel phases containing centered, isolated zirconium clusters, Rb4Zr6Cl18C and Li6Zr6Cl18H . Inorganic Chemistry . en . 31 . 4 . 614–619 . 10.1021/ic00030a017 . 0020-1669.
7. Rohm . Henning W. . Köckerling . Martin . 2008-05-01 . Synthesis and Structure of and Cation Distribution in the Zirconium Cluster Rb[(Zr 6 C)Cl 15 ] . Zeitschrift für Naturforschung B . en . 63 . 5 . 507–512 . 10.1515/znb-2008-0505 . 197327959 . 1865-7117. free .
8. Artelt . Holger M. . Schleid . Thomas . Meyer . Gerd . September 1994 . Cs4[Sc6C]Cl13 und Cs4[Pr6(C2)]I13 ? zwei Beispiele für das fehlende Bindeglied bei der Verknüpfung der Baueinheiten [M6Z]X12iX6a ]. Zeitschrift für anorganische und allgemeine Chemie . de . 620 . 9 . 1521–1526 . 10.1002/zaac.19946200905 . 0044-2313.
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27. Weisser . Martina . Ströbele . Markus . Meyer . H.-Jürgen . November 2005 . A synthesis route for carbon-centered triprismo-hexatungsten cluster compounds and the crystal structure of Cs[W6CCl18]·CH3OH ]. Comptes Rendus Chimie . en . 8 . 11–12 . 1820–1826 . 10.1016/j.crci.2005.02.034.
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29. Welch . Eric J. . Crawford . Nathan R. M. . Bergman . Robert G. . Long . Jeffrey R. . 2003-09-01 . New Routes to Transition Metal-Carbido Species: Synthesis and Characterization of the Carbon-Centered Trigonal Prismatic Clusters [W 6 CCl 18 ] n - (n = 1, 2, 3) ]. Journal of the American Chemical Society . en . 125 . 38 . 11464–11465 . 10.1021/ja035962v . 13129326 . 0002-7863.
30. Mos . Agnieszka . Ströbele . Markus . Meyer . H.-Jürgen . October 2015 . Carbon Centered Trigonal Prismatic Tungsten Clusters [W 6 CCl 18 ] n- (n = 1, 2) containing Copper(I) and Copper(II): Tungsten Clusters [W 6 CCl 18 ] n- (n = 1, 2) with Copper(I) and (II) . Zeitschrift für anorganische und allgemeine Chemie . en . 641 . 12–13 . 2245–2249 . 10.1002/zaac.201500571. free .