Phosphide chloride

A Phosphide chloride is a mixed anion compound containing both phosphide (P³⁻) and chloride (Cl⁻) ions.

A common structural element is P₇³⁻ which is called heptaphosphanortricyclane with a formal IUPAC name of heptaphosphatricyclo[2.2.1.0^2,6]heptane.^[1]

Group 12 elements, cadmium and mercury are in most of the known compounds.

List

name	formula	formula weight	crystal system	space group	unit cell Å	volume	density	comments	ref
	Ca3PCl3		cubic	Pm3m	a=5.713 Z=1	186.48	2.29		[2]
	Cu6PS5Cl	607.96	cubic	P43m	a=9.6962 Z=4	911.6	4.430	red	[3]
	Sr2PCl		cubic		a=6.18				[4]
	Sr2P7Cl		monoclinic	C2/c	a=14.571 b=12.212 c=22.292 β=103.740° Z=16	3853	3.948	P73–, clusters	[1]
	Ag6PS5Cl		cubic	P43m	a=10.3514 Z=4	1109.2	5.234	orange	[3]
	α-Cd3PCl3		hexagonal		a=7.63 c=7.13			pale yellow >530 °C or quenched	[5]
	β-Cd3PCl3		monoclinic		a=6.99 b=7.97 c=7.38 β=118.1°			pale yellow <530 °C	[5]
	Cd4P2Cl3	617.89	cubic	Pa3	a=12.1474 Z=8	1792.5	4.579	yellow; band gap 2.36 eV	[6]
	Cd2P3Cl		monoclinic	C2/c	a=7.98 b=8.98 c=7.55 β=			brown; band gap 1.87	[7]
	Cd2PCl2		monoclinic	P21/n	a=7.736 b=8.957 c=7.880 β=118.92° Z=4	477.93	4.540	yellow	[8][9]
	Cd7P4Cl6		cubic	Pa3	a=11.93			light green	[7]
	Ba2P7Cl		monoclinic	P21/m	a = 11.726, b = 6.829, c = 6.337, β = 95.27°, Z = 2			P73–, clusters	[1][10]
	La3Zn4P6Cl		orthorhombic	Cmcm	a= 4.0576 b 13.632 c 21.547 Z=4	1191.8	5.013	black; thermal conductivity 0.7 Wm−1 K−1 (low)	[11][12]
	Eu2PCl		cubic	Fm3m	a = 6.106, Z = 2				[13]
	W6PCl17		orthorhombic	Imm2	a=6.7835 b=15.8762 c=10.0727 Z=2	1084.79	5.3168	black	[14]
	W4(PCl)Cl10		monoclinic	C2/m	a=13.257 b=9.850 c=11.400 β=91.38 Z=4	1488.2	5.161	black; chloro-phosphinidene ligand	[14]
	[Hg4P2][HfCl6]		orthorhombic	Pbca	a=12.919 b=13.263 c=16.239 Z=8	2783	5.994	yellow	[15]
	Hg2PCl2		monoclinic	I2/m	a=7.643,b=7.977,c=8.539,β=115.23°,Z=4	469.8	7.113	yellow	[16][17]
	Hg2P3Cl		monoclinic	C2/c	a = 7.834, b = 8.844, c = 7.591, β = 98.68°, Z = 4				[18]
	[Hg6P4](TiCl6)Cl		cubic	Pa3	a=11.7675, Z=4	1627.2	6.627	black or dark brown	[19]
	(Hg6P4)(CrCl6)Cl	1627.57	cubic	Pa3	a=11.7364 Z=4	1616.6	6.687	yellow; resistivity is humidity sensitive	[20]
	(Hg6P4)(CuCl3)2		monoclinic	C2/c	a=23.633 b=8.956 c=14.248 β =124.213° Z=6	2493.9	6.660	pinkish-red; ferroelectric below 37 K: 114 μC m−2	[21]
	(Hg23P12)(ZnCl4)6		hexagonal	P62m	a=12.9774 c=11.749 Z=1	1713.6	6.035	yellow	[22]
	(Hg11P4)(GaCl4)4		monoclinic	C2/m	a=12.762 b=7.353 c=22.040 β=100.32 Z=2	2034.7	5.185	yellow	[23]
	[Hg4P2][ZrCl6]		orthorhombic	Pbca	a=12.899 b=13.255 c=16.196 Z=8	2769.1	5.604	yellow	[15]
	Hg4Ag5P8Cl5		orthorhombic	Cmcm	a=11.1426 b=14.5064 c=11.8444 Z=4	1914.5	6.129	high temp	[24]
	Hg4Ag5P8Cl5		monoclinic	C2/m	a=14.490 b=10.904 c=6.2863 β=104.094 Z=2	963.4	6.090		[24]
	[Hg6P4Cl3](SnCl3)		cubic	P213	a = 11.865 Z=4				[25]
	(Hg6P4Cl3)(PbCl3)		cubic	P213	a=11.8837 Z=4	1678.24	6.916	yellow	[22]

References

1. Dolyniuk, Juli-Anna; Tran, Nhon; Lee, Kathleen; Kovnir, Kirill (July 2015). "Sr 2 P 7 X ( X = Cl, Br, and I): Synthesis, Crystal and Electronic Structures of Double Zintl Salts Containing Heptaphosphanortricyclane, P 7 3-: Double Zintl Salts with Heptaphosphanortricyclane, P 7 3-". Zeitschrift für anorganische und allgemeine Chemie. 641 (8–9): 1422–1427. doi:10.1002/zaac.201500140.
2. Hadenfeldt, C.; Herdejürgen, H. (October 1986). "Darstellung, kristallstruktur und thermisches verhalten der calciumphosphidchloride Ca2 − xP1 − xCl1+x (0 ⩽ x ⩽ 0,18) und Ca3PCl3". Journal of the Less Common Metals (in German). 124 (1–2): 93–103. doi:10.1016/0022-5088(86)90480-7.
3. Gao, Lihua; Wu, Xiaowen; Yang, Daqing; Tian, Xinyu; Xu, Jingjing; Zhang, Bingbing; Wu, Kui (2021). "M 6 PS 5 X (M = Ag, Cu; X = Cl, Br) chalcohalides exhibiting strong nonlinear optical responses and high laser damage resistances". Dalton Transactions. 50 (48): 17901–17905. doi:10.1039/D1DT03251H. ISSN 1477-9226. PMID 34851337. S2CID 244148134.
4. Hadenfeldt, Claus (1976-04-01). "Darstellung und Eigenschaften von Ca 2 AsBr, Sr 2 AsCl und Ca 3 AsBr 3 .: Preparation and Properties of Ca 2 AsBr, Sr 2 AsCl, and Ca 3 AsBr 3". Zeitschrift für Naturforschung B. 31 (4): 408–410. doi:10.1515/znb-1976-0403. ISSN 1865-7117. S2CID 95122668.
5. Breitinger, Dietrich; Herrmann, Wolfgang A.; Hiller, Wolfgang (14 May 2014). Synthetic Methods of Organometallic and Inorganic Chemistry, Volume 5, 1999: Volume 5: Copper, Silver, Gold, Zinc, Cadmium and Mercury. Georg Thieme Verlag. p. 177. ISBN 978-3-13-179211-2.
6. Roy, Anand; Shenoy, U. Sandhya; Manjunath, K.; Vishnoi, Pratap; Waghmare, Umesh V.; Rao, C. N. R. (2016-07-21). "Structure and Properties of Cd 4 P 2 Cl 3 , an Analogue of CdS". The Journal of Physical Chemistry C. 120 (28): 15063–15069. doi:10.1021/acs.jpcc.6b04058. ISSN 1932-7447.
7. Roy, Anand; Singh, Anjali; Aravindh, S. Assa; Servottam, Swaraj; Waghmare, Umesh V.; Rao, C. N. R. (2019-05-20). "Structural Features and HER activity of Cadmium Phosphohalides". Angewandte Chemie International Edition. 58 (21): 6926–6931. doi:10.1002/anie.201900936. ISSN 1433-7851. PMID 30908780. S2CID 195661520.
8. Olenev, A. V. (March 2003). "Synthesis, crystal and electronic structure of Cd2PCl2: influence of cation on characteristic structural features of pnictide halides of Group 12 metals". Russian Chemical Bulletin. 52 (3): 570–575. doi:10.1023/A:1023938202282. S2CID 96664638.
9. Olenev, A. V. (2003). "Synthesis, crystal and electronic structure of Cd2PCl2: influence of cation on characteristic structural features of pnictide halides of Group 12 metals". Russian Chemical Bulletin. 52 (3): 570–575. doi:10.1023/A:1023938202282. S2CID 96664638.
10. Schnering, Hans Georg V.; Menge, Günter (October 1981). "Zur Chemie und Strukturchemie der Phosphide und Polyphosphide. 26. Dibariumheptaphosphidchlorid Ba2P7Cl, eine Verbindung mit dem polycyclischen Anion P73?". Zeitschrift für anorganische und allgemeine Chemie. 481 (10): 33–40. doi:10.1002/zaac.19814811005.
11. Wang, Jian; Kaseman, Derrick; Lee, Kathleen; Sen, Sabyasachi; Kovnir, Kirill (2016-07-12). "Enclathration of X@La 4 Tetrahedra in Channels of Zn–P Frameworks in La 3 Zn 4 P 6 X (X = Cl, Br)". Chemistry of Materials. 28 (13): 4741–4750. doi:10.1021/acs.chemmater.6b01752. ISSN 0897-4756.
12. Dolyniuk, Juli-Anna; Kovnir, Kirill (2013-08-26). "Zintl Salts Ba2P7X (X = Cl, Br, and I): Synthesis, Crystal, and Electronic Structures". Crystals. 3 (3): 431–442. doi:10.3390/cryst3030431. ISSN 2073-4352.
13. Hadenfeldt, C.; Held, W. (September 1986). "Darstellung, eigenschaften und kristallstruktur der Europium(ii)-phosphidhalogenide Eu2PCl, Eu2PBr und Eu2PI". Journal of the Less Common Metals (in German). 123 (1–2): 25–35. doi:10.1016/0022-5088(86)90111-6.
14. Ströbele, Markus; Eichele, Klaus; Meyer, H.‐Jürgen (September 2011). "Phosphorus‐Centered and Phosphinidene‐Capped Tungsten Chloride Clusters". European Journal of Inorganic Chemistry. 2011 (26): 4063–4068. doi:10.1002/ejic.201100122. ISSN 1434-1948.
15. Li, Xiao‐Guo; Jiang, Xiao‐Ming; Zhang, Ming‐Jian; Liu, Bin‐Wen; Fan, Yu‐Hang; Guo, Guo‐Cong; Huang, Jin‐Shun (2013-12-02). "Three‐Dimensional Mercury Pnictide [Hg 4 Z 2 ] 2+ Cationic Frameworks Stabilized by Tetravalent Metal Halide Anions in Supramolecular Complexes: [Hg 4 Z 2 ][MCl 6 ] (Z = P, As; M = Zr, Hf)". European Journal of Inorganic Chemistry. 2013 (35): 5980–5986. doi:10.1002/ejic.201300888. ISSN 1434-1948.
16. Breitinger, Dietrich; Herrmann, Wolfgang A.; Hiller, Wolfgang (14 May 2014). Synthetic Methods of Organometallic and Inorganic Chemistry, Volume 5, 1999: Volume 5: Copper, Silver, Gold, Zinc, Cadmium and Mercury. Georg Thieme Verlag. p. 207. ISBN 978-3-13-179211-2.
17. Olenev, Andrei V.; Shevelkov, Andrei V.; Popovkin, Boris A. (January 1999). "Crystal Structure of Hg2PCl2and Electronic Structure of Its Main "Building Unit"—The (P2Hg6) Octahedron". Journal of Solid State Chemistry. 142 (1): 14–18. Bibcode:1999JSSCh.142...14O. doi:10.1006/jssc.1998.7977.
18. Shevelkov, A. V.; Dikarev, E. V.; Popovkin, B. A. (1994-07-01). Shevelkov, A. V.; Dikarev, E. V.; Popovkin, B. A. (eds.). "Helical [unk](P 1− ) chains in the structures of Hg 2 P 3 Br and Hg 2 P 3 Cl". Zeitschrift für Kristallographie - Crystalline Materials. 209 (7): 583–585. Bibcode:1994ZK....209..583S. doi:10.1524/zkri.1994.209.7.583. ISSN 2194-4946.
19. Olenev, Andrei V.; Shevelkov, Andrei V. (August 2001). "Synthesis, Structure, and Properties of [Hg6P4](TiCl6)Cl: The Problem of Host–Guest Interactions". Journal of Solid State Chemistry. 160 (1): 88–92. Bibcode:2001JSSCh.160...88O. doi:10.1006/jssc.2001.9196.
20. Peng, Si-Yan; Yang, Liu-Sai; Yao, Ming-Shui; Yu, Le-Shu (2018). "A new pnictidehalide with van der Waals host–guest interactions exhibiting both geometric spin frustration and resistive humidity sensitivity". New Journal of Chemistry. 42 (3): 1787–1795. doi:10.1039/C7NJ03351F. ISSN 1144-0546.
21. Jiang, Xiao-Ming; Yan, Zhi-Bo; Liu, Dan; Wang, Jing-Xue; Liu, Mei-Feng; Guo, Guo-Cong; Jin, Biao-Bing; Li, Xiao-Guang; Liu, Jun-Ming (December 2013). "Ferroelectric Transition in the Inorganic Supramolecular Complex (Hg 6 P 4 )(CuCl 3 ) 2". Chemistry: An Asian Journal. 8 (12): 2925–2931. doi:10.1002/asia.201301040. PMID 24006192.
22. Jiang, Xiao-Ming; Wang, Guan-E; Liu, Zhi-Fa; Zhang, Ming-Jian; Guo, Guo-Cong (2013-08-05). "Large Mid-IR Second-Order Nonlinear-Optical Effects Designed by the Supramolecular Assembly of Different Bond Types without IR Absorption". Inorganic Chemistry. 52 (15): 8865–8871. doi:10.1021/ic401056t. ISSN 0020-1669. PMID 23837877.
23. Jiang, Xiao-Ming; Li, Xiao-Guo; Fan, Yu-Hang; Liu, Bin-Wen; Zeng, Hui-Yi; Guo, Guo-Cong (2013). "New mercury-contained cationic frameworks stabilized by (GaCl4)− unit via weak electrostatic forces in supramolecular compounds (Hg11P4)(GaCl4)4 and (Hg3AsS)(GaCl4)". Dalton Transactions. 42 (43): 15475–15481. doi:10.1039/c3dt51451j. ISSN 1477-9226. PMID 24022795.
24. Oleneva, Olga S.; Shestimerova, Tatiana A.; Dikarev, Evgeny V.; Shevelkov, Andrei V. (2006-11-27). "P88− Polyanion with Phosphorus Atoms in Three Different Formal Oxidation States Stabilized by a Combination of Ag+ and Hg2+ Cations". Angewandte Chemie (in German). 118 (46): 7883–7886. Bibcode:2006AngCh.118.7883O. doi:10.1002/ange.200601155.
25. Olenev, Andrei V.; Baranov, Alexei I.; Shevelkov, Andrei V.; Popovkin, Boris A. (2002). "A New Family of Supramolecular Complexes with 3D Cationic Hg/Z Frameworks, SnX3− Guest Anions (Z = P, as, Sb; X = Cl, Br, I): Crystal Structures and Host−Guest Interactions". European Journal of Inorganic Chemistry. 2002 (3): 547–553. doi:10.1002/1099-0682(200203)2002:3<547::AID-EJIC547>3.0.CO;2-N.