The phosphidosilicates or phosphosilicides are inorganic compounds containing silicon bonded to phosphorus and one or more other kinds of elements. In the phosphosilicates each silicon atom is surrounded by four phosphorus atoms in a tetrahedron. The triphosphosilicates have a SiP3 unit, that can be a planar triangle like carbonate CO3. The phosphorus atoms can be shared to form different patterns e.g. [Si2P6]10− which forms pairs, and [Si3P7]3− which contains two-dimensional double layer sheets.[1] [SiP4]8− with isolated tetrahedra, and [SiP2]2− with a three dimensional network with shared tetrahedron corners.[2] SiP clusters can be joined, not only by sharing a P atom, but also by way of a P-P bond. This does not happen with nitridosilicates or plain silicates.

The phosphidosilicates can be considered as a subclass of the pnictogenidosilicates, where P can be substituted by N (nitridosilicates), As, or Sb. Also Silicon can be substituted to form other series of compounds by replacement with other +4 oxidation state atoms like germanium, tin, titanium or even tantalum.

List

formula name crystal

system

 space

group

 unit cell Å form MW density properties references
Li2SiP2 tetragonal I41/acd a=12.111 Å, c=18.658 Å, Z=32 V=2732.6 4 SiP4 tetrahedra are linked together to form a supertetrahedron. Supertetrahedrons are linked together by corner sharing. 103.91 2.02 [2][3]
LiSi2P3 I41/a a=18.4757  Å, c=35.0982  Å, Z=100 Interpenetrating networks of bridged supertetrahedra [3]
Li3Si3P7 monoclinic P21/m a = 6.3356 Å, b = 7.2198 Å, c = 10.6176 Å, β = 102.941°, Z = 2 grey [1]
Li5SiP3 Cubic Fm3m a=5.84 Z=1.33 SiP4 tetrahedra, but some Si replace by Li [4]
Li10Si2P6 P21/n a = 7.2051 Å, b = 6.5808 Å, c = 11.6405 Å, β = 90.580°, Z = 4 contains Si2P6 units with two Si atoms linked by two P atoms also known by Li5SiP3 [1]
Li8SiP4 lithium orthophosphidosilicate cubic Pa3 a=11.6784 Z=8 V=1592.76 207.49 1.73 orange red [2]
Li14SiP6 Cubic Fm3m a=5.9393 Z=4 SiP4 tetrahedra, but some Si replace by Li 1.644 [5]
Na19Si13P25 triclinic P1 a =13.3550 Å, b =15.3909 Å, c =15.4609 Å, α =118.05°, β =111.71°, γ =93.05°, Z =2 T3 supertetrahedra sodium ion conductor [6]
Na23Si19P33 monoclinic C2/c a =28.4985 Å, b =16.3175 Å, c = 13.8732 Å, β =102.35°, Z =4 solely T3 supertetrahedra sodium ion conductor [6]
Na23Si28P45 monoclinic P21/c a =19.1630 Å, b =23.4038 Å, c = 19.0220 Å, β =104.30°, Z =4 T3 and T4 supertetrahedra sodium ion conductor [6]
Na23Si37P57 monoclinic C2/c a =34.1017 Å, b =16.5140 Å, c = 19.5764 Å, β =111.53°, Z =4 solely T4 supertetrahedra sodium ion conductor [6]
LT-NaSi2P3 tetragonal I41/a a =19.5431 Å, c = 34.5317 Å, Z =100 fused T4 and T5 supertetrahedra sodium ion conductor [6]
HT-NaSi2P3 tetragonal I41/acd a =20.8976 Å, c = 40.081 Å, Z =128 solely fused T5 supertetrahedra sodium ion conductor [6]
Na2SiP2 disodium diphosphidosilicate Tetrahedral Pccn a = 12.7929 Å, b = 22.3109 Å, c = 6.0522 Å and Z = 16 edge‐shared SiP4 tetrahedra with 1 width chains dark red 0.43 eV [7]
Na5SiP3 monoclinic P21/c Z=4 a= 7.352 Å, b= 7.957, Å c= 13.164 Å, α=90.757° 2.06 also known by Na10Si2P6 band gap 1.292 eV [8][9]
Na3K2SiP3 trisodium dipotassium triphosphidosilicate Orthorhombic Pnma a=14.580 b=4.750 c= 13.020 V=901.7 Z=4 SiP3 triangles [10]
Na4Ca2SiP4 hexagonal P63mc a=913 c=617 V=151.5 SiP4 tetrahedra 2.128 [11]
Na4Sr2SiP4 hexagonal P63mc a=9.283 c=7.295 V=164 2.498 [11]
Na4Eu2SiP4 hexagonal P63mc a=9.251 c=7.198 V=160.7 3.226 [11]
MgSiP2 tetragonal I42d a=5.721 c=10.095 orange yellow; semiconductor band gap 2.24 eV; decomposed by water or acid [12]
AlSiP3 orthorhombic Pmnb a = 9.872, b = 5.861, c = 6.088, Z=4 P-P bonds black [13][14]
K2SiP2 orthorhombic Ibam a = 12.926, b = 6.867, c= 6.107, Z=4, V=542.07 one dimensional chain 2.061 [13][15]
KSi2P3 monoclinic C2/c a=10.1327 Å, b=10.1382 Å, c=21.118 Å, β=96.88°, Z=8 V=2153.8Å3 solely fused T3 supertetrahedra 2.321 dark red, band gap 1.72 eV [8]
KSi2P3 tetragonal I41/acd a =21.922 Å, c = 39.868 Å, Z =128 solely fused T5 supertetrahedra potassium ion conductor [16][17]
Ca2Si2P4 P41212 a = 7.173, c = 26.295 band gap 0.984 eV [18]
Ca3Si2P4 monoclinic a = 7.073 Å, b = 17.210 Å, c = 6.918 Å, β = 111.791° band gap 0.826 eV [18]
Ca3Si8P14 monoclinic P21/c a = 12.138 Å, b = 13.476 Å, c = 6.2176 Å, β = 90.934° band gap 0.829 eV [18]
Ca4SiP4 cubic a=11.875 V=1675 2.48 [19]
MnSiP2 tetrahedral I 4 2 d a 5.5823 c 10.230 metallic; SHG 32.8 pm/V [20]
Fe5SiP a=6.766 c=12.456 V=493.8 Z=6 6.83 [21]
CoSi3P3 monoclinic P21 (pseudo orthrhombic) a = 5.899, b = 5.703, c = 12.736, β = 90.00° Z=4 resistivity 0.62 Ohm cm band gap 0.12 eV [22]
NiSi3P4 tetragonal I42m a = 5.1598 c =10.350 Z = 2 3.22 [13][23]
NiSi2P3 Imm2 a = 3.505, b = 11.071, c = 5.307, Z = 2 [13][24]
FeSi4P4 a = 4.876, b = 5.545, c = 6.064, α = 85.33°, β = 68.40°, γ = 70.43° Z=4 P and Si random 3.38 resistivity 0.3 Ohm cm band gap 0.15, can take in Li or Na [13][22][25]
Cu4SiP8 I41/a a = 12.186, c = 5.732, Z = 8 P-P bonds [13][26]
ZnSiP2 Tetragonal I42d a = 5.399 Å c = 10.435 Å Z=4 V=304.173 Å3 chalcopyrite structure SiP4 and Zn4 tetrahedra 154.936 3.3 (measured) dark red clear; red luminescent; semiconductor; band gap 2.01 eV [13][27][28]
ZnSiP2 Cubic over 27 GPa Superconductor Tc = 8.2K [28]
Sr2SiP4 band gap 1.41 eV [29]
Sr4SiP4 cubic a=12.426 V=1919 3.48 [19]
SrSi7P10 triclinic P1 a =6.1521 Å, b =8.0420 Å, c =8.1374 Å, α =106.854°, β =99.020°, γ =105.190°, Z =1 tetrahedral network derived from T2 supertetrahedra band gap 1.1 eV [30][29]
RhSi3P3 monoclinic C2 a=5.525, b=7.210, c=5.522 β=118.31°, Z=2

P and Si random

 4.005 black [13][31]
RuSi4P4 triclinic P1 a = 4.936, b = 5.634, c = 6.162, α = 85.51°, β = 68.26°, γ = 70.69° Z=1 V=150 3.74 metallic [22][32]
RuSi4P4 triclinic P1 a=4.9362 b=5.6326 c=6.1649 α=85.5073° β=68.2559° γ=70.6990° 3.732 dark red;band gap 1.9 eV [33]
AgSiP2 Tetragonal I42d 6.5275, c = 8.550, Z = 4; V = 364.3 SiP4 corner sharing 305.77 5.58 shiny black [13]
Mg2In3Si2P7 monoclinic P21 a 6.9375 b 6.5646 c 14.469 β 103.87° Z=2 639.7 3.458 SHG 7.1 × AgGaS2; band gap 2.21 [34]
Sn4.2Si9P16 rhombohedral R3 a = 9.504 Å, α = 111.00°, and Z = 1 band gap 0.2 [35]
CdSiP2 tetragonal I42d a = 5.680 c = 10.431 Å Z=4 V=336.494 Å3 chalcopyrite structure 202.434 3.995 carmine colour; red luminescent [13][36][37]
Cs2SiP2 Dicesium catena-diphosphidosilicate Orthorhombic Ibam [13]
Cs5SiP3 Pentacesium triphosphidosilicate Orthorhombic Pnma a=6.064, b=14.336, c=15.722 SiP3 planar triangles dark metallic, air sensitive [38]
BaSi7P10 triclinic P1 a =6.1537 Å, b =8.0423 Å, c =8.1401 Å, α =106.863°, β =99.050°, γ =105.188°, Z =1 tetrahedral network derived from T2 supertetrahedra [30]
Ba2SiP4 Tetragonal I42d a = 9.90.57 Å, c = 7.31.80 Å; Z = 4 V=718.06 Å contains P-P bonds 426.65 band gap 1.45 eV [39][29]
Ba2SiP4 Orthorhombic Pnma a=12.3710 b=4.6296 c=7.9783 Z= 8 V=1443.9 chains of Si-P-Si 426.65 3.925 black band gap 1.7 eV [40]
Ba2Si3P6 band gap 1.88 [29]
Ba3Si4P6 monoclinic P21/m a=1153.7 Å, b=728.1 Å, c=752.7 Å, β = 99.41° V=623.76 Z=2 Zintl compound P-P and Si-Si bonds 3.78 black metallic [13][41]
Ba4SiP4 cubic a=13.023 V=2219 4.22 [13][19]
BaCuSi2P3 monoclinic a=4.5659 b=10.1726 c=6.8236 β = 109.311 V=299.10 layered [42]
LaSiP3 monoclinic a = 5.972, b = 25.255, c = 4.168, β= 135.71°, Z = 4 two dimensional network of boat-shaped six-membered rings of Si-P-Si-P-Si-P [43]
LaSi2P6 Cmc21 a= 10.129,b= 28.17,c= 10.374,Z= 16 P-P bonds 380.9 3.42 grey [13][44]
CeSiP3 orthorhombic Pn21a a = 5.861, b= 5.712, c= 25.295 Å, V=846.7 Å3, Z=8 P-P bonds 261.13 4.095 [13][45]
CeSi2P6 Cmc21 a= 10.118 Å,b= 28.03 Å,c= 10.311 Å,Z= 16, V=2.924 P-P bonds 382.1 3.47 grey [44]
PrSi2P6 Cmc21 a= 10.085 Å,b= 27.95 Å,c= 10.267 Å,Z= 16, V=2.895 nm3 P-P bonds grey [44]
NdSi2P6 Cmc21 a= 10.031,b= 27.81,c= 10.245,Z= 16, V=2.857 P-P bonds grey [44]
ReSi4P4
OsSi4P4 triclinic P1 a = 4.948, b = 5.620, c = 6.175, α = 85.65, β = 68.36, γ = 70.89, Z=4 V=150.6 4.72 metallic [22][32]
IrSi3P3 monoclinic C2 a=6.577, b=7.229, c=5.484 β=117.91°, Z=2 black [22][31]
IrSi3P3 monoclinic Cm a=6.5895 b=7.2470 c=5.4916 β=117.892 dark red;band gap 1.8 eV [33]
PtSi2P2 monoclinic P21 a=6.025 Å, b=9.468 Å, c=11.913 Å, β=102.91°,Z=8, V=552.2 6.327 high resistance metallic,shiny black, air sensitive [46]
PtSi3P2 triclinic P1 a=4.840 Å,b=5.482 Å,c=8.052 Å, α=91.57°, β=93.52°, γ=108.14°, Z=2 V=202.3 5.656 shiny black [46]
AuSiP rhombohedral R3m a=3.459, c = 17.200, Z = 3; V = 178.19 256.03 7.16 shiny black [13]
Th2SiP5 triclinic a=4.04.3 Å, b=4.04.5 Å, c = 10.279 pm, α = 90.09°, β = 90.09° and γ = 89.50°, Z = 1 chains of corner linked SiP4 tetrahedra, and square net of P [43]

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  38. ↑ Eisenmann, Brigitte; Klein, Jürgen; Somer, Mehmet (1990-01-01). "CO 32−-isostere Anionen in Cs5SiP3, Cs5SiAs3, Cs5GeP3 und Cs5GeAs3". Angewandte Chemie. 102 (1): 92–93. Bibcode:1990AngCh.102...92E. doi:10.1002/ange.19901020127. ISSN 1521-3757.
  39. ↑ Johrendt, Dirk; Arthur, Haffner (2017). "Synthesis, Crystal Structure, and Chemical Bonding of Ba2SiP4". Zeitschrift für Anorganische und Allgemeine Chemie. 643 (21): 1717–1720. doi:10.1002/zaac.201700320. ISSN 1521-3749.
  40. ↑ Haffner, Arthur; Weippert, Valentin; Johrendt, Dirk (2019-11-08). "Polymorphism of Ba 2 SiP 4: Polymorphism of Ba 2 SiP 4". Zeitschrift für anorganische und allgemeine Chemie. doi:10.1002/zaac.201900188.
  41. ↑ Eisenmann, Brigitte; Jordan, Hanna; Schäfer, Herbert (1984). "Ba3Si4P6, eine neue Zintlphase mit vernetzten Si4P5-Käfigen/On Ba3Si4P6, a New Zintl Phase with Connected Si4P5 Cages" (PDF). Zeitschrift für Naturforschung B. 39 (7): 864–867. doi:10.1515/znb-1984-0705. S2CID 94537299.
  42. ↑ Yox, Philip; Lee, Shannon J.; Wang, Lin-lin; Jing, Dapeng; Kovnir, Kirill (2021-04-01). "Crystal Structure and Properties of Layered Pnictides BaCuSi 2 Pn 3 (Pn = P, As)". Inorganic Chemistry. 60 (8): 5627–5634. doi:10.1021/acs.inorgchem.0c03636. ISSN 0020-1669. PMID 33794094. S2CID 232762736.
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  44. 1 2 3 4 Kaiser, Peter; Jeitschko, Wolfgang (July 1996). "The Rare Earth Silicon PhosphidesLnSi2P6(Ln= La, Ce, Pr, and Nd)". Journal of Solid State Chemistry. 124 (2): 346–352. Bibcode:1996JSSCh.124..346K. doi:10.1006/jssc.1996.0248.
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  46. 1 2 Perrier, Ch.; Kirschen, M.; Vincent, H.; Gottlieb, U.; Chenevier, B.; Madar, R. (1997). "Synthesis and Crystal Structures of Two New Platinum Phosphosilicides, PtSi3P2and PtSi2P2; Electrical Resistivity of PtSi3P2". Journal of Solid State Chemistry. 133 (2): 473–478. Bibcode:1997JSSCh.133..473P. doi:10.1006/jssc.1997.7512.
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