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CrP is Modderite structured and crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Cr3+ is bonded to six equivalent P3- atoms to form a mixture of distorted face, edge, and corner-sharing CrP6 pentagonal pyramids. There are a spread of Cr–P bond distances ranging from 2.31–2.41 Å. P3- is bonded in a 6-coordinate geometry to six equivalent Cr3+ atoms.
Cr2P crystallizes in the orthorhombic Imm2 space group. The structure is three-dimensional. there are six inequivalent Cr sites. In the first Cr site, Cr is bonded to four P atoms to form distorted CrP4 tetrahedra that share corners with two equivalent CrP5 square pyramids, corners with ten CrP4 tetrahedra, edges with two equivalent CrP5 square pyramids, and edges with two equivalent CrP4 tetrahedra. There are a spread of Cr–P bond distances ranging from 2.24–2.29 Å. In the second Cr site, Cr is bonded to four P atoms to form distorted CrP4 tetrahedra that share corners with two equivalent CrP5 square pyramids, corners with ten CrP4 tetrahedra, edges with two equivalent CrP5 square pyramids, and edges with two CrP4 tetrahedra. There are a spread of Cr–P bond distances ranging from 2.29–2.42 Å. In the third Cr site, Cr is bonded to five P atoms to form distorted CrP5 square pyramids that share corners with five equivalent CrP5 square pyramids, corners with six CrP4 tetrahedra, and edges with six CrP4 tetrahedra. There are a spread of Cr–P bond distances ranging from 2.37–2.51 Å. In the fourth Cr site, Cr is bonded in a 3-coordinate geometry to five P atoms. There are a spread of Cr–P bond distances ranging from 2.36–2.73 Å. In the fifth Cr site, Cr is bonded in a distorted square co-planar geometry to four equivalent P atoms. All Cr–P bond lengths are 2.47 Å. In the sixth Cr site, Cr is bonded in a 5-coordinate geometry to five P atoms. There are one shorter (2.20 Å) and four longer (2.39 Å) Cr–P bond lengths. There are three inequivalent P sites. In the first P site, P is bonded in a 9-coordinate geometry to nine Cr atoms. In the second P site, P is bonded in a 8-coordinate geometry to eight Cr atoms. In the third P site, P is bonded in a 9-coordinate geometry to nine Cr atoms.
Cr12P7 crystallizes in the hexagonal P-6 space group. The structure is three-dimensional. there are four inequivalent Cr sites. In the first Cr site, Cr is bonded in a 5-coordinate geometry to five P atoms. There are a spread of Cr–P bond distances ranging from 2.33–2.37 Å. In the second Cr site, Cr is bonded in a 4-coordinate geometry to four P atoms. There are a spread of Cr–P bond distances ranging from 2.26–2.42 Å. In the third Cr site, Cr is bonded in a 5-coordinate geometry to five P atoms. There are a spread of Cr–P bond distances ranging from 2.33–2.49 Å. In the fourth Cr site, Cr is bonded in a 5-coordinate geometry to five P atoms. There are a spread of Cr–P bond distances ranging from 2.40–2.54 Å. There are three inequivalent P sites. In the first P site, P is bonded in a 9-coordinate geometry to nine Cr atoms. In the second P site, P is bonded in a 8-coordinate geometry to eight Cr atoms. In the third P site, P is bonded in a 8-coordinate geometry to eight Cr atoms.
CrP2 crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. Cr6+ is bonded in a 8-coordinate geometry to eight P3- atoms. There are a spread of Cr–P bond distances ranging from 2.34–2.48 Å. There are two inequivalent P3- sites. In the first P3- site, P3- is bonded in a 4-coordinate geometry to three equivalent Cr6+ and three equivalent P3- atoms. There are one shorter (2.19 Å) and two longer (2.47 Å) P–P bond lengths. In the second P3- site, P3- is bonded in a 5-coordinate geometry to five equivalent Cr6+ atoms.
CrP4 is Sylvanite-derived structured and crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Cr4+ is bonded to six P1- atoms to form edge-sharing CrP6 octahedra. There are a spread of Cr–P bond distances ranging from 2.28–2.37 Å. There are two inequivalent P1- sites. In the first P1- site, P1- is bonded in a distorted rectangular see-saw-like geometry to one Cr4+ and three P1- atoms. There are two shorter (2.22 Å) and one longer (2.24 Å) P–P bond lengths. In the second P1- site, P1- is bonded in a 4-coordinate geometry to two equivalent Cr4+ and two P1- atoms. The P–P bond length is 2.22 Å.
Cr3P crystallizes in the tetragonal I-4 space group. The structure is three-dimensional. there are three inequivalent Cr sites. In the first Cr site, Cr is bonded in a 4-coordinate geometry to four equivalent P atoms. There are a spread of Cr–P bond distances ranging from 2.32–2.36 Å. In the second Cr site, Cr is bonded in a 2-coordinate geometry to two equivalent P atoms. Both Cr–P bond lengths are 2.35 Å. In the third Cr site, Cr is bonded in a 3-coordinate geometry to three equivalent P atoms. There are a spread of Cr–P bond distances ranging from 2.30–2.40 Å. P is bonded in a 9-coordinate geometry to nine Cr atoms.