The novel high-pressure/high-temperature compound Co₁₂P₇ determined from synchrotron data

Co₁₂P₇, synthesized at high pressure/temperature conditions, crystallizes isotypically with ordered Cr₁₂P₇ in space-group type P .

Abstract

The structural properties of cobalt phosphides were investigated at high pressures and temperatures to better understand the behavior of metal-rich phosphides in Earth and planetary inter­iors. Using single-crystal X-ray diffraction synchrotron data and a laser-heated diamond anvil cell, we discovered a new high pressure–temperature (HP–HT) cobalt phosphide, Co₁₂P₇, dodeca­cobalt hepta­phosphide, synthesized at 27 GPa and 1740 K, and at 48 GPa and 1790 K. Co₁₂P₇ adopts a structure initially proposed for Cr₁₂P₇ (space-group type P , Z =1), consisting of chains of edge-sharing CoP₅ square pyramids and chains of corner-sharing CoP₄ tetra­hedra. This arrangement leaves space for trigonal–prismatic channels running parallel to the c axis. Coupled disordering of metal and phospho­rus atoms has been observed in this structure for related M ₁₂P₇ (M = Cr, V) compounds, but all Co and P sites are ordered in Co₁₂P₇. All atomic sites in this crystal structure are situated on special positions. Upon decompression to ambient conditions, peak broadening and loss of reflections at high angles was observed, suggesting phase instability.

Chemical context  

Cobalt phosphides have previously been examined in the context of binary phase relations and thermodynamics (Okamoto & Massalski, 1990 ▸; Schlesinger, 2002 ▸) and have gained attention for their unique conductive properties (Prins & Bussell, 2012 ▸; Popczun et al., 2014 ▸; Pan et al., 2016 ▸; Pramanik et al., 2017 ▸), magnetic properties (Fujii et al., 1988 ▸; Jeitschko et al., 1978 ▸; Jeitschko & Jaberg, 1980 ▸; Reehuis & Jeitschko, 1989 ▸), and ability to store lanthanide cations (Jeitschko et al., 1978 ▸). Cobalt phosphides also serve as structural analogs to iron-rich phosphides and sulfides in planetary core-forming alloys. Previous studies of CoP and Co₂P indicate that their phase relations tend to precede in pressure the stability of isostructural Fe-phosphides and Fe-sulfides (Rundqvist, 1960 ▸; Ellner & Mittemeijer, 2001 ▸; Dera et al., 2008 ▸; Tateno et al., 2019 ▸; Rundqvist, 1962 ▸; Ono & Kikegawa, 2006 ▸; Ono et al. 2008 ▸). Hence, understanding the behavior of cobalt phosphides at high pressures provides insight into the ultra-high pressure behavior of iron sulfides and phosphides.

There are few structures reported in the literature for transition-metal phosphides with the composition M ₁₂P₇. Baurecht et al. (1971 ▸) first examined Cr₁₂P₇ and determined that it adopts a hexa­gonal lattice with space group P , Z = 1. The structure consists of columns of alternating tetra­hedral and pyramidal polyhedra and columns of stacked triangular–prismatic polyhedra extending along the c-axis direction. Chromium atoms occupy half of all possible tetra­hedral and pyramidal sites while the triangular–prismatic sites are empty (Baurecht et al., 1971 ▸). The polyhedra in the unit cell can be described as Cr₉ ^PCr₃ ^T[] ₂ ^PrP₇ (P = pyramidal, T = tetra­hedral, Pr = trigonal–prismatic, [] = empty site) (Maaref et al., 1981 ▸). Coupled disordering of two half-atoms of the corresponding metal with two half-atoms of phospho­rus within the tetra­hedral and pyramidal sites has been observed in this structure for compounds Th₇S₁₂, V₁₂P₇, and Cr₁₂P₇, increasing the symmetry to the P6₃/m space group (Zachariasen, 1949 ▸; Olofsson & Ganglberger 1970 ▸; Chun & Carpenter, 1979 ▸).

At ambient conditions the M ₁₂P₇ composition is not observed in the binary systems with M = Co, Ni, Fe. Dhahri (1996 ▸) concluded that Co₁₂P₇, Ni₁₂P₇ and Fe₁₂P₇ do not occur in the Cr₁₂P₇ structure type at ambient conditions because, unlike Cr and V, the elements Co, Ni and Fe do not preferentially occupy pyramidal sites. In support of this conclusion, the Zn₂Fe₁₂P₇ structure type (P , Z = 1) with many structural similarities to the Cr₁₂P₇ structure type, has been observed in Ln ₂ M ₁₂P₇ (Ln = rare-earth element; M = Co, Ni, Fe) compounds where the pyramidal-to-tetra­hedral site ratio is 1:3 (Jeitschko et al., 1978 ▸; Jeitschko & Jaberg, 1980 ▸; Reehuis & Jeitschko, 1989 ▸). Ordering is present in the Co-, Fe-, Ni-rich Zn₂Fe₁₂P₇ isomorphs (Jeitschko et al., 1984 ▸). No other structure types for the composition M ₁₂P₇ (M = Co, Ni, Fe) have been reported so far.

The effect of pressure and temperature on stabilizing Co in both the tetra­hedral and pyramidal sites and ordering of Co and P in the Cr₁₂P₇-type structure has not been examined previously. In the current study, we report the synthesis of a Co₁₂P₇ phase at 27 GPa and 1750 K, and at 48 GPa and 1790 K; both phases are isostructural and crystallize in space group P . Structure refinements revealed that Co and P sites are ordered in the high P–T structure and Co atoms occupy tetra­hedral and pyramidal coordinations. Using single-crystal diffraction techniques, we report refined atomic coordinate sites of Co₁₂P₇ at 48 GPa and 15 GPa.

Structural commentary  

Refinement of the structure confirms that Co₁₂P₇ assumes the ordered Cr₁₂P₇ structure type (Baurecht et al., 1971 ▸; Chun & Carpenter, 1979 ▸). Two of the Co sites (Co0, Co1) occupy Wyckoff position 3 j (point group symmetry m..), the other two Co sites (Co2, Co3) Wyckoff position 3 k (m..), one P site (P5) Wyckoff position 3 j, one P site (P4) Wyckoff position 3 k, and one P site (P6) Wyckoff position 1 a (..). The Co sites occupy tetra­hedral (cyan) and pyramidal (violet) sites as imaged in Fig. 1 ▸. Chains of edge-sharing CoP₅ square pyramids and chains of corner-sharing CoP₄ tetra­hedra build up the framework with trigonal–prismatic channels running parallel to the c axis.

Figure 1.

Crystal structure of Co₁₂P₇ based on the 48 GPa data set with atoms of the asymmetric unit labeled. CoP₄ tetra­hedra are shaded in cyan and CoP₅ square pyramids are shaded in violet.

Ranges of inter­atomic Co—P distances and polyhedral volumes are provided in Table 1 ▸ and Fig. 2 ▸ with CoP₄ tetra­hedra represented by a cyan polyhedron and CoP₅ pyramids represented by violet polyhedra. Co0 atoms occupy a distorted tetra­hedral site with one P atom at a short distance, two at inter­mediate distances and one at a long distance (Table 1 ▸, Fig. 2 ▸). Co1 and Co2 atoms occupy square pyramids with two inter­mediate and two long inter­atomic distances at the base. Co3 atoms occupy a less distorted square pyramid with two elongated and two truncated bonds at the base (Fig. 2 ▸). Inter­atomic distances at 48 GPa range from 2.063 (2)–2.102 (2) Å in the tetra­hedral polyhedra, 2.147 (4)–2.220 (4) Å for Co1—P polyhedra, 2.197 (4)–2.317 (2) Å for Co2—P polyhedra and 2.194 (3)–2.219 (3) Å for Co3—P polyhedra (Table 1 ▸). These inter­atomic distances are comparable to those observed in Co₂P and CoP (Rundqvist 1960 ▸, 1962 ▸).

Table 1. Selected structural parameters for Co₁₂P₇ at 48 GPa.

Group	Maximal bond length (Å)	minimal bond length (Å)	Polyhedron volume (Å3)	Distortion index
CoP4 (Co0—P4, —P5, —P6)	2.102 (2)	2.063 (2)	4.5433	0.00656
CoP5 (Co1—P4, —P5)	2.220 (4)	2.147 (4)	8.1257	0.01085
CoP5 (Co2—P4, —P5, —P6)	2.317 (2)	2.197 (4)	9.0766	0.01432
CoP5 (Co3—P4, —P5)	2.219 (3)	2.194 (3)	8.3239	0.00514

Figure 2.

Co—P polyhedra as observed in the Co₁₂P₇ structure (48 GPa data set) showing varying degrees of volume and distortion, qu­anti­fied in Table 1 ▸. CoP₄ tetra­hedra are shaded in cyan and CoP₅ square pyramids are shaded in violet. Displacement ellipsoids are drawn at the 50% probability level.

A grain of Co₁₂P₇ was decompressed to ambient conditions where 44 total reflections were identified in reciprocal space and indexed to a unit cell of a = 8.47 (1) Å, c = 3.37 (1) Å. These unit-cell parameters are in agreement with the pressure–volume trend observed, but peak broadening and loss of reflections at high angles may reflect the onset of phase instability on decompression.

Synthesis and crystallization  

The synthesis of Co₁₂P₇ was performed at high pressures and temperatures in a laser-heated diamond anvil cell (LHDAC). Two samples were loaded for this study in which Co₁₂P₇ was synthesized at 26.9 (8) GPa and 1740 (110) K and 48.2 (5) GPa and 1790 (200) K, respectively. Pressure was generated in BX-90-type (70° angular opening) diamond anvil cells (DACs) with 300 µm culet, Boehler–Almax type diamonds and seats. Co–P samples and a ruby sphere for pressure calibration were loaded into a sample chamber drilled from a rhenium gasket. The chamber was subsequently filled with compressed neon gas (Rivers et al., 2008 ▸). Pressure was determined using the ruby fluorescence scale and the Ne equation of state (Mao & Bell, 1976 ▸; Fei et al., 2007 ▸).

Samples were heated from both sides with 100W Yb-doped fiber lasers at beamline 13-ID-D (GeoSoilEnviroCARS) of the Advanced Photon Source (APS), Argonne National Laboratory. Heating cycles typically lasted ∼15 minutes at target temperatures prior to quench. The lasers were shaped with ∼15 µm flat tops and temperature was measured spectroradiometrically from a 6 µm central region of the laser heated spot using a gray body approximation (Heinz & Jeanloz, 1987 ▸). Axial temperature gradients through the sample were accounted for by applying a 3% correction on temperature measurements (Campbell et al., 2007 ▸, 2009 ▸).

Upon quench from high temperatures, high-pressure samples consisted of agglomerates of Co₁₂P₇ and Pnma Co₂P (Rundqvist, 1960 ▸) crystals of variable grain sizes up to ∼5 µm in diameter. Grains of target phases were identified in reciprocal space and sorted out from the scattering contribution of other grains, neon and diamond. Diffraction data were processed using Dioptas (Prescher & Prakapenka, 2015 ▸) and CrysAlis Pro (Rigaku OD, 2018 ▸). Decompression data were collected for both samples in two experimental stations; here we report two selected refinements of the Co₁₂P₇ structure at 48.2 (5) GPa and 15.4 (2) GPa.

Refinement  

Crystal data, data collection and structure refinement details at 48 GPa and 15 GPa are summarized in Table 2 ▸.

Table 2. Experimental details.

	48 GPa	15 GPa
Crystal data
Chemical formula	Co12P7	Co12P7
M r	923.95	923.95
Crystal system, space group	Hexagonal, P	Hexagonal, P
Temperature (K)	293	293
a, c (Å)	7.9700 (14), 3.2034 (4)	8.253 (5), 3.2902 (18)
V (Å3)	176.22 (7)	194.1 (3)
Z	1	1
Radiation type	Synchrotron, λ = 0.29521 Å	Synchrotron, λ = 0.3344 Å
μ (mm−1)	2.47	3.17
Crystal size (mm)	0.01 × 0.01 × 0.01	0.01 × 0.01 × 0.01
Data collection
Diffractometer	13IDD @ APS	13BMD @ APS
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)	Multi-scan (CrysAlis PRO; Rigaku OD, 2018 ▸)
T min, T max	0.789, 1.000	0.546, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	336, 292, 279	592, 321, 253
R int	0.006	0.055
(sin θ/λ)max (Å−1)	0.874	0.762
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.037, 0.096, 1.12	0.053, 0.105, 1.11
No. of reflections	292	321
No. of parameters	32	32
Δρmax, Δρmin (e Å−3)	2.35, −1.81	1.70, −1.74
Absolute structure	Flack x determined using 75 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)	Flack x determined using 78 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸)
Absolute structure parameter	0.42 (6)	0.4 (2)

Computer programs: CrysAlis PRO (Rigaku OD, 2018 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014/7 (Sheldrick, 2015b ▸), VESTA (Momma & Izumi, 2011 ▸) and publCIF (Westrip, 2010 ▸).

Monochromatic X-ray diffraction measurements took place at beamlines 13-ID-D (2 µm x 3 µm beam, λ = 0.2952 Å) and 13-BM-D (5 µm × 8 µm beam, λ = 0.3344 Å) at APS (Table 2 ▸). Diffraction measurements were collected at synthesis pressures and upon decompression. At target pressure steps, 10 x 10 µm still image maps were collected in 2 µm steps around the heated region. At selected map locations exhibiting the largest crystallites, rotation images were collected spanning ±30° at a rate of 1s per 0.5° step.

Grains of Co₁₂P₇ identified in reciprocal space were indexed to a primitive hexa­gonal lattice. Analysis of systematic absences indicated space group P with Z = 1. Two grains from distinct loadings and measured at different beamlines were selected for structural refinements as they showed the largest number of observed reflections and good statistical parameters (Table 2 ▸). Structure factors measured in microdiffraction in the LHDAC show some well-known limitations, such as limited resolution and redundancy, reflections overlapped by parasitic scattering, diamond diffraction (Loveday et al., 1990 ▸) and, more notably, variable volume of illuminated crystal during rotation. As could be expected, we identified eight and five outlier reflections in the refinements for the 48 GPa and 15 GPa data sets, respectively, and omitted them in the final calculations. Based on the ratio ‘observed reflections/refined parameters’ and statistical tests (Hamilton, 1965 ▸), we concluded that the P sites should be refined with isotropic displacement parameters (U _iso) whereas the Co sites could be refined with anisotropic displacement parameters. After convergence, site occupancies of Co atoms and P atoms were released in alternate runs. Within uncertainty (< 1.2% for Co and < 1.3% for P), all sites are fully occupied.

Supplementary Material

CCDC references: 2032430, 2032429

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Dodecacobalt heptaphosphide (Co12P7_at_48GPa). Crystal data

Co12P7	Dx = 8.706 Mg m−3
Mr = 923.95	Synchrotron radiation, λ = 0.29521 Å
Hexagonal, P6	Cell parameters from 292 reflections
a = 7.9700 (14) Å	θ = 2.3–14.9°
c = 3.2034 (4) Å	µ = 2.47 mm−1
V = 176.22 (7) Å3	T = 293 K
Z = 1	Irregular, black
F(000) = 429	0.01 × 0.01 × 0.01 mm

Dodecacobalt heptaphosphide (Co12P7_at_48GPa). Data collection

13IDD @ APS diffractometer	279 reflections with I > 2σ(I)
Radiation source: synchrotron	Rint = 0.006
ω scans	θmax = 15.0°, θmin = 2.1°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	h = −6→8
Tmin = 0.789, Tmax = 1.000	k = −10→9
336 measured reflections	l = −5→5
292 independent reflections

Dodecacobalt heptaphosphide (Co12P7_at_48GPa). Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0802P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.037	(Δ/σ)max < 0.001
wR(F2) = 0.096	Δρmax = 2.35 e Å−3
S = 1.12	Δρmin = −1.81 e Å−3
292 reflections	Absolute structure: Flack x determined using 75 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
32 parameters	Absolute structure parameter: 0.42 (6)

Dodecacobalt heptaphosphide (Co12P7_at_48GPa). Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Dodecacobalt heptaphosphide (Co12P7_at_48GPa). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co0	0.0185 (3)	0.2676 (3)	0.0000	0.0047 (4)
Co1	0.1313 (3)	0.6239 (3)	0.0000	0.0047 (4)
Co2	0.2161 (3)	0.2037 (4)	0.5000	0.0071 (4)
Co3	0.5185 (3)	0.1341 (3)	0.5000	0.0051 (4)
P4	0.1693 (5)	0.4529 (5)	0.5000	0.0062 (6)*
P5	0.4454 (5)	0.2795 (6)	0.0000	0.0050 (6)*
P6	0.0000	0.0000	0.0000	0.0069 (9)*

Dodecacobalt heptaphosphide (Co12P7_at_48GPa). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co0	0.0044 (8)	0.0030 (8)	0.0062 (5)	0.0015 (7)	0.000	0.000
Co1	0.0038 (8)	0.0024 (7)	0.0071 (8)	0.0009 (6)	0.000	0.000
Co2	0.0081 (8)	0.0069 (9)	0.0079 (6)	0.0049 (7)	0.000	0.000
Co3	0.0038 (8)	0.0028 (8)	0.0069 (7)	0.0005 (6)	0.000	0.000

Dodecacobalt heptaphosphide (Co12P7_at_48GPa). Geometric parameters (Å, º)

Co0—P6	2.0629 (18)	Co2—Co3	2.730 (2)
Co0—P5i	2.091 (4)	Co3—P5xi	2.194 (3)
Co0—P4	2.102 (2)	Co3—P5xii	2.194 (3)
Co0—P4ii	2.102 (2)	Co3—P4viii	2.197 (5)
Co0—Co3iii	2.458 (2)	Co3—P5vii	2.218 (3)
Co0—Co3i	2.458 (2)	Co3—P5	2.219 (3)
Co0—Co2ii	2.4710 (19)	Co3—Co0viii	2.458 (2)
Co0—Co2	2.4710 (19)	Co3—Co0ix	2.458 (2)
Co0—Co2iii	2.497 (2)	Co3—Co3xii	2.474 (3)
Co0—Co2i	2.497 (2)	Co3—Co3xiii	2.475 (3)
Co0—Co1	2.514 (3)	Co3—Co1viii	2.578 (2)
Co0—Co1iv	2.515 (2)	Co3—Co1ix	2.578 (2)
Co1—P5v	2.147 (4)	P4—Co0vii	2.102 (2)
Co1—P4v	2.180 (3)	P4—Co1x	2.180 (3)
Co1—P4vi	2.180 (3)	P4—Co1iv	2.180 (3)
Co1—P4ii	2.220 (3)	P4—Co3i	2.197 (5)
Co1—P4	2.220 (3)	P4—Co1vii	2.220 (3)
Co1—Co0v	2.515 (2)	P4—P4iv	2.674 (6)
Co1—Co1v	2.546 (3)	P4—P4v	2.674 (6)
Co1—Co1iv	2.546 (3)	P5—Co0viii	2.091 (4)
Co1—Co3iii	2.578 (2)	P5—Co1iv	2.147 (4)
Co1—Co3i	2.578 (2)	P5—Co3xiii	2.194 (3)
Co1—Co2v	2.639 (2)	P5—Co3xiv	2.194 (3)
Co2—P4	2.197 (4)	P5—Co3ii	2.218 (3)
Co2—P5	2.273 (3)	P5—Co2ii	2.273 (3)
Co2—P5vii	2.273 (3)	P6—Co0i	2.0629 (18)
Co2—P6	2.3174 (17)	P6—Co0viii	2.0629 (18)
Co2—P6vii	2.3174 (17)	P6—Co2xv	2.3174 (17)
Co2—Co0vii	2.4710 (19)	P6—Co2viii	2.3174 (17)
Co2—Co0viii	2.497 (2)	P6—Co2ii	2.3174 (17)
Co2—Co0ix	2.497 (2)	P6—Co2iii	2.3175 (17)
Co2—Co1x	2.639 (2)	P6—Co2i	2.3175 (17)
Co2—Co1iv	2.639 (2)
P6—Co0—P5i	96.84 (13)	P4—Co2—Co3	138.57 (14)
P6—Co0—P4	116.54 (11)	P5—Co2—Co3	51.66 (8)
P5i—Co0—P4	114.33 (11)	P5vii—Co2—Co3	51.66 (8)
P6—Co0—P4ii	116.54 (11)	P6—Co2—Co3	106.26 (8)
P5i—Co0—P4ii	114.33 (11)	P6vii—Co2—Co3	106.26 (8)
P4—Co0—P4ii	99.31 (14)	Co0vii—Co2—Co3	139.47 (4)
P6—Co0—Co3iii	126.74 (6)	Co0—Co2—Co3	139.47 (4)
P5i—Co0—Co3iii	57.69 (9)	Co0viii—Co2—Co3	55.89 (7)
P4—Co0—Co3iii	116.61 (12)	Co0ix—Co2—Co3	55.89 (7)
P4ii—Co0—Co3iii	56.96 (11)	Co1x—Co2—Co3	96.63 (8)
P6—Co0—Co3i	126.74 (6)	Co1iv—Co2—Co3	96.63 (8)
P5i—Co0—Co3i	57.69 (9)	P5xi—Co3—P5xii	93.78 (15)
P4—Co0—Co3i	56.96 (11)	P5xi—Co3—P4viii	107.43 (14)
P4ii—Co0—Co3i	116.61 (12)	P5xii—Co3—P4viii	107.43 (14)
Co3iii—Co0—Co3i	81.31 (9)	P5xi—Co3—P5vii	77.38 (14)
P6—Co0—Co2ii	60.69 (6)	P5xii—Co3—P5vii	146.69 (16)
P5i—Co0—Co2ii	129.60 (8)	P4viii—Co3—P5vii	105.86 (14)
P4—Co0—Co2ii	116.07 (13)	P5xi—Co3—P5	146.69 (16)
P4ii—Co0—Co2ii	56.73 (11)	P5xii—Co3—P5	77.38 (14)
Co3iii—Co0—Co2ii	98.20 (5)	P4viii—Co3—P5	105.86 (14)
Co3i—Co0—Co2ii	170.85 (9)	P5vii—Co3—P5	92.44 (15)
P6—Co0—Co2	60.69 (6)	P5xi—Co3—Co0viii	160.35 (15)
P5i—Co0—Co2	129.60 (8)	P5xii—Co3—Co0viii	89.46 (9)
P4—Co0—Co2	56.73 (11)	P4viii—Co3—Co0viii	53.31 (7)
P4ii—Co0—Co2	116.07 (13)	P5vii—Co3—Co0viii	109.66 (12)
Co3iii—Co0—Co2	170.85 (9)	P5—Co3—Co0viii	52.82 (11)
Co3i—Co0—Co2	98.20 (5)	P5xi—Co3—Co0ix	89.46 (9)
Co2ii—Co0—Co2	80.81 (8)	P5xii—Co3—Co0ix	160.35 (15)
P6—Co0—Co2iii	60.19 (6)	P4viii—Co3—Co0ix	53.31 (7)
P5i—Co0—Co2iii	58.60 (11)	P5vii—Co3—Co0ix	52.82 (11)
P4—Co0—Co2iii	169.97 (10)	P5—Co3—Co0ix	109.66 (12)
P4ii—Co0—Co2iii	90.40 (8)	Co0viii—Co3—Co0ix	81.32 (9)
Co3iii—Co0—Co2iii	66.85 (7)	P5xi—Co3—Co3xii	56.36 (10)
Co3i—Co0—Co2iii	116.27 (10)	P5xii—Co3—Co3xii	56.36 (10)
Co2ii—Co0—Co2iii	71.44 (10)	P4viii—Co3—Co3xii	151.84 (16)
Co2—Co0—Co2iii	120.88 (10)	P5vii—Co3—Co3xii	93.38 (11)
P6—Co0—Co2i	60.19 (6)	P5—Co3—Co3xii	93.38 (11)
P5i—Co0—Co2i	58.60 (11)	Co0viii—Co3—Co3xii	138.36 (5)
P4—Co0—Co2i	90.40 (8)	Co0ix—Co3—Co3xii	138.36 (5)
P4ii—Co0—Co2i	169.97 (10)	P5xi—Co3—Co3xiii	93.99 (11)
Co3iii—Co0—Co2i	116.27 (10)	P5xii—Co3—Co3xiii	93.99 (11)
Co3i—Co0—Co2i	66.85 (7)	P4viii—Co3—Co3xiii	148.16 (16)
Co2ii—Co0—Co2i	120.88 (10)	P5vii—Co3—Co3xiii	55.42 (11)
Co2—Co0—Co2i	71.44 (10)	P5—Co3—Co3xiii	55.42 (11)
Co2iii—Co0—Co2i	79.79 (9)	Co0viii—Co3—Co3xiii	105.12 (10)
P6—Co0—Co1	165.52 (9)	Co0ix—Co3—Co3xiii	105.12 (10)
P5i—Co0—Co1	97.64 (13)	Co3xii—Co3—Co3xiii	60.0
P4—Co0—Co1	56.65 (9)	P5xi—Co3—Co1viii	107.55 (12)
P4ii—Co0—Co1	56.65 (9)	P5xii—Co3—Co1viii	52.72 (10)
Co3iii—Co0—Co1	62.44 (6)	P4viii—Co3—Co1viii	54.71 (8)
Co3i—Co0—Co1	62.44 (6)	P5vii—Co3—Co1viii	160.55 (15)
Co2ii—Co0—Co1	109.16 (7)	P5—Co3—Co1viii	92.62 (8)
Co2—Co0—Co1	109.16 (7)	Co0viii—Co3—Co1viii	59.83 (7)
Co2iii—Co0—Co1	128.86 (7)	Co0ix—Co3—Co1viii	107.89 (10)
Co2i—Co0—Co1	128.86 (7)	Co3xii—Co3—Co1viii	105.04 (11)
P6—Co0—Co1iv	104.70 (9)	Co3xiii—Co3—Co1viii	140.36 (4)
P5i—Co0—Co1iv	158.46 (14)	P5xi—Co3—Co1ix	52.72 (10)
P4—Co0—Co1iv	55.49 (9)	P5xii—Co3—Co1ix	107.55 (12)
P4ii—Co0—Co1iv	55.49 (9)	P4viii—Co3—Co1ix	54.71 (8)
Co3iii—Co0—Co1iv	107.42 (7)	P5vii—Co3—Co1ix	92.62 (8)
Co3i—Co0—Co1iv	107.42 (7)	P5—Co3—Co1ix	160.55 (15)
Co2ii—Co0—Co1iv	63.90 (7)	Co0viii—Co3—Co1ix	107.89 (10)
Co2—Co0—Co1iv	63.90 (7)	Co0ix—Co3—Co1ix	59.83 (7)
Co2iii—Co0—Co1iv	133.74 (7)	Co3xii—Co3—Co1ix	105.04 (11)
Co2i—Co0—Co1iv	133.74 (7)	Co3xiii—Co3—Co1ix	140.36 (4)
Co1—Co0—Co1iv	60.82 (8)	Co1viii—Co3—Co1ix	76.82 (8)
P5v—Co1—P4v	108.68 (12)	P5xi—Co3—Co2	130.38 (8)
P5v—Co1—P4vi	108.68 (12)	P5xii—Co3—Co2	130.38 (8)
P4v—Co1—P4vi	94.55 (18)	P4viii—Co3—Co2	82.57 (13)
P5v—Co1—P4ii	108.29 (12)	P5vii—Co3—Co2	53.49 (10)
P4v—Co1—P4ii	143.01 (13)	P5—Co3—Co2	53.49 (10)
P4vi—Co1—P4ii	74.85 (14)	Co0viii—Co3—Co2	57.26 (7)
P5v—Co1—P4	108.29 (12)	Co0ix—Co3—Co2	57.26 (7)
P4v—Co1—P4	74.85 (14)	Co3xii—Co3—Co2	125.59 (11)
P4vi—Co1—P4	143.01 (13)	Co3xiii—Co3—Co2	65.59 (11)
P4ii—Co1—P4	92.36 (16)	Co1viii—Co3—Co2	116.75 (8)
P5v—Co1—Co0	89.08 (13)	Co1ix—Co3—Co2	116.75 (8)
P4v—Co1—Co0	127.10 (9)	Co0—P4—Co0vii	99.31 (14)
P4vi—Co1—Co0	127.10 (9)	Co0—P4—Co1x	144.1 (2)
P4ii—Co1—Co0	52.26 (8)	Co0vii—P4—Co1x	71.92 (7)
P4—Co1—Co0	52.26 (8)	Co0—P4—Co1iv	71.92 (7)
P5v—Co1—Co0v	91.74 (12)	Co0vii—P4—Co1iv	144.1 (2)
P4v—Co1—Co0v	52.58 (9)	Co1x—P4—Co1iv	94.55 (17)
P4vi—Co1—Co0v	52.58 (9)	Co0—P4—Co2	70.15 (11)
P4ii—Co1—Co0v	127.40 (9)	Co0vii—P4—Co2	70.15 (11)
P4—Co1—Co0v	127.40 (9)	Co1x—P4—Co2	74.16 (12)
Co0—Co1—Co0v	179.18 (8)	Co1iv—P4—Co2	74.16 (12)
P5v—Co1—Co1v	151.31 (16)	Co0—P4—Co3i	69.73 (11)
P4v—Co1—Co1v	55.38 (11)	Co0vii—P4—Co3i	69.73 (11)
P4vi—Co1—Co1v	55.38 (11)	Co1x—P4—Co3i	132.68 (9)
P4ii—Co1—Co1v	91.21 (10)	Co1iv—P4—Co3i	132.68 (9)
P4—Co1—Co1v	91.21 (10)	Co2—P4—Co3i	116.01 (16)
Co0—Co1—Co1v	119.61 (8)	Co0—P4—Co1	71.09 (7)
Co0v—Co1—Co1v	59.56 (10)	Co0vii—P4—Co1	140.9 (2)
P5v—Co1—Co1iv	148.69 (16)	Co1x—P4—Co1	136.84 (16)
P4v—Co1—Co1iv	92.13 (10)	Co1iv—P4—Co1	70.69 (9)
P4vi—Co1—Co1iv	92.13 (10)	Co2—P4—Co1	133.80 (8)
P4ii—Co1—Co1iv	53.93 (10)	Co3i—P4—Co1	71.42 (12)
P4—Co1—Co1iv	53.93 (10)	Co0—P4—Co1vii	140.9 (2)
Co0—Co1—Co1iv	59.61 (8)	Co0vii—P4—Co1vii	71.09 (7)
Co0v—Co1—Co1iv	119.56 (10)	Co1x—P4—Co1vii	70.69 (9)
Co1v—Co1—Co1iv	60.0	Co1iv—P4—Co1vii	136.84 (17)
P5v—Co1—Co3iii	54.42 (8)	Co2—P4—Co1vii	133.80 (8)
P4v—Co1—Co3iii	163.07 (13)	Co3i—P4—Co1vii	71.42 (12)
P4vi—Co1—Co3iii	92.51 (9)	Co1—P4—Co1vii	92.36 (16)
P4ii—Co1—Co3iii	53.87 (11)	Co0—P4—P4iv	125.14 (14)
P4—Co1—Co3iii	107.88 (12)	Co0vii—P4—P4iv	125.14 (14)
Co0—Co1—Co3iii	57.72 (8)	Co1x—P4—P4iv	53.25 (12)
Co0v—Co1—Co3iii	122.84 (8)	Co1iv—P4—P4iv	53.25 (12)
Co1v—Co1—Co3iii	139.67 (4)	Co2—P4—P4iv	94.4 (2)
Co1iv—Co1—Co3iii	102.97 (11)	Co3i—P4—P4iv	149.6 (2)
P5v—Co1—Co3i	54.42 (8)	Co1—P4—P4iv	87.91 (10)
P4v—Co1—Co3i	92.51 (9)	Co1vii—P4—P4iv	87.91 (10)
P4vi—Co1—Co3i	163.07 (13)	Co0—P4—P4v	122.98 (14)
P4ii—Co1—Co3i	107.88 (12)	Co0vii—P4—P4v	122.98 (14)
P4—Co1—Co3i	53.87 (11)	Co1x—P4—P4v	88.73 (10)
Co0—Co1—Co3i	57.72 (8)	Co1iv—P4—P4v	88.73 (10)
Co0v—Co1—Co3i	122.84 (8)	Co2—P4—P4v	154.4 (2)
Co1v—Co1—Co3i	139.67 (4)	Co3i—P4—P4v	89.6 (2)
Co1iv—Co1—Co3i	102.97 (11)	Co1—P4—P4v	51.90 (11)
Co3iii—Co1—Co3i	76.82 (8)	Co1vii—P4—P4v	51.90 (11)
P5v—Co1—Co2v	55.58 (8)	P4iv—P4—P4v	60.0
P4v—Co1—Co2v	53.20 (10)	Co0viii—P5—Co1iv	126.72 (19)
P4vi—Co1—Co2v	107.02 (11)	Co0viii—P5—Co3xiii	132.10 (9)
P4ii—Co1—Co2v	163.76 (12)	Co1iv—P5—Co3xiii	72.86 (12)
P4—Co1—Co2v	94.83 (9)	Co0viii—P5—Co3xiv	132.10 (9)
Co0—Co1—Co2v	123.33 (7)	Co1iv—P5—Co3xiv	72.86 (12)
Co0v—Co1—Co2v	57.23 (6)	Co3xiii—P5—Co3xiv	93.78 (15)
Co1v—Co1—Co2v	103.16 (10)	Co0viii—P5—Co3ii	69.48 (13)
Co1iv—Co1—Co2v	140.65 (5)	Co1iv—P5—Co3ii	133.45 (8)
Co3iii—Co1—Co2v	109.96 (9)	Co3xiii—P5—Co3ii	133.08 (18)
Co3i—Co1—Co2v	65.62 (7)	Co3xiv—P5—Co3ii	68.22 (10)
P4—Co2—P5	103.71 (12)	Co0viii—P5—Co3	69.48 (13)
P4—Co2—P5vii	103.71 (12)	Co1iv—P5—Co3	133.45 (8)
P5—Co2—P5vii	89.59 (15)	Co3xiii—P5—Co3	68.22 (10)
P4—Co2—P6	103.35 (9)	Co3xiv—P5—Co3	133.08 (18)
P5—Co2—P6	85.20 (8)	Co3ii—P5—Co3	92.44 (15)
P5vii—Co2—P6	152.92 (13)	Co0viii—P5—Co2	69.66 (13)
P4—Co2—P6vii	103.35 (9)	Co1iv—P5—Co2	73.26 (11)
P5—Co2—P6vii	152.92 (13)	Co3xiii—P5—Co2	78.50 (8)
P5vii—Co2—P6vii	85.20 (8)	Co3xiv—P5—Co2	146.03 (19)
P6—Co2—P6vii	87.44 (8)	Co3ii—P5—Co2	139.1 (2)
P4—Co2—Co0vii	53.12 (8)	Co3—P5—Co2	74.85 (8)
P5—Co2—Co0vii	155.85 (14)	Co0viii—P5—Co2ii	69.66 (13)
P5vii—Co2—Co0vii	89.95 (7)	Co1iv—P5—Co2ii	73.25 (11)
P6—Co2—Co0vii	105.40 (8)	Co3xiii—P5—Co2ii	146.03 (19)
P6vii—Co2—Co0vii	50.91 (5)	Co3xiv—P5—Co2ii	78.50 (8)
P4—Co2—Co0	53.12 (8)	Co3ii—P5—Co2ii	74.85 (8)
P5—Co2—Co0	89.95 (7)	Co3—P5—Co2ii	139.1 (2)
P5vii—Co2—Co0	155.85 (14)	Co2—P5—Co2ii	89.59 (15)
P6—Co2—Co0	50.91 (5)	Co0i—P6—Co0	120.0
P6vii—Co2—Co0	105.40 (8)	Co0i—P6—Co0viii	120.0
Co0vii—Co2—Co0	80.81 (8)	Co0—P6—Co0viii	120.0
P4—Co2—Co0viii	140.08 (4)	Co0i—P6—Co2xv	69.24 (6)
P5—Co2—Co0viii	51.74 (11)	Co0—P6—Co2xv	136.27 (4)
P5vii—Co2—Co0viii	106.53 (11)	Co0viii—P6—Co2xv	68.40 (6)
P6—Co2—Co0viii	50.57 (5)	Co0i—P6—Co2viii	69.24 (6)
P6vii—Co2—Co0viii	104.56 (10)	Co0—P6—Co2viii	136.27 (4)
Co0vii—Co2—Co0viii	149.98 (11)	Co0viii—P6—Co2viii	68.40 (6)
Co0—Co2—Co0viii	91.97 (7)	Co2xv—P6—Co2viii	87.45 (8)
P4—Co2—Co0ix	140.08 (4)	Co0i—P6—Co2	136.27 (4)
P5—Co2—Co0ix	106.54 (11)	Co0—P6—Co2	68.40 (6)
P5vii—Co2—Co0ix	51.74 (11)	Co0viii—P6—Co2	69.24 (6)
P6—Co2—Co0ix	104.56 (10)	Co2xv—P6—Co2	137.63 (3)
P6vii—Co2—Co0ix	50.57 (5)	Co2viii—P6—Co2	77.49 (6)
Co0vii—Co2—Co0ix	91.97 (7)	Co0i—P6—Co2ii	136.27 (4)
Co0—Co2—Co0ix	149.98 (11)	Co0—P6—Co2ii	68.40 (6)
Co0viii—Co2—Co0ix	79.79 (9)	Co0viii—P6—Co2ii	69.24 (6)
P4—Co2—Co1x	52.64 (9)	Co2xv—P6—Co2ii	77.49 (6)
P5—Co2—Co1x	103.19 (12)	Co2viii—P6—Co2ii	137.64 (3)
P5vii—Co2—Co1x	51.16 (10)	Co2—P6—Co2ii	87.44 (8)
P6—Co2—Co1x	155.65 (9)	Co0i—P6—Co2iii	68.40 (6)
P6vii—Co2—Co1x	94.13 (4)	Co0—P6—Co2iii	69.24 (6)
Co0vii—Co2—Co1x	58.87 (6)	Co0viii—P6—Co2iii	136.27 (4)
Co0—Co2—Co1x	105.65 (9)	Co2xv—P6—Co2iii	77.49 (6)
Co0viii—Co2—Co1x	149.97 (10)	Co2viii—P6—Co2iii	137.63 (3)
Co0ix—Co2—Co1x	95.00 (6)	Co2—P6—Co2iii	137.63 (3)
P4—Co2—Co1iv	52.64 (9)	Co2ii—P6—Co2iii	77.49 (6)
P5—Co2—Co1iv	51.16 (10)	Co0i—P6—Co2i	68.40 (6)
P5vii—Co2—Co1iv	103.19 (13)	Co0—P6—Co2i	69.24 (6)
P6—Co2—Co1iv	94.13 (4)	Co0viii—P6—Co2i	136.27 (4)
P6vii—Co2—Co1iv	155.65 (9)	Co2xv—P6—Co2i	137.63 (3)
Co0vii—Co2—Co1iv	105.65 (9)	Co2viii—P6—Co2i	77.49 (6)
Co0—Co2—Co1iv	58.87 (6)	Co2—P6—Co2i	77.49 (6)
Co0viii—Co2—Co1iv	95.00 (6)	Co2ii—P6—Co2i	137.63 (3)
Co0ix—Co2—Co1iv	149.97 (10)	Co2iii—P6—Co2i	87.44 (8)
Co1x—Co2—Co1iv	74.74 (7)

Symmetry codes: (i) −y, x−y, z; (ii) x, y, z−1; (iii) −y, x−y, z−1; (iv) −y+1, x−y+1, z; (v) −x+y, −x+1, z; (vi) −x+y, −x+1, z−1; (vii) x, y, z+1; (viii) −x+y, −x, z; (ix) −x+y, −x, z+1; (x) −y+1, x−y+1, z+1; (xi) −y+1, x−y, z+1; (xii) −y+1, x−y, z; (xiii) −x+y+1, −x+1, z; (xiv) −x+y+1, −x+1, z−1; (xv) −x+y, −x, z−1.

(Co12P7_at_15GPa). Crystal data

Co12P7	Dx = 7.905 Mg m−3
Mr = 923.95	Synchrotron radiation, λ = 0.3344 Å
Hexagonal, P6	Cell parameters from 249 reflections
a = 8.253 (5) Å	θ = 2.9–14.7°
c = 3.2902 (18) Å	µ = 3.17 mm−1
V = 194.1 (3) Å3	T = 293 K
Z = 1	Irregular, black
F(000) = 429	0.01 × 0.01 × 0.01 mm

(Co12P7_at_15GPa). Data collection

13BMD @ APS diffractometer	253 reflections with I > 2σ(I)
Radiation source: synchrotron	Rint = 0.055
/w scan	θmax = 14.8°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018)	h = −11→12
Tmin = 0.546, Tmax = 1.000	k = −9→8
592 measured reflections	l = −4→4
321 independent reflections

(Co12P7_at_15GPa). Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0219P)2 + 2.8589P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.053	(Δ/σ)max < 0.001
wR(F2) = 0.105	Δρmax = 1.70 e Å−3
S = 1.11	Δρmin = −1.74 e Å−3
321 reflections	Absolute structure: Flack x determined using 78 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
32 parameters	Absolute structure parameter: 0.4 (2)

(Co12P7_at_15GPa). Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

(Co12P7_at_15GPa). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co0	0.0153 (6)	0.2651 (6)	0.0000	0.0114 (8)
Co1	0.1320 (7)	0.6234 (7)	0.0000	0.0123 (9)
Co2	0.2135 (6)	0.2038 (8)	0.5000	0.0151 (9)
Co3	0.5195 (7)	0.1363 (7)	0.5000	0.0107 (9)
P4	0.1656 (11)	0.4503 (11)	0.5000	0.0102 (15)*
P5	0.4425 (12)	0.2809 (13)	0.0000	0.0086 (15)*
P6	0.0000	0.0000	0.0000	0.012 (3)*

(Co12P7_at_15GPa). Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co0	0.014 (2)	0.016 (2)	0.0072 (18)	0.009 (2)	0.000	0.000
Co1	0.019 (2)	0.016 (2)	0.003 (2)	0.0101 (18)	0.000	0.000
Co2	0.024 (2)	0.020 (3)	0.005 (2)	0.014 (2)	0.000	0.000
Co3	0.011 (2)	0.012 (2)	0.008 (2)	0.0052 (16)	0.000	0.000

(Co12P7_at_15GPa). Geometric parameters (Å, º)

Co0—P6	2.128 (5)	Co2—Co1iv	2.731 (5)
Co0—P5i	2.148 (10)	Co2—Co3	2.846 (7)
Co0—P4	2.165 (6)	Co3—P5xi	2.263 (7)
Co0—P4ii	2.165 (6)	Co3—P5xii	2.263 (7)
Co0—Co3iii	2.538 (5)	Co3—P4viii	2.266 (10)
Co0—Co3i	2.538 (5)	Co3—P5vii	2.301 (8)
Co0—Co2ii	2.543 (6)	Co3—P5	2.301 (8)
Co0—Co2	2.543 (6)	Co3—Co3xiii	2.536 (9)
Co0—Co2iii	2.571 (6)	Co3—Co3xii	2.536 (9)
Co0—Co2i	2.571 (6)	Co3—Co0viii	2.538 (5)
Co0—Co1	2.612 (7)	Co3—Co0ix	2.538 (5)
Co0—Co1iv	2.634 (7)	Co3—Co1viii	2.674 (5)
Co1—P5v	2.202 (10)	Co3—Co1ix	2.674 (5)
Co1—P4v	2.266 (7)	P4—Co0vii	2.165 (6)
Co1—P4vi	2.266 (7)	P4—Co1x	2.266 (7)
Co1—P4ii	2.284 (7)	P4—Co1iv	2.266 (7)
Co1—P4	2.285 (7)	P4—Co3i	2.266 (10)
Co1—Co1v	2.624 (9)	P4—Co1vii	2.285 (7)
Co1—Co1iv	2.624 (9)	P5—Co0viii	2.148 (10)
Co1—Co0v	2.634 (7)	P5—Co1iv	2.202 (10)
Co1—Co3iii	2.674 (5)	P5—Co3xiii	2.263 (7)
Co1—Co3i	2.674 (5)	P5—Co3xiv	2.263 (7)
Co1—Co2v	2.731 (5)	P5—Co3ii	2.301 (8)
Co2—P4	2.258 (9)	P5—Co2ii	2.341 (7)
Co2—P5vii	2.341 (7)	P6—Co0i	2.128 (5)
Co2—P5	2.341 (7)	P6—Co0viii	2.128 (5)
Co2—P6	2.383 (4)	P6—Co2xv	2.383 (4)
Co2—P6vii	2.383 (4)	P6—Co2iii	2.383 (4)
Co2—Co0vii	2.543 (6)	P6—Co2i	2.383 (4)
Co2—Co0viii	2.571 (6)	P6—Co2viii	2.383 (4)
Co2—Co0ix	2.571 (6)	P6—Co2ii	2.383 (4)
Co2—Co1x	2.731 (5)
P6—Co0—P5i	96.9 (3)	P5vii—Co2—Co1iv	102.3 (3)
P6—Co0—P4	116.4 (2)	P5—Co2—Co1iv	50.7 (2)
P5i—Co0—P4	114.7 (3)	P6—Co2—Co1iv	94.84 (11)
P6—Co0—P4ii	116.4 (2)	P6vii—Co2—Co1iv	156.4 (2)
P5i—Co0—P4ii	114.7 (3)	Co0vii—Co2—Co1iv	106.0 (2)
P4—Co0—P4ii	98.9 (4)	Co0—Co2—Co1iv	59.81 (15)
P6—Co0—Co3iii	127.43 (16)	Co0viii—Co2—Co1iv	94.89 (12)
P5i—Co0—Co3iii	58.1 (2)	Co0ix—Co2—Co1iv	148.9 (2)
P4—Co0—Co3iii	116.1 (3)	Co1x—Co2—Co1iv	74.08 (17)
P4ii—Co0—Co3iii	56.9 (2)	P4—Co2—Co3	138.5 (3)
P6—Co0—Co3i	127.43 (16)	P5vii—Co2—Co3	51.6 (2)
P5i—Co0—Co3i	58.1 (2)	P5—Co2—Co3	51.6 (2)
P4—Co0—Co3i	56.9 (2)	P6—Co2—Co3	106.1 (2)
P4ii—Co0—Co3i	116.1 (3)	P6vii—Co2—Co3	106.1 (2)
Co3iii—Co0—Co3i	80.8 (2)	Co0vii—Co2—Co3	139.57 (11)
P6—Co0—Co2ii	60.57 (16)	Co0—Co2—Co3	139.58 (11)
P5i—Co0—Co2ii	129.6 (2)	Co0viii—Co2—Co3	55.61 (16)
P4—Co0—Co2ii	115.7 (3)	Co0ix—Co2—Co3	55.61 (16)
P4ii—Co0—Co2ii	56.6 (2)	Co1x—Co2—Co3	95.9 (2)
Co3iii—Co0—Co2ii	98.44 (12)	Co1iv—Co2—Co3	95.9 (2)
Co3i—Co0—Co2ii	170.2 (3)	P5xi—Co3—P5xii	93.3 (4)
P6—Co0—Co2	60.57 (16)	P5xi—Co3—P4viii	106.5 (3)
P5i—Co0—Co2	129.6 (2)	P5xii—Co3—P4viii	106.5 (3)
P4—Co0—Co2	56.6 (2)	P5xi—Co3—P5vii	79.0 (4)
P4ii—Co0—Co2	115.7 (3)	P5xii—Co3—P5vii	148.1 (4)
Co3iii—Co0—Co2	170.2 (3)	P4viii—Co3—P5vii	105.3 (3)
Co3i—Co0—Co2	98.44 (12)	P5xi—Co3—P5	148.1 (4)
Co2ii—Co0—Co2	80.6 (2)	P5xii—Co3—P5	79.0 (4)
P6—Co0—Co2iii	60.07 (15)	P4viii—Co3—P5	105.3 (3)
P5i—Co0—Co2iii	58.7 (2)	P5vii—Co3—P5	91.3 (4)
P4—Co0—Co2iii	170.1 (3)	P5xi—Co3—Co3xiii	95.1 (3)
P4ii—Co0—Co2iii	90.7 (2)	P5xii—Co3—Co3xiii	95.1 (3)
Co3iii—Co0—Co2iii	67.70 (14)	P4viii—Co3—Co3xiii	148.1 (4)
Co3i—Co0—Co2iii	116.8 (2)	P5vii—Co3—Co3xiii	55.5 (3)
Co2ii—Co0—Co2iii	71.4 (2)	P5—Co3—Co3xiii	55.5 (3)
Co2—Co0—Co2iii	120.6 (2)	P5xi—Co3—Co3xii	57.0 (3)
P6—Co0—Co2i	60.07 (15)	P5xii—Co3—Co3xii	57.0 (3)
P5i—Co0—Co2i	58.7 (2)	P4viii—Co3—Co3xii	151.9 (4)
P4—Co0—Co2i	90.7 (2)	P5vii—Co3—Co3xii	94.1 (3)
P4ii—Co0—Co2i	170.1 (3)	P5—Co3—Co3xii	94.1 (3)
Co3iii—Co0—Co2i	116.8 (2)	Co3xiii—Co3—Co3xii	60.0
Co3i—Co0—Co2i	67.70 (14)	P5xi—Co3—Co0viii	159.3 (3)
Co2ii—Co0—Co2i	120.6 (2)	P5xii—Co3—Co0viii	89.59 (18)
Co2—Co0—Co2i	71.4 (2)	P4viii—Co3—Co0viii	53.20 (19)
Co2iii—Co0—Co2i	79.6 (2)	P5vii—Co3—Co0viii	108.5 (3)
P6—Co0—Co1	164.3 (3)	P5—Co3—Co0viii	52.4 (2)
P5i—Co0—Co1	98.8 (3)	Co3xiii—Co3—Co0viii	105.1 (2)
P4—Co0—Co1	56.2 (2)	Co3xii—Co3—Co0viii	138.58 (11)
P4ii—Co0—Co1	56.2 (2)	P5xi—Co3—Co0ix	89.59 (18)
Co3iii—Co0—Co1	62.53 (14)	P5xii—Co3—Co0ix	159.3 (3)
Co3i—Co0—Co1	62.53 (14)	P4viii—Co3—Co0ix	53.20 (19)
Co2ii—Co0—Co1	108.4 (2)	P5vii—Co3—Co0ix	52.4 (2)
Co2—Co0—Co1	108.4 (2)	P5—Co3—Co0ix	108.5 (3)
Co2iii—Co0—Co1	129.67 (15)	Co3xiii—Co3—Co0ix	105.1 (2)
Co2i—Co0—Co1	129.67 (15)	Co3xii—Co3—Co0ix	138.58 (11)
P6—Co0—Co1iv	104.29 (19)	Co0viii—Co3—Co0ix	80.8 (2)
P5i—Co0—Co1iv	158.8 (3)	P5xi—Co3—Co1viii	106.4 (3)
P4—Co0—Co1iv	55.3 (2)	P5xii—Co3—Co1viii	52.2 (2)
P4ii—Co0—Co1iv	55.3 (2)	P4viii—Co3—Co1viii	54.34 (19)
Co3iii—Co0—Co1iv	107.12 (19)	P5vii—Co3—Co1viii	159.6 (3)
Co3i—Co0—Co1iv	107.12 (19)	P5—Co3—Co1viii	93.3 (2)
Co2ii—Co0—Co1iv	63.65 (16)	Co3xiii—Co3—Co1viii	140.83 (9)
Co2—Co0—Co1iv	63.65 (16)	Co3xii—Co3—Co1viii	105.3 (2)
Co2iii—Co0—Co1iv	133.59 (16)	Co0viii—Co3—Co1viii	60.09 (15)
Co2i—Co0—Co1iv	133.59 (16)	Co0ix—Co3—Co1viii	107.4 (2)
Co1—Co0—Co1iv	60.0 (2)	P5xi—Co3—Co1ix	52.2 (2)
P5v—Co1—P4v	108.1 (2)	P5xii—Co3—Co1ix	106.4 (3)
P5v—Co1—P4vi	108.1 (2)	P4viii—Co3—Co1ix	54.34 (19)
P4v—Co1—P4vi	93.1 (4)	P5vii—Co3—Co1ix	93.3 (2)
P5v—Co1—P4ii	108.0 (3)	P5—Co3—Co1ix	159.6 (3)
P4v—Co1—P4ii	144.0 (3)	Co3xiii—Co3—Co1ix	140.83 (9)
P4vi—Co1—P4ii	76.3 (3)	Co3xii—Co3—Co1ix	105.3 (2)
P5v—Co1—P4	108.0 (3)	Co0viii—Co3—Co1ix	107.4 (2)
P4v—Co1—P4	76.3 (3)	Co0ix—Co3—Co1ix	60.09 (15)
P4vi—Co1—P4	144.0 (3)	Co1viii—Co3—Co1ix	75.95 (16)
P4ii—Co1—P4	92.1 (4)	P5xi—Co3—Co2	131.18 (19)
P5v—Co1—Co0	89.0 (3)	P5xii—Co3—Co2	131.18 (19)
P4v—Co1—Co0	128.2 (2)	P4viii—Co3—Co2	82.0 (3)
P4vi—Co1—Co0	128.2 (2)	P5vii—Co3—Co2	52.8 (2)
P4ii—Co1—Co0	51.9 (2)	P5—Co3—Co2	52.8 (2)
P4—Co1—Co0	51.9 (2)	Co3xiii—Co3—Co2	66.1 (3)
P5v—Co1—Co1v	150.6 (4)	Co3xii—Co3—Co2	126.1 (3)
P4v—Co1—Co1v	55.1 (2)	Co0viii—Co3—Co2	56.70 (15)
P4vi—Co1—Co1v	55.1 (2)	Co0ix—Co3—Co2	56.70 (15)
P4ii—Co1—Co1v	92.1 (2)	Co1viii—Co3—Co2	116.37 (18)
P4—Co1—Co1v	92.1 (2)	Co1ix—Co3—Co2	116.37 (18)
Co0—Co1—Co1v	120.4 (2)	Co0—P4—Co0vii	98.9 (4)
P5v—Co1—Co1iv	149.4 (4)	Co0—P4—Co2	70.2 (2)
P4v—Co1—Co1iv	92.6 (2)	Co0vii—P4—Co2	70.2 (2)
P4vi—Co1—Co1iv	92.6 (2)	Co0—P4—Co1x	144.1 (4)
P4ii—Co1—Co1iv	54.4 (2)	Co0vii—P4—Co1x	72.93 (17)
P4—Co1—Co1iv	54.4 (2)	Co2—P4—Co1x	74.3 (3)
Co0—Co1—Co1iv	60.4 (2)	Co0—P4—Co1iv	72.93 (17)
Co1v—Co1—Co1iv	60.0	Co0vii—P4—Co1iv	144.1 (4)
P5v—Co1—Co0v	91.0 (3)	Co2—P4—Co1iv	74.3 (3)
P4v—Co1—Co0v	51.8 (2)	Co1x—P4—Co1iv	93.1 (4)
P4vi—Co1—Co0v	51.8 (2)	Co0—P4—Co3i	69.9 (3)
P4ii—Co1—Co0v	128.0 (2)	Co0vii—P4—Co3i	69.9 (3)
P4—Co1—Co0v	128.0 (2)	Co2—P4—Co3i	116.5 (4)
Co0—Co1—Co0v	180.0 (2)	Co1x—P4—Co3i	133.35 (18)
Co1v—Co1—Co0v	59.6 (2)	Co1iv—P4—Co3i	133.35 (18)
Co1iv—Co1—Co0v	119.6 (2)	Co0—P4—Co1	71.84 (17)
P5v—Co1—Co3iii	54.26 (19)	Co0vii—P4—Co1	141.5 (4)
P4v—Co1—Co3iii	162.3 (3)	Co2—P4—Co1	133.94 (18)
P4vi—Co1—Co3iii	93.40 (17)	Co1x—P4—Co1	135.3 (4)
P4ii—Co1—Co3iii	53.7 (2)	Co1iv—P4—Co1	70.4 (2)
P4—Co1—Co3iii	107.1 (3)	Co3i—P4—Co1	72.0 (3)
Co0—Co1—Co3iii	57.38 (16)	Co0—P4—Co1vii	141.5 (4)
Co1v—Co1—Co3iii	140.25 (9)	Co0vii—P4—Co1vii	71.84 (17)
Co1iv—Co1—Co3iii	103.5 (2)	Co2—P4—Co1vii	133.94 (18)
Co0v—Co1—Co3iii	122.64 (18)	Co1x—P4—Co1vii	70.4 (2)
P5v—Co1—Co3i	54.26 (19)	Co1iv—P4—Co1vii	135.3 (4)
P4v—Co1—Co3i	93.40 (17)	Co3i—P4—Co1vii	72.0 (3)
P4vi—Co1—Co3i	162.3 (3)	Co1—P4—Co1vii	92.1 (4)
P4ii—Co1—Co3i	107.1 (3)	Co0viii—P5—Co1iv	127.8 (5)
P4—Co1—Co3i	53.7 (2)	Co0viii—P5—Co3xiii	131.9 (2)
Co0—Co1—Co3i	57.38 (15)	Co1iv—P5—Co3xiii	73.6 (3)
Co1v—Co1—Co3i	140.25 (9)	Co0viii—P5—Co3xiv	131.9 (2)
Co1iv—Co1—Co3i	103.5 (2)	Co1iv—P5—Co3xiv	73.6 (3)
Co0v—Co1—Co3i	122.64 (18)	Co3xiii—P5—Co3xiv	93.3 (4)
Co3iii—Co1—Co3i	75.95 (16)	Co0viii—P5—Co3	69.5 (3)
P5v—Co1—Co2v	55.41 (19)	Co1iv—P5—Co3	133.9 (2)
P4v—Co1—Co2v	52.7 (2)	Co3xiii—P5—Co3	67.5 (2)
P4vi—Co1—Co2v	105.6 (3)	Co3xiv—P5—Co3	131.1 (4)
P4ii—Co1—Co2v	163.3 (3)	Co0viii—P5—Co3ii	69.5 (3)
P4—Co1—Co2v	95.17 (19)	Co1iv—P5—Co3ii	133.9 (2)
Co0—Co1—Co2v	123.5 (2)	Co3xiii—P5—Co3ii	131.1 (4)
Co1v—Co1—Co2v	102.6 (2)	Co3xiv—P5—Co3ii	67.5 (2)
Co1iv—Co1—Co2v	140.73 (11)	Co3—P5—Co3ii	91.3 (4)
Co0v—Co1—Co2v	56.54 (14)	Co0viii—P5—Co2	69.7 (3)
Co3iii—Co1—Co2v	109.6 (2)	Co1iv—P5—Co2	73.8 (2)
Co3i—Co1—Co2v	66.10 (15)	Co3xiii—P5—Co2	79.62 (16)
P4—Co2—P5vii	103.7 (3)	Co3xiv—P5—Co2	147.3 (4)
P4—Co2—P5	103.7 (3)	Co3—P5—Co2	75.6 (2)
P5vii—Co2—P5	89.3 (3)	Co3ii—P5—Co2	139.2 (4)
P4—Co2—P6	103.6 (2)	Co0viii—P5—Co2ii	69.7 (3)
P5vii—Co2—P6	152.7 (3)	Co1iv—P5—Co2ii	73.8 (2)
P5—Co2—P6	85.31 (18)	Co3xiii—P5—Co2ii	147.3 (4)
P4—Co2—P6vii	103.6 (2)	Co3xiv—P5—Co2ii	79.62 (16)
P5vii—Co2—P6vii	85.30 (18)	Co3—P5—Co2ii	139.2 (4)
P5—Co2—P6vii	152.7 (3)	Co3ii—P5—Co2ii	75.6 (2)
P6—Co2—P6vii	87.33 (17)	Co2—P5—Co2ii	89.3 (3)
P4—Co2—Co0vii	53.20 (19)	Co0i—P6—Co0viii	120.0
P5vii—Co2—Co0vii	90.21 (18)	Co0i—P6—Co0	120.0
P5—Co2—Co0vii	155.9 (3)	Co0viii—P6—Co0	120.0
P6—Co2—Co0vii	105.4 (2)	Co0i—P6—Co2xv	69.23 (17)
P6vii—Co2—Co0vii	51.06 (12)	Co0viii—P6—Co2xv	68.36 (17)
P4—Co2—Co0	53.20 (19)	Co0—P6—Co2xv	136.33 (9)
P5vii—Co2—Co0	155.9 (3)	Co0i—P6—Co2iii	68.36 (17)
P5—Co2—Co0	90.21 (18)	Co0viii—P6—Co2iii	136.33 (9)
P6—Co2—Co0	51.06 (12)	Co0—P6—Co2iii	69.23 (17)
P6vii—Co2—Co0	105.4 (2)	Co2xv—P6—Co2iii	77.58 (13)
Co0vii—Co2—Co0	80.6 (2)	Co0i—P6—Co2i	68.36 (17)
P4—Co2—Co0viii	140.20 (12)	Co0viii—P6—Co2i	136.33 (9)
P5vii—Co2—Co0viii	106.2 (3)	Co0—P6—Co2i	69.23 (17)
P5—Co2—Co0viii	51.6 (2)	Co2xv—P6—Co2i	137.59 (6)
P6—Co2—Co0viii	50.70 (12)	Co2iii—P6—Co2i	87.34 (17)
P6vii—Co2—Co0viii	104.5 (2)	Co0i—P6—Co2viii	69.23 (17)
Co0vii—Co2—Co0viii	150.1 (2)	Co0viii—P6—Co2viii	68.36 (17)
Co0—Co2—Co0viii	92.22 (16)	Co0—P6—Co2viii	136.33 (9)
P4—Co2—Co0ix	140.20 (12)	Co2xv—P6—Co2viii	87.34 (17)
P5vii—Co2—Co0ix	51.6 (2)	Co2iii—P6—Co2viii	137.59 (6)
P5—Co2—Co0ix	106.2 (3)	Co2i—P6—Co2viii	77.58 (13)
P6—Co2—Co0ix	104.5 (2)	Co0i—P6—Co2ii	136.33 (9)
P6vii—Co2—Co0ix	50.70 (12)	Co0viii—P6—Co2ii	69.23 (17)
Co0vii—Co2—Co0ix	92.22 (16)	Co0—P6—Co2ii	68.37 (17)
Co0—Co2—Co0ix	150.1 (2)	Co2xv—P6—Co2ii	77.58 (13)
Co0viii—Co2—Co0ix	79.6 (2)	Co2iii—P6—Co2ii	77.58 (13)
P4—Co2—Co1x	52.99 (19)	Co2i—P6—Co2ii	137.59 (6)
P5vii—Co2—Co1x	50.7 (2)	Co2viii—P6—Co2ii	137.59 (6)
P5—Co2—Co1x	102.3 (3)	Co0i—P6—Co2	136.33 (9)
P6—Co2—Co1x	156.4 (2)	Co0viii—P6—Co2	69.23 (17)
P6vii—Co2—Co1x	94.84 (11)	Co0—P6—Co2	68.37 (17)
Co0vii—Co2—Co1x	59.81 (15)	Co2xv—P6—Co2	137.59 (6)
Co0—Co2—Co1x	106.0 (2)	Co2iii—P6—Co2	137.59 (6)
Co0viii—Co2—Co1x	148.9 (2)	Co2i—P6—Co2	77.58 (13)
Co0ix—Co2—Co1x	94.89 (12)	Co2viii—P6—Co2	77.58 (13)
P4—Co2—Co1iv	52.99 (19)	Co2ii—P6—Co2	87.33 (17)

Symmetry codes: (i) −y, x−y, z; (ii) x, y, z−1; (iii) −y, x−y, z−1; (iv) −y+1, x−y+1, z; (v) −x+y, −x+1, z; (vi) −x+y, −x+1, z−1; (vii) x, y, z+1; (viii) −x+y, −x, z; (ix) −x+y, −x, z+1; (x) −y+1, x−y+1, z+1; (xi) −y+1, x−y, z+1; (xii) −y+1, x−y, z; (xiii) −x+y+1, −x+1, z; (xiv) −x+y+1, −x+1, z−1; (xv) −x+y, −x, z−1.

Funding Statement

This work was funded by National Science Foundation grant EAR – 1651017 to A. Campbell.