Phase identification and structure determination from multiphase crystalline powder samples by rotation electron diffraction

Phase identification and structure characterization are important in synthetic and materials science. It is difficult to characterize the individual phases from multiphase crystalline powder samples, especially if some of the phases are unknown. This problem can be solved by combining rotation electron diffraction (RED) and powder X-ray diffraction (PXRD). Four phases were identified on the same transmission electron microscopy grid from a multiphase sample in the Ni-Se-O-Cl system, and their structures were solved from the RED data. Phase 1 (NiSeO₃) was found in the Inorganic Crystal Structure Database using the information from RED. Phase 2 (Ni₃Se₄O₁₀Cl₂) is an unknown compound, but it is isostructural to Co₃Se₄O₁₀Cl₂, which was recently solved by single-crystal X-ray diffraction. Phase 3 (Ni₅Se₆O₁₆Cl₄H₂) and Phase 4 (Ni₅Se₄O₁₂Cl₂) are new compounds. The fact that there are at least four different compounds in the as-synthesized material explains why the phase identification and structure determination could not be done by PXRD alone. The RED method makes phase identification from such multiphase powder samples much easier than would be the case using powder X-ray diffraction. The RED method also makes structure determination of submicrometre-sized crystals from multiphase samples possible.

Computing details

Program(s) used to solve structure: SHELXS97 (Sheldrick, 1990) for Phase_1_NiSeO3, Phase_2_Ni3Se4O10Cl2, Phase_3_Ni5Se6O16Cl4H2, Phase_4_Ni5Se4O12Cl2. Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for Phase_1_NiSeO3, Phase_2_Ni3Se4O10Cl2, Phase_3_Ni5Se6O16Cl4H2, Phase_4_Ni5Se4O12Cl2.

(Phase_1_NiSeO3)

Crystal data

NiO3Se	V = 2158.95 Å^3
Mr = 185.65	Z = 32
Monoclinic, C2/c	F(000) = 631
a = 15.58 Å	Dx = 4.569 Mg m^−3
b = 9.96 Å	Electrons radiation, λ = 0.02510 Å
c = 14.82 Å	µ = 0.00 mm^−1
β = 110.2°	× × mm

Data collection

TEM diffractometer	Rint = 0.296
Radiation source: 200 kV accerelating voltage	θmax = 0.8°, θmin = 0.1°
Rotation electron diffraction scans	h = −15→15
3389 measured reflections	k = −10→10
1142 independent reflections	l = −15→15
662 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.250	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.551	(Δ/σ)max = 0.188
S = 1.75	Δρmax = 0.85 e Å^−3
1142 reflections	Δρmin = −0.49 e Å^−3
82 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 2861 (156)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Se1	0.3804 (9)	0.1333 (10)	0.1052 (8)	0.043 (3)*
Se2	0.0845 (9)	0.1140 (10)	0.3643 (8)	0.041 (3)*
Se3	0.3844 (9)	0.3192 (10)	0.3504 (8)	0.041 (3)*
Se4	0.0958 (9)	0.3817 (9)	0.1810 (8)	0.040 (3)*
Ni1	0.0672 (10)	0.1155 (11)	0.0344 (9)	0.043 (3)*
Ni2	0.2608 (10)	0.3629 (11)	0.0876 (9)	0.041 (3)*
Ni3	0.2322 (10)	0.3567 (12)	0.4157 (9)	0.042 (3)*
Ni4	0.2232 (10)	0.0928 (11)	0.2413 (9)	0.041 (3)*
O1	0.349 (3)	0.266 (3)	0.025 (2)	0.052 (9)*
O2	0.315 (3)	0.018 (3)	0.027 (2)	0.050 (8)*
O3	0.310 (2)	0.182 (3)	0.168 (2)	0.041 (7)*
O4	0.167 (2)	0.196 (2)	0.454 (2)	0.032 (6)*
O5	0.030 (2)	0.013 (3)	0.419 (2)	0.038 (7)*
O6	0.144 (2)	0.006 (3)	0.324 (2)	0.045 (8)*
O7	0.467 (2)	0.261 (3)	0.453 (2)	0.046 (8)*
O8	0.292 (3)	0.229 (3)	0.344 (2)	0.045 (8)*
O9	0.339 (2)	0.473 (3)	0.384 (2)	0.043 (8)*
O10	0.119 (2)	0.394 (2)	0.301 (2)	0.034 (7)*
O11	0.111 (3)	0.213 (3)	0.166 (2)	0.047 (8)*
O12	0.203 (3)	0.442 (3)	0.183 (3)	0.052 (8)*

Geometric parameters (Å, º)

Se1—O2	1.70 (3)	Ni2—Se1^i	2.943 (18)
Se1—O1	1.73 (3)	Ni3—O2^vi	2.07 (3)
Se1—O3	1.74 (3)	Ni3—O8	2.07 (3)
Se1—Ni2^i	2.943 (18)	Ni3—O4	2.08 (3)
Se2—O4	1.71 (3)	Ni3—O4^vii	2.09 (3)
Se2—O5	1.70 (3)	Ni3—O10	2.02 (4)
Se2—O6	1.66 (3)	Ni3—O9	2.21 (4)
Se3—O9	1.82 (3)	Ni4—O12^v	1.98 (4)
Se3—O8	1.67 (4)	Ni4—O3	2.19 (3)
Se3—O7	1.72 (4)	Ni4—O11	2.09 (4)
Se3—Ni3	2.877 (19)	Ni4—O8	2.05 (3)
Se4—O10	1.69 (3)	Ni4—O6	2.19 (3)
Se4—O12	1.77 (4)	Ni4—O9^v	2.14 (3)
Se4—O11	1.72 (3)	O1—Ni1^i	2.16 (4)
Ni1—O7^ii	2.02 (4)	O1—Ni2^i	2.32 (4)
Ni1—O1^i	2.16 (4)	O2—Ni2^i	2.07 (4)
Ni1—O5^iii	2.05 (3)	O2—Ni3^v	2.07 (3)
Ni1—O11	2.07 (3)	O4—Ni3^vii	2.09 (3)
Ni1—O5^iv	2.12 (3)	O5—Ni1^viii	2.05 (3)
Ni1—O9^v	2.10 (3)	O5—Ni1^iv	2.12 (3)
Ni2—O6^vi	2.15 (3)	O6—Ni2^v	2.15 (3)
Ni2—O2^i	2.07 (4)	O7—Ni1^ix	2.02 (4)
Ni2—O12	2.08 (4)	O9—Ni4^vi	2.14 (3)
Ni2—O1^i	2.32 (4)	O9—Ni1^vi	2.10 (3)
Ni2—O3	2.15 (3)	O12—Ni4^vi	1.98 (4)
Ni2—O1	2.14 (4)
O2—Se1—O1	94.9 (16)	O2^vi—Ni3—O9	94.7 (13)
O2—Se1—O3	102.4 (18)	O8—Ni3—O9	73.1 (13)
O1—Se1—O3	94.2 (17)	O4—Ni3—O9	159.7 (14)
O2—Se1—Ni2^i	43.5 (11)	O4^vii—Ni3—O9	86.9 (13)
O1—Se1—Ni2^i	51.9 (13)	O10—Ni3—O9	103.1 (13)
O3—Se1—Ni2^i	96.8 (13)	O2^vi—Ni3—Se3	133.7 (11)
O4—Se2—O5	106.0 (15)	O8—Ni3—Se3	35.0 (10)
O4—Se2—O6	103.1 (17)	O4—Ni3—Se3	122.0 (10)
O5—Se2—O6	103.2 (15)	O4^vii—Ni3—Se3	80.4 (10)
O9—Se3—O8	93.5 (17)	O10—Ni3—Se3	108.7 (11)
O9—Se3—O7	106.7 (15)	O9—Ni3—Se3	39.4 (8)
O8—Se3—O7	103.6 (17)	O12^v—Ni4—O3	104.7 (15)
O9—Se3—Ni3	50.1 (11)	O12^v—Ni4—O11	161.4 (16)
O8—Se3—Ni3	45.2 (11)	O3—Ni4—O11	92.4 (13)
O7—Se3—Ni3	101.7 (13)	O12^v—Ni4—O8	91.6 (15)
O10—Se4—O12	95.6 (17)	O3—Ni4—O8	81.2 (13)
O10—Se4—O11	103.0 (14)	O11—Ni4—O8	98.4 (14)
O12—Se4—O11	99.0 (17)	O12^v—Ni4—O6	73.3 (14)
O7^ii—Ni1—O1^i	82.7 (14)	O3—Ni4—O6	176.0 (15)
O7^ii—Ni1—O5^iii	86.7 (13)	O11—Ni4—O6	90.1 (14)
O1^i—Ni1—O5^iii	92.3 (13)	O8—Ni4—O6	95.4 (14)
O7^ii—Ni1—O11	102.3 (14)	O12^v—Ni4—O9^v	93.8 (14)
O1^i—Ni1—O11	94.1 (14)	O3—Ni4—O9^v	88.3 (12)
O5^iii—Ni1—O11	169.4 (13)	O11—Ni4—O9^v	79.1 (13)
O7^ii—Ni1—O5^iv	90.0 (14)	O8—Ni4—O9^v	169.1 (14)
O1^i—Ni1—O5^iv	172.7 (14)	O6—Ni4—O9^v	95.2 (13)
O5^iii—Ni1—O5^iv	86.6 (13)	Se1—O1—Ni1^i	129 (2)
O11—Ni1—O5^iv	88.0 (14)	Se1—O1—Ni2^i	92.0 (15)
O7^ii—Ni1—O9^v	174.4 (14)	Ni1^i—O1—Ni2^i	114.2 (14)
O1^i—Ni1—O9^v	101.8 (15)	Se1—O1—Ni2	96.7 (16)
O5^iii—Ni1—O9^v	89.9 (13)	Ni1^i—O1—Ni2	120.1 (15)
O11—Ni1—O9^v	80.6 (14)	Ni2^i—O1—Ni2	98.1 (16)
O5^iv—Ni1—O9^v	85.3 (13)	Se1—O2—Ni2^i	102.1 (15)
O6^vi—Ni2—O2^i	101.3 (13)	Se1—O2—Ni3^v	117.3 (18)
O6^vi—Ni2—O12	72.3 (15)	Ni2^i—O2—Ni3^v	126.8 (19)
O2^i—Ni2—O12	94.8 (15)	Se1—O3—Ni4	139.7 (16)
O6^vi—Ni2—O1^i	171.4 (13)	Se1—O3—Ni2	96.1 (14)
O2^i—Ni2—O1^i	70.1 (13)	Ni4—O3—Ni2	117.0 (16)
O12—Ni2—O1^i	108.6 (15)	Se2—O4—Ni3	117.4 (15)
O6^vi—Ni2—O3	100.4 (13)	Se2—O4—Ni3^vii	136.4 (14)
O2^i—Ni2—O3	158.0 (14)	Ni3—O4—Ni3^vii	99.5 (14)
O12—Ni2—O3	95.4 (13)	Se2—O5—Ni1^viii	136 (2)
O1^i—Ni2—O3	88.1 (12)	Se2—O5—Ni1^iv	113.7 (14)
O6^vi—Ni2—O1	99.0 (14)	Ni1^viii—O5—Ni1^iv	93.4 (13)
O2^i—Ni2—O1	99.8 (15)	Se2—O6—Ni2^v	124.1 (17)
O12—Ni2—O1	164.3 (16)	Se2—O6—Ni4	116.1 (16)
O1^i—Ni2—O1	81.9 (16)	Ni2^v—O6—Ni4	101.7 (15)
O3—Ni2—O1	72.9 (12)	Se3—O7—Ni1^ix	120.8 (17)
O6^vi—Ni2—Se1^i	135.3 (10)	Se3—O8—Ni3	99.8 (15)
O2^i—Ni2—Se1^i	34.4 (9)	Se3—O8—Ni4	128 (2)
O12—Ni2—Se1^i	107.8 (12)	Ni3—O8—Ni4	125 (2)
O1^i—Ni2—Se1^i	36.1 (8)	Se3—O9—Ni4^vi	109.6 (15)
O3—Ni2—Se1^i	123.6 (10)	Se3—O9—Ni1^vi	117.9 (19)
O1—Ni2—Se1^i	87.6 (11)	Ni4^vi—O9—Ni1^vi	98.0 (13)
O2^vi—Ni3—O8	167.1 (15)	Se3—O9—Ni3	90.5 (13)
O2^vi—Ni3—O4	102.0 (13)	Ni4^vi—O9—Ni3	109.2 (16)
O8—Ni3—O4	90.8 (12)	Ni1^vi—O9—Ni3	131.2 (16)
O2^vi—Ni3—O4^vii	94.3 (13)	Se4—O10—Ni3	133 (2)
O8—Ni3—O4^vii	89.3 (13)	Se4—O11—Ni4	128 (2)
O4—Ni3—O4^vii	80.5 (14)	Se4—O11—Ni1	124.6 (18)
O2^vi—Ni3—O10	82.7 (13)	Ni4—O11—Ni1	100.3 (14)
O8—Ni3—O10	95.7 (14)	Se4—O12—Ni4^vi	128.8 (19)
O4—Ni3—O10	90.5 (13)	Se4—O12—Ni2	119.0 (19)
O4^vii—Ni3—O10	169.7 (15)	Ni4^vi—O12—Ni2	112.0 (18)

Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) x, −y, z−1/2; (iv) −x, y, −z+1/2; (v) −x+1/2, y−1/2, −z+1/2; (vi) −x+1/2, y+1/2, −z+1/2; (vii) −x+1/2, −y+1/2, −z+1; (viii) x, −y, z+1/2; (ix) x+1/2, −y+1/2, z+1/2.

(Phase_2_Ni3Se4O10Cl2)

Crystal data

Cl2Ni3O10Se4	γ = 90°
Mr = 722.81	V = 529.3 Å^3
?, C2/m	Z = 2
a = 7.17 Å	F(000) = 156
b = 13.70 Å	Dx = 4.535 Mg m^−3
c = 5.63 Å	Electrons radiation, λ = 0.02510 Å
α = 90°	µ = 0.00 mm^−1
β = 106.8°	× × mm

Data collection

TEM diffractometer	Rint = 0.283
Radiation source: 200 kV accerelating voltage	θmax = 0.7°, θmin = 0.1°
Rotation electron diffraction scans	h = −6→6
751 measured reflections	k = −14→14
248 independent reflections	l = −5→5
194 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.207	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.521	(Δ/σ)max = 0.299
S = 1.96	Δρmax = 0.32 e Å^−3
248 reflections	Δρmin = −0.55 e Å^−3
22 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 3284 (159)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.5000	0.0000	0.023 (6)*
Ni2	0.0000	0.3741 (11)	−0.5000	0.029 (5)*
Se1	0.3473 (19)	0.3367 (7)	0.224 (2)	0.029 (4)*
Cl1	0.210 (4)	0.5000	−0.252 (4)	0.035 (7)*
O1	0.309 (6)	0.223 (3)	0.284 (6)	0.051 (10)*
O2	0.141 (5)	0.3891 (18)	0.235 (5)	0.022 (7)*
O3	0.5000	0.394 (4)	0.5000	0.071 (18)*

Geometric parameters (Å, º)

Ni1—O2^i	2.07 (3)	Ni2—Cl1	2.44 (2)
Ni1—O2^ii	2.07 (3)	Ni2—Cl1^vii	2.44 (2)
Ni1—O2^iii	2.07 (3)	Se1—O1	1.64 (4)
Ni1—O2	2.07 (3)	Se1—O2	1.66 (3)
Ni1—Cl1	2.35 (2)	Se1—O3	1.80 (3)
Ni1—Cl1^iii	2.35 (2)	Cl1—Ni2^vii	2.44 (2)
Ni2—O1^iv	2.04 (4)	O1—Ni2^v	2.04 (4)
Ni2—O1^v	2.04 (4)	O2—Ni2^viii	2.04 (3)
Ni2—O2^ii	2.04 (3)	O3—Se1^ix	1.80 (3)
Ni2—O2^vi	2.04 (3)
O2^i—Ni1—O2^ii	180.000 (2)	O1^iv—Ni2—Cl1	175.5 (14)
O2^i—Ni1—O2^iii	85.8 (16)	O1^v—Ni2—Cl1	85.5 (13)
O2^ii—Ni1—O2^iii	94.2 (16)	O2^ii—Ni2—Cl1	82.2 (10)
O2^i—Ni1—O2	94.2 (16)	O2^vi—Ni2—Cl1	89.6 (10)
O2^ii—Ni1—O2	85.8 (16)	O1^iv—Ni2—Cl1^vii	85.5 (13)
O2^iii—Ni1—O2	180.0 (9)	O1^v—Ni2—Cl1^vii	175.5 (14)
O2^i—Ni1—Cl1	96.1 (9)	O2^ii—Ni2—Cl1^vii	89.6 (10)
O2^ii—Ni1—Cl1	83.9 (8)	O2^vi—Ni2—Cl1^vii	82.2 (10)
O2^iii—Ni1—Cl1	83.9 (8)	Cl1—Ni2—Cl1^vii	90.3 (11)
O2—Ni1—Cl1	96.1 (8)	O1—Se1—O2	101.5 (17)
O2^i—Ni1—Cl1^iii	83.9 (8)	O1—Se1—O3	110 (2)
O2^ii—Ni1—Cl1^iii	96.1 (8)	O2—Se1—O3	96.1 (15)
O2^iii—Ni1—Cl1^iii	96.1 (8)	Ni1—Cl1—Ni2	87.0 (8)
O2—Ni1—Cl1^iii	83.9 (8)	Ni1—Cl1—Ni2^vii	87.0 (8)
Cl1—Ni1—Cl1^iii	180.000 (3)	Ni2—Cl1—Ni2^vii	89.7 (10)
O1^iv—Ni2—O1^v	99 (2)	Se1—O1—Ni2^v	128 (3)
O1^iv—Ni2—O2^ii	96.4 (12)	Se1—O2—Ni2^viii	128.1 (16)
O1^v—Ni2—O2^ii	91.1 (12)	Se1—O2—Ni1	124.6 (15)
O1^iv—Ni2—O2^vi	91.1 (12)	Ni2^viii—O2—Ni1	106.7 (14)
O1^v—Ni2—O2^vi	96.4 (12)	Se1—O3—Se1^ix	128 (4)
O2^ii—Ni2—O2^vi	168.5 (18)

Symmetry codes: (i) x, −y+1, z; (ii) −x, y, −z; (iii) −x, −y+1, −z; (iv) x−1/2, −y+1/2, z−1; (v) −x+1/2, −y+1/2, −z; (vi) x, y, z−1; (vii) −x, −y+1, −z−1; (viii) x, y, z+1; (ix) −x+1, y, −z+1.

(Phase_3_Ni5Se6O16Cl4H2)

Crystal data

H2Cl4Ni5O16Se6	γ = 90°
Mr = 1167.03	V = 2058.3 Å^3
?, C2/c	Z = 4
a = 21.94 Å	F(000) = 512
b = 8.38 Å	Dx = 3.766 Mg m^−3
c = 12.68 Å	Electrons radiation, λ = 0.02510 Å
α = 90°	µ = 0.00 mm^−1
β = 118.1°	× × mm

Data collection

TEM diffractometer	Rint = 0.210
Radiation source: 200 kV accerelating voltage	θmax = 0.5°, θmin = 0.1°
Rotation electron diffraction scans	h = −16→16
1205 measured reflections	k = −6→6
351 independent reflections	l = −9→9
245 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.239	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.556	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 2.27	(Δ/σ)max = 0.006
351 reflections	Δρmax = 0.46 e Å^−3
64 parameters	Δρmin = −0.56 e Å^−3
8 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 1100 (270)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Se1	0.3213 (14)	0.057 (3)	0.213 (2)	0.114 (12)*
Se2	0.6143 (17)	0.212 (3)	0.595 (2)	0.129 (12)*
Se3	0.4030 (16)	0.304 (3)	0.595 (2)	0.137 (13)*
Ni1	0.3349 (15)	0.416 (3)	0.307 (3)	0.119 (13)*
Ni2	0.2412 (16)	0.189 (3)	0.374 (2)	0.105 (12)*
Ni3	0.5000	0.5000	0.5000	0.128 (16)*
Cl1	0.4402 (17)	0.375 (5)	0.299 (3)	0.137 (16)*
Cl2	0.256 (2)	0.409 (3)	0.087 (3)	0.113 (14)*
O1	0.323 (4)	0.181 (8)	0.320 (6)	0.12 (2)*
O2	0.530 (2)	0.262 (9)	0.544 (5)	0.13 (3)*
O3	0.404 (3)	0.431 (5)	0.492 (4)	0.08 (2)*
O4	0.256 (3)	−0.077 (7)	0.170 (6)	0.12 (2)*
O5	0.336 (4)	0.656 (9)	0.296 (6)	0.17 (3)*
O6	0.383 (5)	−0.080 (11)	0.303 (8)	0.16 (3)*
O7	0.179 (2)	0.259 (7)	0.449 (5)	0.11 (2)*
O8	0.438 (5)	0.131 (6)	0.579 (9)	0.15 (3)*
H8	0.4762	0.1494	0.5843	0.232*

Geometric parameters (Å, º)

Se1—O4	1.70 (2)	Ni2—O4^iv	2.05 (6)
Se1—O6	1.73 (10)	Ni2—O7	2.09 (6)
Se1—O1	1.70 (6)	Ni2—Cl2^v	2.390 (19)
Se2—O6^i	1.68 (8)	Ni3—O2^ii	2.09 (7)
Se2—O2	1.69 (2)	Ni3—O2	2.09 (7)
Se2—O5^ii	1.71 (2)	Ni3—O3	2.14 (6)
Se3—O7^iii	1.69 (2)	Ni3—O3^ii	2.14 (6)
Se3—O8	1.70 (2)	Ni3—Cl1^ii	2.48 (4)
Se3—O3	1.70 (2)	Ni3—Cl1	2.48 (4)
Ni1—O1	2.00 (7)	Cl2—Ni2^iv	2.390 (19)
Ni1—O5	2.02 (8)	O4—Ni2^v	2.05 (6)
Ni1—O3	2.12 (6)	O4—Ni1^v	2.15 (6)
Ni1—O4^iv	2.15 (6)	O5—Se2^ii	1.71 (2)
Ni1—Cl1	2.39 (2)	O5—Ni2^iv	2.03 (8)
Ni1—Cl2	2.50 (5)	O6—Se2^i	1.68 (8)
Ni2—O1	2.20 (8)	O7—Se3^iii	1.69 (2)
Ni2—O7^iii	2.15 (6)	O7—Ni2^iii	2.15 (6)
Ni2—O5^v	2.03 (8)
O4—Se1—O6	93 (4)	O4^iv—Ni2—Cl2^v	174 (2)
O4—Se1—O1	111 (4)	O7—Ni2—Cl2^v	98 (2)
O6—Se1—O1	99 (4)	O2^ii—Ni3—O2	180.000 (11)
O6^i—Se2—O2	96 (4)	O2^ii—Ni3—O3	93.7 (18)
O6^i—Se2—O5^ii	92 (4)	O2—Ni3—O3	86.3 (19)
O2—Se2—O5^ii	108 (4)	O2^ii—Ni3—O3^ii	86.3 (19)
O7^iii—Se3—O8	99 (4)	O2—Ni3—O3^ii	93.7 (18)
O7^iii—Se3—O3	110 (3)	O3—Ni3—O3^ii	180.000 (5)
O8—Se3—O3	106 (4)	O2^ii—Ni3—Cl1^ii	79.5 (19)
O1—Ni1—O5	173 (3)	O2—Ni3—Cl1^ii	100.5 (19)
O1—Ni1—O3	91 (3)	O3—Ni3—Cl1^ii	101.2 (15)
O5—Ni1—O3	90 (2)	O3^ii—Ni3—Cl1^ii	78.8 (15)
O1—Ni1—O4^iv	81 (3)	O2^ii—Ni3—Cl1	100.5 (19)
O5—Ni1—O4^iv	91 (3)	O2—Ni3—Cl1	79.5 (19)
O3—Ni1—O4^iv	94 (3)	O3—Ni3—Cl1	78.8 (15)
O1—Ni1—Cl1	92 (3)	O3^ii—Ni3—Cl1	101.2 (15)
O5—Ni1—Cl1	96 (3)	Cl1^ii—Ni3—Cl1	180.000 (2)
O3—Ni1—Cl1	81 (2)	Ni1—Cl1—Ni3	87.1 (13)
O4^iv—Ni1—Cl1	172 (2)	Ni2^iv—Cl2—Ni1	79.1 (13)
O1—Ni1—Cl2	91 (2)	Se1—O1—Ni1	119 (3)
O5—Ni1—Cl2	88 (2)	Se1—O1—Ni2	124 (4)
O3—Ni1—Cl2	177.0 (19)	Ni1—O1—Ni2	99 (3)
O4^iv—Ni1—Cl2	88 (2)	Se2—O2—Ni3	120 (4)
Cl1—Ni1—Cl2	96.9 (16)	Se3—O3—Ni1	124 (3)
O1—Ni2—O7^iii	87 (3)	Se3—O3—Ni3	121 (3)
O1—Ni2—O5^v	93 (3)	Ni1—O3—Ni3	104.2 (17)
O7^iii—Ni2—O5^v	176 (3)	Se1—O4—Ni2^v	126 (4)
O1—Ni2—O4^iv	79 (2)	Se1—O4—Ni1^v	132 (4)
O7^iii—Ni2—O4^iv	89 (3)	Ni2^v—O4—Ni1^v	99.0 (18)
O5^v—Ni2—O4^iv	88 (3)	Se2^ii—O5—Ni1	128 (5)
O1—Ni2—O7	163 (3)	Se2^ii—O5—Ni2^iv	132 (5)
O7^iii—Ni2—O7	81.9 (19)	Ni1—O5—Ni2^iv	100.4 (19)
O5^v—Ni2—O7	97 (3)	Se2^i—O6—Se1	133 (6)
O4^iv—Ni2—O7	88 (2)	Se3^iii—O7—Ni2^iii	129 (3)
O1—Ni2—Cl2^v	95 (2)	Se3^iii—O7—Ni2	125 (3)
O7^iii—Ni2—Cl2^v	93 (2)	Ni2^iii—O7—Ni2	98.1 (19)
O5^v—Ni2—Cl2^v	91 (2)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1/2, −y+1/2, −z+1; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1/2, y−1/2, −z+1/2.

(Phase_4_Ni5Se4O12Cl2)

Crystal data

Cl2Ni5O12Se4	γ = 101.6°
Mr = 872.19	V = 684.2 Å^3
?, P1	Z = 2
a = 9.44 Å	F(000) = 190
b = 9.44 Å	Dx = 4.234 Mg m^−3
c = 8.14 Å	Electrons radiation, λ = 0.02510 Å
α = 105.1°	µ = 0.00 mm^−1
β = 91.6°	× × mm

Data collection

TEM diffractometer	Rint = 0.228
Radiation source: 200 kV accerelating voltage	θmax = 0.8°, θmin = 0.1°
Rotation electron diffraction scans	h = −10→10
2888 measured reflections	k = −10→10
1464 independent reflections	l = −9→9
425 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.330	w = 1/[σ^2(Fo^2) + (0.2P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.660	(Δ/σ)max = 0.431
S = 1.47	Δρmax = 0.97 e Å^−3
1464 reflections	Δρmin = −0.68 e Å^−3
94 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
19 restraints	Extinction coefficient: 6040 (146)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Se1	0.230 (3)	−0.094 (2)	0.178 (2)	0.030 (6)*
Se2	0.680 (3)	0.882 (2)	1.286 (2)	0.023 (5)*
Se3	0.621 (2)	0.323 (2)	0.442 (2)	0.027 (5)*
Se4	0.894 (3)	0.572 (2)	0.840 (2)	0.025 (5)*
Ni1	0.254 (2)	0.277 (3)	0.417 (3)	0.037 (7)*
Ni2	0.806 (3)	0.563 (2)	0.238 (3)	0.029 (6)*
Ni3	0.512 (3)	0.180 (2)	0.104 (2)	0.032 (6)*
Ni4	0.893 (4)	0.869 (3)	1.019 (3)	0.059 (9)*
Ni5	1.102 (2)	0.801 (2)	0.745 (2)	0.019 (5)*
Cl1	0.621 (4)	0.392 (4)	0.013 (4)	0.029 (8)*
Cl2	0.981 (3)	0.725 (4)	0.464 (3)	0.046 (10)*
O1	0.852 (6)	0.976 (5)	1.290 (5)	0.007 (10)*
O2	0.421 (7)	−0.036 (3)	0.093 (6)	0.035 (15)*
O3	0.456 (3)	0.299 (4)	0.331 (3)	0.011 (11)*
O4	0.683 (7)	0.837 (6)	1.053 (6)	0.020 (13)*
O5	0.274 (8)	0.500 (7)	0.564 (7)	0.029 (14)*
O6	0.907 (8)	0.661 (7)	0.056 (7)	0.031 (15)*
O7	0.246 (7)	0.058 (6)	0.335 (6)	0.020 (12)*
O8	0.111 (3)	0.268 (3)	0.220 (4)	0.16 (6)*
O9	0.297 (8)	0.273 (5)	0.658 (4)	0.07 (2)*
O10	0.922 (9)	0.399 (7)	0.195 (7)	0.036 (16)*
O11	0.688 (3)	0.218 (6)	0.272 (4)	0.043 (18)*
O12	0.108 (4)	−0.075 (4)	0.008 (7)	0.040 (17)*

Geometric parameters (Å, º)

Se1—O7	1.63 (5)	Ni3—O3	2.044 (19)
Se1—O2	1.98 (5)	Ni3—Cl1	2.38 (4)
Se1—O12	1.85 (5)	Ni4—O12^ii	2.01 (2)
Se2—O9^i	1.695 (19)	Ni4—O12^vi	2.00 (2)
Se2—O4	1.84 (5)	Ni4—O1	2.25 (5)
Se2—O1	1.68 (6)	Ni4—O8^ii	2.03 (2)
Se2—Ni4	3.00 (4)	Ni4—O6^iv	2.09 (7)
Se3—O3	1.718 (19)	Ni4—O4	1.98 (7)
Se3—O11	1.700 (19)	Ni5—O1^vii	2.16 (5)
Se3—O5^ii	1.77 (6)	Ni5—O11^iii	2.037 (19)
Se4—O10^iii	1.75 (8)	Ni5—O10^iii	2.04 (7)
Se4—O8^ii	1.71 (2)	Ni5—O12^vi	2.16 (6)
Se4—O6^iv	1.73 (6)	Ni5—Cl2	2.39 (3)
Se4—Ni4	2.81 (3)	O1—Ni5^vii	2.16 (5)
Ni1—O7	1.99 (6)	O2—Ni3^v	2.02 (2)
Ni1—O8	2.045 (19)	O4—Ni3^ii	2.17 (7)
Ni1—O5	2.10 (6)	O5—Se3^ii	1.77 (6)
Ni1—O9	2.01 (2)	O5—Ni2^ii	1.97 (6)
Ni1—O3	2.042 (19)	O6—Se4^viii	1.73 (6)
Ni1—Ni2^ii	2.95 (3)	O6—Ni4^viii	2.09 (7)
Ni2—O6	2.10 (7)	O8—Se4^ii	1.71 (2)
Ni2—O9^ii	2.01 (2)	O8—Ni4^ii	2.03 (2)
Ni2—O5^ii	1.97 (6)	O9—Se2^i	1.695 (19)
Ni2—O10	2.03 (8)	O9—Ni2^ii	2.01 (2)
Ni2—Cl1	2.48 (4)	O10—Se4^iii	1.75 (8)
Ni2—Cl2	2.406 (19)	O10—Ni5^iii	2.04 (7)
Ni2—Ni1^ii	2.95 (3)	O11—Ni5^iii	2.037 (19)
Ni3—O4^ii	2.17 (7)	O12—Ni4^ii	2.01 (2)
Ni3—O2	2.02 (2)	O12—Ni4^ix	2.00 (2)
Ni3—O2^v	2.02 (2)	O12—Ni5^ix	2.16 (6)
Ni3—O11	2.035 (19)
O7—Se1—O2	96 (3)	O12^vi—Ni4—O8^ii	86 (2)
O7—Se1—O12	106 (3)	O1—Ni4—O8^ii	166 (2)
O2—Se1—O12	101 (2)	O12^ii—Ni4—O6^iv	176 (4)
O9^i—Se2—O4	106 (2)	O12^vi—Ni4—O6^iv	92 (3)
O9^i—Se2—O1	102 (3)	O1—Ni4—O6^iv	96 (2)
O4—Se2—O1	85 (3)	O8^ii—Ni4—O6^iv	74.9 (18)
O9^i—Se2—Ni4	97 (2)	O12^ii—Ni4—O4	90 (3)
O4—Se2—Ni4	40 (2)	O12^vi—Ni4—O4	173 (3)
O1—Se2—Ni4	47.9 (16)	O1—Ni4—O4	68 (2)
O3—Se3—O11	93.0 (14)	O8^ii—Ni4—O4	101 (2)
O3—Se3—O5^ii	107 (3)	O6^iv—Ni4—O4	93 (3)
O11—Se3—O5^ii	97 (3)	O12^ii—Ni4—Se2	95 (2)
O10^iii—Se4—O8^ii	88 (3)	O12^vi—Ni4—Se2	138 (2)
O10^iii—Se4—O6^iv	100 (3)	O1—Ni4—Se2	33.6 (16)
O8^ii—Se4—O6^iv	94 (2)	O8^ii—Ni4—Se2	132.9 (18)
O10^iii—Se4—Ni4	97 (2)	O6^iv—Ni4—Se2	86 (2)
O8^ii—Se4—Ni4	45.9 (10)	O4—Ni4—Se2	36.6 (15)
O6^iv—Se4—Ni4	48 (2)	O12^ii—Ni4—Se4	144 (2)
O7—Ni1—O8	92 (2)	O12^vi—Ni4—Se4	89.7 (19)
O7—Ni1—O5	165 (2)	O1—Ni4—Se4	132.7 (17)
O8—Ni1—O5	101 (2)	O8^ii—Ni4—Se4	37.1 (8)
O7—Ni1—O9	91 (2)	O6^iv—Ni4—Se4	37.8 (15)
O8—Ni1—O9	151 (2)	O4—Ni4—Se4	97 (2)
O5—Ni1—O9	74.9 (19)	Se2—Ni4—Se4	111.8 (12)
O7—Ni1—O3	85 (2)	O1^vii—Ni5—O11^iii	93 (2)
O8—Ni1—O3	107.5 (14)	O1^vii—Ni5—O10^iii	172 (3)
O5—Ni1—O3	98 (2)	O11^iii—Ni5—O10^iii	83 (3)
O9—Ni1—O3	102 (2)	O1^vii—Ni5—O12^vi	81.8 (15)
O7—Ni1—Ni2^ii	125.5 (18)	O11^iii—Ni5—O12^vi	101.0 (16)
O8—Ni1—Ni2^ii	116.4 (13)	O10^iii—Ni5—O12^vi	93 (2)
O5—Ni1—Ni2^ii	41.9 (17)	O1^vii—Ni5—Cl2	85.6 (17)
O9—Ni1—Ni2^ii	42.7 (8)	O11^iii—Ni5—Cl2	109.1 (13)
O3—Ni1—Ni2^ii	123.6 (12)	O10^iii—Ni5—Cl2	102 (2)
O6—Ni2—O9^ii	97 (2)	O12^vi—Ni5—Cl2	147.8 (16)
O6—Ni2—O5^ii	171 (3)	Ni2—Cl1—Ni3	109.5 (14)
O9^ii—Ni2—O5^ii	78 (2)	Ni5—Cl2—Ni2	154.1 (18)
O6—Ni2—O10	93 (3)	Se2—O1—Ni5^vii	121 (3)
O9^ii—Ni2—O10	166 (2)	Se2—O1—Ni4	98 (2)
O5^ii—Ni2—O10	91 (3)	Ni5^vii—O1—Ni4	92.9 (19)
O6—Ni2—Cl1	90 (2)	Se1—O2—Ni3	122 (2)
O9^ii—Ni2—Cl1	102 (2)	Se1—O2—Ni3^v	120 (2)
O5^ii—Ni2—Cl1	98 (2)	Ni3—O2—Ni3^v	111 (2)
O10—Ni2—Cl1	88 (2)	Se3—O3—Ni1	129.0 (19)
O6—Ni2—Cl2	92 (2)	Se3—O3—Ni3	95.6 (13)
O9^ii—Ni2—Cl2	78 (2)	Ni1—O3—Ni3	126.3 (17)
O5^ii—Ni2—Cl2	80 (2)	Se2—O4—Ni3^ii	120 (3)
O10—Ni2—Cl2	92 (2)	Se2—O4—Ni4	103 (3)
Cl1—Ni2—Cl2	178.1 (16)	Ni3^ii—O4—Ni4	135 (3)
O6—Ni2—Ni1^ii	126.4 (18)	Se3^ii—O5—Ni1	135 (3)
O9^ii—Ni2—Ni1^ii	42.7 (8)	Se3^ii—O5—Ni2^ii	129 (3)
O5^ii—Ni2—Ni1^ii	45.3 (18)	Ni1—O5—Ni2^ii	93 (3)
O10—Ni2—Ni1^ii	123 (2)	Se4^viii—O6—Ni2	124 (3)
Cl1—Ni2—Ni1^ii	125.4 (14)	Se4^viii—O6—Ni4^viii	94 (3)
Cl2—Ni2—Ni1^ii	53.0 (6)	Ni2—O6—Ni4^viii	127 (3)
O4^ii—Ni3—O2	83 (3)	Se1—O7—Ni1	150 (3)
O4^ii—Ni3—O2^v	90 (3)	Se4^ii—O8—Ni1	119.6 (18)
O2—Ni3—O2^v	69 (2)	Se4^ii—O8—Ni4^ii	97.0 (16)
O4^ii—Ni3—O11	173 (2)	Ni1—O8—Ni4^ii	123.0 (19)
O2—Ni3—O11	101 (3)	Se2^i—O9—Ni1	124 (2)
O2^v—Ni3—O11	97 (2)	Se2^i—O9—Ni2^ii	133 (3)
O4^ii—Ni3—O3	98.5 (19)	Ni1—O9—Ni2^ii	94.6 (14)
O2—Ni3—O3	104.0 (19)	Se4^iii—O10—Ni5^iii	99 (3)
O2^v—Ni3—O3	169 (3)	Se4^iii—O10—Ni2	124 (4)
O11—Ni3—O3	74.8 (11)	Ni5^iii—O10—Ni2	133 (4)
O4^ii—Ni3—Cl1	88.5 (19)	Se3—O11—Ni5^iii	125.8 (19)
O2—Ni3—Cl1	159.5 (17)	Se3—O11—Ni3	96.4 (13)
O2^v—Ni3—Cl1	92.6 (16)	Ni5^iii—O11—Ni3	135.9 (18)
O11—Ni3—Cl1	90 (2)	Se1—O12—Ni4^ii	120 (3)
O3—Ni3—Cl1	95.8 (16)	Se1—O12—Ni4^ix	119 (3)
O12^ii—Ni4—O12^vi	85 (3)	Ni4^ii—O12—Ni4^ix	95 (3)
O12^ii—Ni4—O1	83 (2)	Se1—O12—Ni5^ix	123 (2)
O12^vi—Ni4—O1	106 (3)	Ni4^ii—O12—Ni5^ix	100 (2)
O12^ii—Ni4—O8^ii	106 (2)	Ni4^ix—O12—Ni5^ix	94 (2)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+1, −z+1; (iv) x, y, z+1; (v) −x+1, −y, −z; (vi) x+1, y+1, z+1; (vii) −x+2, −y+2, −z+2; (viii) x, y, z−1; (ix) x−1, y−1, z−1.

(Phase_1_PXRD)

Crystal data

Ni4Se4O12	V = 2091.14 Å^3
Mr = 742.6	Z = 1
Monoclinic, C2/c	Dx = 0.122 Mg m^−3
Hall symbol: -C 2yc	Cu Kα radiation, λ = 1.5418 Å
a = 15.4691 Å	µ = 0.66 mm^−1
b = 9.8078 Å	T = 0 K
c = 14.7312 Å	× × mm
β = 110.6685°

Data collection

X-Pert diffractometer	k = ?→?
Radiation source: X-ray tube	l = ?→?
h = ?→?

Refinement

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

	x	y	z	Uiso*/Ueq
Se11	0.37786	0.13642	0.10606	0.0066*
Se21	0.08573	0.11577	0.3684	0.0066*
Se31	0.38846	0.31264	0.35376	0.0066*
Se41	0.0949	0.38271	0.1831	0.0066*
Ni11	0.0684	0.11764	0.03442	0.0066*
Ni21	0.25919	0.36657	0.08686	0.0066*
Ni31	0.23777	0.35699	0.4154	0.0066*
Ni41	0.22462	0.09267	0.24273	0.0066*
O11	0.34222	0.26455	0.01836	0.0091*
O21	0.32079	0.01053	0.02284	0.0091*
O31	0.30572	0.1922	0.16749	0.0091*
O41	0.16841	0.19931	0.44951	0.0091*
O51	0.03524	0.01886	0.4258	0.0091*
O61	0.15326	0.00811	0.33208	0.0091*
O71	0.47046	0.24875	0.45176	0.0091*
O81	0.30099	0.20473	0.3611	0.0091*
O91	0.34563	0.46688	0.38237	0.0091*
O101	0.11163	0.4085	0.29924	0.0091*
O111	0.10729	0.21251	0.17251	0.0091*
O121	0.19961	0.43141	0.18637	0.0091*

Bond lengths (Å)

Se11—O11	1.7463	Ni21—O11	2.141
Se11—O21	1.7444	Ni21—O11^i	2.1911
Se11—O31	1.754	Ni21—O21^i	2.0454
Se21—O41	1.6297	Ni21—O31	2.0616
Se21—O51	1.6415	Ni21—O61^vi	2.0114
Se21—O61	1.6991	Ni21—O121	2.0872
Se31—O71	1.6713	Ni31—O21^vi	2.1208
Se31—O81	1.751	Ni31—O41	2.0435
Se31—O91	1.7613	Ni31—O41^vii	2.0815
Se41—O101	1.657	Ni31—O81	2.0925
Se41—O111	1.6937	Ni31—O91	2.1807
Se41—O121	1.673	Ni31—O101	2.1526
Ni11—O11^i	2.1471	Ni41—O31	2.1764
Ni11—O51^ii	2.125	Ni41—O61	2.1597
Ni11—O51^iii	2.0091	Ni41—O81	2.0469
Ni11—O71^iv	2.0477	Ni41—O91^v	2.1646
Ni11—O91^v	2.0753	Ni41—O111	2.1025
Ni11—O111	2.1218	Ni41—O121^v	2.0253

Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) −x, y, −z+1/2; (iii) x, −y, z−1/2; (iv) x−1/2, −y+1/2, z−1/2; (v) −x+1/2, y−1/2, −z+1/2; (vi) −x+1/2, y+1/2, −z+1/2; (vii) −x+1/2, −y+1/2, −z+1.

(Phase_4_PXRD)

Crystal data

Cl2Ni5O12Se4	γ = 101.948°
Mr = 872.2	V = 659.13 Å^3
Triclinic, P1	Z = 1
Hall symbol: -P 1	Dx = 0.476 Mg m^−3
a = 9.2823 Å	Cu Kα radiation, λ = 1.5418 Å
b = 9.3756 Å	µ = 2.18 mm^−1
c = 8.0733 Å	T = 0 K
α = 105.6114°	× × mm
β = 91.8441°

Data collection

X-Pert diffractometer	k = ?→?
Radiation source: X-ray tube	l = ?→?
h = ?→?

Refinement

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

	x	y	z	Uiso*/Ueq
Se14	0.23738	−0.09743	0.18299	0.0068*
Se24	0.6844	0.89103	1.29069	0.0068*
Se34	0.61572	0.33059	0.45087	0.0068*
Se44	0.89741	0.56941	0.84824	0.0068*
Ni14	0.24867	0.2752	0.42919	0.0068*
Ni24	0.80505	0.56071	0.23607	0.0068*
Ni34	0.51355	0.17738	0.09904	0.0068*
Ni44	0.88874	0.86475	1.03152	0.0068*
Ni54	1.12121	0.80645	0.75091	0.0068*
Cl14	0.62844	0.39784	0.0224	0.0101*
Cl24	1.0122	0.7191	0.4586	0.0101*
O14	0.87569	0.98261	1.29505	0.0106*
O24	0.39097	−0.03945	0.08591	0.0106*
O34	0.44694	0.28911	0.33225	0.0106*
O44	0.66127	0.82065	1.07102	0.0106*
O54	0.29491	0.48985	0.55052	0.0106*
O64	0.91903	0.66645	0.0732	0.0106*
O74	0.21439	0.04515	0.34718	0.0106*
O84	0.10521	0.27356	0.21534	0.0106*
O94	0.32207	0.28143	0.68945	0.0106*
O104	0.91789	0.38988	0.17594	0.0106*
O114	0.66924	0.19209	0.30172	0.0106*
O124	0.12813	−0.07604	0.01175	0.0106*

Bond lengths (Å)

Se14—O24	1.7096	Ni24—O64	2.0465
Se14—O74	1.665	Ni24—O94^ii	2.0577
Se14—O124	1.7672	Ni24—O104	2.0511
Se24—O14	1.7999	Ni34—Cl14	2.3687
Se24—O44	1.7069	Ni34—O24	2.0874
Se24—O94^i	1.6564	Ni34—O24^v	2.0513
Se34—O34	1.7244	Ni34—O34	2.0751
Se34—O54^ii	1.719	Ni34—O44^ii	2.0979
Se34—O114	1.6873	Ni34—O114	2.1045
Se44—O64^iii	1.7827	Ni44—O14	2.1375
Se44—O84^ii	1.6889	Ni44—O44	2.1175
Se44—O104^iv	1.707	Ni44—O64^iii	2.0484
Ni14—Cl24^ii	2.6184	Ni44—O84^ii	2.0744
Ni14—O34	2.0161	Ni44—O124^vi	2.198
Ni14—O54	1.936	Ni44—O124^ii	2.1373
Ni14—O74	2.0311	Ni54—Cl24	2.3931
Ni14—O84	2.1409	Ni54—O14^vii	2.1028
Ni14—O94	2.1697	Ni54—O84^ii	2.1326
Ni24—Cl14	2.3149	Ni54—O104^iv	2.0472
Ni24—Cl24	2.5079	Ni54—O114^iv	2.0024
Ni24—O54^ii	2.1011	Ni54—O124^vi	2.0894

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y+1, −z+1; (iii) x, y, z+1; (iv) −x+2, −y+1, −z+1; (v) −x+1, −y, −z; (vi) x+1, y+1, z+1; (vii) −x+2, −y+2, −z+2.