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.
Supporting information
CCDC references: 1031643; 1031644; 1031645; 1031646; 1031647; 1031648
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.
Crystal data top
NiO3Se | V = 2158.95 Å3 |
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 top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.250 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 2861 (156) |
Crystal data top
NiO3Se | β = 110.2° |
Mr = 185.65 | V = 2158.95 Å3 |
Monoclinic, C2/c | Z = 32 |
a = 15.58 Å | Electrons radiation, λ = 0.02510 Å |
b = 9.96 Å | µ = 0.00 mm−1 |
c = 14.82 Å | × × mm |
Data collection top
TEM diffractometer | 662 reflections with I > 2σ(I) |
3389 measured reflections | Rint = 0.296 |
1142 independent reflections | θmax = 0.8° |
Refinement top
R[F2 > 2σ(F2)] = 0.250 | 0 restraints |
wR(F2) = 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 | |
Special details top
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 (Å2) top | 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) top
Se1—O2 | 1.70 (3) | Ni2—Se1i | 2.943 (18) |
Se1—O1 | 1.73 (3) | Ni3—O2vi | 2.07 (3) |
Se1—O3 | 1.74 (3) | Ni3—O8 | 2.07 (3) |
Se1—Ni2i | 2.943 (18) | Ni3—O4 | 2.08 (3) |
Se2—O4 | 1.71 (3) | Ni3—O4vii | 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—O12v | 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—O9v | 2.14 (3) |
Se4—O11 | 1.72 (3) | O1—Ni1i | 2.16 (4) |
Ni1—O7ii | 2.02 (4) | O1—Ni2i | 2.32 (4) |
Ni1—O1i | 2.16 (4) | O2—Ni2i | 2.07 (4) |
Ni1—O5iii | 2.05 (3) | O2—Ni3v | 2.07 (3) |
Ni1—O11 | 2.07 (3) | O4—Ni3vii | 2.09 (3) |
Ni1—O5iv | 2.12 (3) | O5—Ni1viii | 2.05 (3) |
Ni1—O9v | 2.10 (3) | O5—Ni1iv | 2.12 (3) |
Ni2—O6vi | 2.15 (3) | O6—Ni2v | 2.15 (3) |
Ni2—O2i | 2.07 (4) | O7—Ni1ix | 2.02 (4) |
Ni2—O12 | 2.08 (4) | O9—Ni4vi | 2.14 (3) |
Ni2—O1i | 2.32 (4) | O9—Ni1vi | 2.10 (3) |
Ni2—O3 | 2.15 (3) | O12—Ni4vi | 1.98 (4) |
Ni2—O1 | 2.14 (4) | | |
| | | |
O2—Se1—O1 | 94.9 (16) | O2vi—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—Ni2i | 43.5 (11) | O4vii—Ni3—O9 | 86.9 (13) |
O1—Se1—Ni2i | 51.9 (13) | O10—Ni3—O9 | 103.1 (13) |
O3—Se1—Ni2i | 96.8 (13) | O2vi—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) | O4vii—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) | O12v—Ni4—O3 | 104.7 (15) |
O9—Se3—Ni3 | 50.1 (11) | O12v—Ni4—O11 | 161.4 (16) |
O8—Se3—Ni3 | 45.2 (11) | O3—Ni4—O11 | 92.4 (13) |
O7—Se3—Ni3 | 101.7 (13) | O12v—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) | O12v—Ni4—O6 | 73.3 (14) |
O7ii—Ni1—O1i | 82.7 (14) | O3—Ni4—O6 | 176.0 (15) |
O7ii—Ni1—O5iii | 86.7 (13) | O11—Ni4—O6 | 90.1 (14) |
O1i—Ni1—O5iii | 92.3 (13) | O8—Ni4—O6 | 95.4 (14) |
O7ii—Ni1—O11 | 102.3 (14) | O12v—Ni4—O9v | 93.8 (14) |
O1i—Ni1—O11 | 94.1 (14) | O3—Ni4—O9v | 88.3 (12) |
O5iii—Ni1—O11 | 169.4 (13) | O11—Ni4—O9v | 79.1 (13) |
O7ii—Ni1—O5iv | 90.0 (14) | O8—Ni4—O9v | 169.1 (14) |
O1i—Ni1—O5iv | 172.7 (14) | O6—Ni4—O9v | 95.2 (13) |
O5iii—Ni1—O5iv | 86.6 (13) | Se1—O1—Ni1i | 129 (2) |
O11—Ni1—O5iv | 88.0 (14) | Se1—O1—Ni2i | 92.0 (15) |
O7ii—Ni1—O9v | 174.4 (14) | Ni1i—O1—Ni2i | 114.2 (14) |
O1i—Ni1—O9v | 101.8 (15) | Se1—O1—Ni2 | 96.7 (16) |
O5iii—Ni1—O9v | 89.9 (13) | Ni1i—O1—Ni2 | 120.1 (15) |
O11—Ni1—O9v | 80.6 (14) | Ni2i—O1—Ni2 | 98.1 (16) |
O5iv—Ni1—O9v | 85.3 (13) | Se1—O2—Ni2i | 102.1 (15) |
O6vi—Ni2—O2i | 101.3 (13) | Se1—O2—Ni3v | 117.3 (18) |
O6vi—Ni2—O12 | 72.3 (15) | Ni2i—O2—Ni3v | 126.8 (19) |
O2i—Ni2—O12 | 94.8 (15) | Se1—O3—Ni4 | 139.7 (16) |
O6vi—Ni2—O1i | 171.4 (13) | Se1—O3—Ni2 | 96.1 (14) |
O2i—Ni2—O1i | 70.1 (13) | Ni4—O3—Ni2 | 117.0 (16) |
O12—Ni2—O1i | 108.6 (15) | Se2—O4—Ni3 | 117.4 (15) |
O6vi—Ni2—O3 | 100.4 (13) | Se2—O4—Ni3vii | 136.4 (14) |
O2i—Ni2—O3 | 158.0 (14) | Ni3—O4—Ni3vii | 99.5 (14) |
O12—Ni2—O3 | 95.4 (13) | Se2—O5—Ni1viii | 136 (2) |
O1i—Ni2—O3 | 88.1 (12) | Se2—O5—Ni1iv | 113.7 (14) |
O6vi—Ni2—O1 | 99.0 (14) | Ni1viii—O5—Ni1iv | 93.4 (13) |
O2i—Ni2—O1 | 99.8 (15) | Se2—O6—Ni2v | 124.1 (17) |
O12—Ni2—O1 | 164.3 (16) | Se2—O6—Ni4 | 116.1 (16) |
O1i—Ni2—O1 | 81.9 (16) | Ni2v—O6—Ni4 | 101.7 (15) |
O3—Ni2—O1 | 72.9 (12) | Se3—O7—Ni1ix | 120.8 (17) |
O6vi—Ni2—Se1i | 135.3 (10) | Se3—O8—Ni3 | 99.8 (15) |
O2i—Ni2—Se1i | 34.4 (9) | Se3—O8—Ni4 | 128 (2) |
O12—Ni2—Se1i | 107.8 (12) | Ni3—O8—Ni4 | 125 (2) |
O1i—Ni2—Se1i | 36.1 (8) | Se3—O9—Ni4vi | 109.6 (15) |
O3—Ni2—Se1i | 123.6 (10) | Se3—O9—Ni1vi | 117.9 (19) |
O1—Ni2—Se1i | 87.6 (11) | Ni4vi—O9—Ni1vi | 98.0 (13) |
O2vi—Ni3—O8 | 167.1 (15) | Se3—O9—Ni3 | 90.5 (13) |
O2vi—Ni3—O4 | 102.0 (13) | Ni4vi—O9—Ni3 | 109.2 (16) |
O8—Ni3—O4 | 90.8 (12) | Ni1vi—O9—Ni3 | 131.2 (16) |
O2vi—Ni3—O4vii | 94.3 (13) | Se4—O10—Ni3 | 133 (2) |
O8—Ni3—O4vii | 89.3 (13) | Se4—O11—Ni4 | 128 (2) |
O4—Ni3—O4vii | 80.5 (14) | Se4—O11—Ni1 | 124.6 (18) |
O2vi—Ni3—O10 | 82.7 (13) | Ni4—O11—Ni1 | 100.3 (14) |
O8—Ni3—O10 | 95.7 (14) | Se4—O12—Ni4vi | 128.8 (19) |
O4—Ni3—O10 | 90.5 (13) | Se4—O12—Ni2 | 119.0 (19) |
O4vii—Ni3—O10 | 169.7 (15) | Ni4vi—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)
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Crystal data top
Cl2Ni3O10Se4 | γ = 90° |
Mr = 722.81 | V = 529.3 Å3 |
?, 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 top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.207 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 3284 (159) |
Crystal data top
Cl2Ni3O10Se4 | β = 106.8° |
Mr = 722.81 | γ = 90° |
?, C2/m | V = 529.3 Å3 |
a = 7.17 Å | Z = 2 |
b = 13.70 Å | Electrons radiation, λ = 0.02510 Å |
c = 5.63 Å | µ = 0.00 mm−1 |
α = 90° | × × mm |
Data collection top
TEM diffractometer | 194 reflections with I > 2σ(I) |
751 measured reflections | Rint = 0.283 |
248 independent reflections | θmax = 0.7° |
Refinement top
R[F2 > 2σ(F2)] = 0.207 | 0 restraints |
wR(F2) = 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 | |
Special details top
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 (Å2) top | 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) top
Ni1—O2i | 2.07 (3) | Ni2—Cl1 | 2.44 (2) |
Ni1—O2ii | 2.07 (3) | Ni2—Cl1vii | 2.44 (2) |
Ni1—O2iii | 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—Cl1iii | 2.35 (2) | Cl1—Ni2vii | 2.44 (2) |
Ni2—O1iv | 2.04 (4) | O1—Ni2v | 2.04 (4) |
Ni2—O1v | 2.04 (4) | O2—Ni2viii | 2.04 (3) |
Ni2—O2ii | 2.04 (3) | O3—Se1ix | 1.80 (3) |
Ni2—O2vi | 2.04 (3) | | |
| | | |
O2i—Ni1—O2ii | 180.000 (2) | O1iv—Ni2—Cl1 | 175.5 (14) |
O2i—Ni1—O2iii | 85.8 (16) | O1v—Ni2—Cl1 | 85.5 (13) |
O2ii—Ni1—O2iii | 94.2 (16) | O2ii—Ni2—Cl1 | 82.2 (10) |
O2i—Ni1—O2 | 94.2 (16) | O2vi—Ni2—Cl1 | 89.6 (10) |
O2ii—Ni1—O2 | 85.8 (16) | O1iv—Ni2—Cl1vii | 85.5 (13) |
O2iii—Ni1—O2 | 180.0 (9) | O1v—Ni2—Cl1vii | 175.5 (14) |
O2i—Ni1—Cl1 | 96.1 (9) | O2ii—Ni2—Cl1vii | 89.6 (10) |
O2ii—Ni1—Cl1 | 83.9 (8) | O2vi—Ni2—Cl1vii | 82.2 (10) |
O2iii—Ni1—Cl1 | 83.9 (8) | Cl1—Ni2—Cl1vii | 90.3 (11) |
O2—Ni1—Cl1 | 96.1 (8) | O1—Se1—O2 | 101.5 (17) |
O2i—Ni1—Cl1iii | 83.9 (8) | O1—Se1—O3 | 110 (2) |
O2ii—Ni1—Cl1iii | 96.1 (8) | O2—Se1—O3 | 96.1 (15) |
O2iii—Ni1—Cl1iii | 96.1 (8) | Ni1—Cl1—Ni2 | 87.0 (8) |
O2—Ni1—Cl1iii | 83.9 (8) | Ni1—Cl1—Ni2vii | 87.0 (8) |
Cl1—Ni1—Cl1iii | 180.000 (3) | Ni2—Cl1—Ni2vii | 89.7 (10) |
O1iv—Ni2—O1v | 99 (2) | Se1—O1—Ni2v | 128 (3) |
O1iv—Ni2—O2ii | 96.4 (12) | Se1—O2—Ni2viii | 128.1 (16) |
O1v—Ni2—O2ii | 91.1 (12) | Se1—O2—Ni1 | 124.6 (15) |
O1iv—Ni2—O2vi | 91.1 (12) | Ni2viii—O2—Ni1 | 106.7 (14) |
O1v—Ni2—O2vi | 96.4 (12) | Se1—O3—Se1ix | 128 (4) |
O2ii—Ni2—O2vi | 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)
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Crystal data top
H2Cl4Ni5O16Se6 | γ = 90° |
Mr = 1167.03 | V = 2058.3 Å3 |
?, 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 top
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 top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.239 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.556 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 1100 (270) |
Crystal data top
H2Cl4Ni5O16Se6 | β = 118.1° |
Mr = 1167.03 | γ = 90° |
?, C2/c | V = 2058.3 Å3 |
a = 21.94 Å | Z = 4 |
b = 8.38 Å | Electrons radiation, λ = 0.02510 Å |
c = 12.68 Å | µ = 0.00 mm−1 |
α = 90° | × × mm |
Data collection top
TEM diffractometer | 245 reflections with I > 2σ(I) |
1205 measured reflections | Rint = 0.210 |
351 independent reflections | θmax = 0.5° |
Refinement top
R[F2 > 2σ(F2)] = 0.239 | 8 restraints |
wR(F2) = 0.556 | H atoms treated by a mixture of independent and constrained refinement |
S = 2.27 | Δρmax = 0.46 e Å−3 |
351 reflections | Δρmin = −0.56 e Å−3 |
64 parameters | |
Special details top
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 (Å2) top | 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) top
Se1—O4 | 1.70 (2) | Ni2—O4iv | 2.05 (6) |
Se1—O6 | 1.73 (10) | Ni2—O7 | 2.09 (6) |
Se1—O1 | 1.70 (6) | Ni2—Cl2v | 2.390 (19) |
Se2—O6i | 1.68 (8) | Ni3—O2ii | 2.09 (7) |
Se2—O2 | 1.69 (2) | Ni3—O2 | 2.09 (7) |
Se2—O5ii | 1.71 (2) | Ni3—O3 | 2.14 (6) |
Se3—O7iii | 1.69 (2) | Ni3—O3ii | 2.14 (6) |
Se3—O8 | 1.70 (2) | Ni3—Cl1ii | 2.48 (4) |
Se3—O3 | 1.70 (2) | Ni3—Cl1 | 2.48 (4) |
Ni1—O1 | 2.00 (7) | Cl2—Ni2iv | 2.390 (19) |
Ni1—O5 | 2.02 (8) | O4—Ni2v | 2.05 (6) |
Ni1—O3 | 2.12 (6) | O4—Ni1v | 2.15 (6) |
Ni1—O4iv | 2.15 (6) | O5—Se2ii | 1.71 (2) |
Ni1—Cl1 | 2.39 (2) | O5—Ni2iv | 2.03 (8) |
Ni1—Cl2 | 2.50 (5) | O6—Se2i | 1.68 (8) |
Ni2—O1 | 2.20 (8) | O7—Se3iii | 1.69 (2) |
Ni2—O7iii | 2.15 (6) | O7—Ni2iii | 2.15 (6) |
Ni2—O5v | 2.03 (8) | | |
| | | |
O4—Se1—O6 | 93 (4) | O4iv—Ni2—Cl2v | 174 (2) |
O4—Se1—O1 | 111 (4) | O7—Ni2—Cl2v | 98 (2) |
O6—Se1—O1 | 99 (4) | O2ii—Ni3—O2 | 180.000 (11) |
O6i—Se2—O2 | 96 (4) | O2ii—Ni3—O3 | 93.7 (18) |
O6i—Se2—O5ii | 92 (4) | O2—Ni3—O3 | 86.3 (19) |
O2—Se2—O5ii | 108 (4) | O2ii—Ni3—O3ii | 86.3 (19) |
O7iii—Se3—O8 | 99 (4) | O2—Ni3—O3ii | 93.7 (18) |
O7iii—Se3—O3 | 110 (3) | O3—Ni3—O3ii | 180.000 (5) |
O8—Se3—O3 | 106 (4) | O2ii—Ni3—Cl1ii | 79.5 (19) |
O1—Ni1—O5 | 173 (3) | O2—Ni3—Cl1ii | 100.5 (19) |
O1—Ni1—O3 | 91 (3) | O3—Ni3—Cl1ii | 101.2 (15) |
O5—Ni1—O3 | 90 (2) | O3ii—Ni3—Cl1ii | 78.8 (15) |
O1—Ni1—O4iv | 81 (3) | O2ii—Ni3—Cl1 | 100.5 (19) |
O5—Ni1—O4iv | 91 (3) | O2—Ni3—Cl1 | 79.5 (19) |
O3—Ni1—O4iv | 94 (3) | O3—Ni3—Cl1 | 78.8 (15) |
O1—Ni1—Cl1 | 92 (3) | O3ii—Ni3—Cl1 | 101.2 (15) |
O5—Ni1—Cl1 | 96 (3) | Cl1ii—Ni3—Cl1 | 180.000 (2) |
O3—Ni1—Cl1 | 81 (2) | Ni1—Cl1—Ni3 | 87.1 (13) |
O4iv—Ni1—Cl1 | 172 (2) | Ni2iv—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) |
O4iv—Ni1—Cl2 | 88 (2) | Se2—O2—Ni3 | 120 (4) |
Cl1—Ni1—Cl2 | 96.9 (16) | Se3—O3—Ni1 | 124 (3) |
O1—Ni2—O7iii | 87 (3) | Se3—O3—Ni3 | 121 (3) |
O1—Ni2—O5v | 93 (3) | Ni1—O3—Ni3 | 104.2 (17) |
O7iii—Ni2—O5v | 176 (3) | Se1—O4—Ni2v | 126 (4) |
O1—Ni2—O4iv | 79 (2) | Se1—O4—Ni1v | 132 (4) |
O7iii—Ni2—O4iv | 89 (3) | Ni2v—O4—Ni1v | 99.0 (18) |
O5v—Ni2—O4iv | 88 (3) | Se2ii—O5—Ni1 | 128 (5) |
O1—Ni2—O7 | 163 (3) | Se2ii—O5—Ni2iv | 132 (5) |
O7iii—Ni2—O7 | 81.9 (19) | Ni1—O5—Ni2iv | 100.4 (19) |
O5v—Ni2—O7 | 97 (3) | Se2i—O6—Se1 | 133 (6) |
O4iv—Ni2—O7 | 88 (2) | Se3iii—O7—Ni2iii | 129 (3) |
O1—Ni2—Cl2v | 95 (2) | Se3iii—O7—Ni2 | 125 (3) |
O7iii—Ni2—Cl2v | 93 (2) | Ni2iii—O7—Ni2 | 98.1 (19) |
O5v—Ni2—Cl2v | 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)
top
Crystal data top
Cl2Ni5O12Se4 | γ = 101.6° |
Mr = 872.19 | V = 684.2 Å3 |
?, 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 top
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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.330 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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+0.001xFc2λ3/sin(2θ)]-1/4 |
19 restraints | Extinction coefficient: 6040 (146) |
Crystal data top
Cl2Ni5O12Se4 | β = 91.6° |
Mr = 872.19 | γ = 101.6° |
?, P1 | V = 684.2 Å3 |
a = 9.44 Å | Z = 2 |
b = 9.44 Å | Electrons radiation, λ = 0.02510 Å |
c = 8.14 Å | µ = 0.00 mm−1 |
α = 105.1° | × × mm |
Data collection top
TEM diffractometer | 425 reflections with I > 2σ(I) |
2888 measured reflections | Rint = 0.228 |
1464 independent reflections | θmax = 0.8° |
Refinement top
R[F2 > 2σ(F2)] = 0.330 | 19 restraints |
wR(F2) = 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 | |
Special details top
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 (Å2) top | 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) top
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—O12ii | 2.01 (2) |
Se2—O9i | 1.695 (19) | Ni4—O12vi | 2.00 (2) |
Se2—O4 | 1.84 (5) | Ni4—O1 | 2.25 (5) |
Se2—O1 | 1.68 (6) | Ni4—O8ii | 2.03 (2) |
Se2—Ni4 | 3.00 (4) | Ni4—O6iv | 2.09 (7) |
Se3—O3 | 1.718 (19) | Ni4—O4 | 1.98 (7) |
Se3—O11 | 1.700 (19) | Ni5—O1vii | 2.16 (5) |
Se3—O5ii | 1.77 (6) | Ni5—O11iii | 2.037 (19) |
Se4—O10iii | 1.75 (8) | Ni5—O10iii | 2.04 (7) |
Se4—O8ii | 1.71 (2) | Ni5—O12vi | 2.16 (6) |
Se4—O6iv | 1.73 (6) | Ni5—Cl2 | 2.39 (3) |
Se4—Ni4 | 2.81 (3) | O1—Ni5vii | 2.16 (5) |
Ni1—O7 | 1.99 (6) | O2—Ni3v | 2.02 (2) |
Ni1—O8 | 2.045 (19) | O4—Ni3ii | 2.17 (7) |
Ni1—O5 | 2.10 (6) | O5—Se3ii | 1.77 (6) |
Ni1—O9 | 2.01 (2) | O5—Ni2ii | 1.97 (6) |
Ni1—O3 | 2.042 (19) | O6—Se4viii | 1.73 (6) |
Ni1—Ni2ii | 2.95 (3) | O6—Ni4viii | 2.09 (7) |
Ni2—O6 | 2.10 (7) | O8—Se4ii | 1.71 (2) |
Ni2—O9ii | 2.01 (2) | O8—Ni4ii | 2.03 (2) |
Ni2—O5ii | 1.97 (6) | O9—Se2i | 1.695 (19) |
Ni2—O10 | 2.03 (8) | O9—Ni2ii | 2.01 (2) |
Ni2—Cl1 | 2.48 (4) | O10—Se4iii | 1.75 (8) |
Ni2—Cl2 | 2.406 (19) | O10—Ni5iii | 2.04 (7) |
Ni2—Ni1ii | 2.95 (3) | O11—Ni5iii | 2.037 (19) |
Ni3—O4ii | 2.17 (7) | O12—Ni4ii | 2.01 (2) |
Ni3—O2 | 2.02 (2) | O12—Ni4ix | 2.00 (2) |
Ni3—O2v | 2.02 (2) | O12—Ni5ix | 2.16 (6) |
Ni3—O11 | 2.035 (19) | | |
| | | |
O7—Se1—O2 | 96 (3) | O12vi—Ni4—O8ii | 86 (2) |
O7—Se1—O12 | 106 (3) | O1—Ni4—O8ii | 166 (2) |
O2—Se1—O12 | 101 (2) | O12ii—Ni4—O6iv | 176 (4) |
O9i—Se2—O4 | 106 (2) | O12vi—Ni4—O6iv | 92 (3) |
O9i—Se2—O1 | 102 (3) | O1—Ni4—O6iv | 96 (2) |
O4—Se2—O1 | 85 (3) | O8ii—Ni4—O6iv | 74.9 (18) |
O9i—Se2—Ni4 | 97 (2) | O12ii—Ni4—O4 | 90 (3) |
O4—Se2—Ni4 | 40 (2) | O12vi—Ni4—O4 | 173 (3) |
O1—Se2—Ni4 | 47.9 (16) | O1—Ni4—O4 | 68 (2) |
O3—Se3—O11 | 93.0 (14) | O8ii—Ni4—O4 | 101 (2) |
O3—Se3—O5ii | 107 (3) | O6iv—Ni4—O4 | 93 (3) |
O11—Se3—O5ii | 97 (3) | O12ii—Ni4—Se2 | 95 (2) |
O10iii—Se4—O8ii | 88 (3) | O12vi—Ni4—Se2 | 138 (2) |
O10iii—Se4—O6iv | 100 (3) | O1—Ni4—Se2 | 33.6 (16) |
O8ii—Se4—O6iv | 94 (2) | O8ii—Ni4—Se2 | 132.9 (18) |
O10iii—Se4—Ni4 | 97 (2) | O6iv—Ni4—Se2 | 86 (2) |
O8ii—Se4—Ni4 | 45.9 (10) | O4—Ni4—Se2 | 36.6 (15) |
O6iv—Se4—Ni4 | 48 (2) | O12ii—Ni4—Se4 | 144 (2) |
O7—Ni1—O8 | 92 (2) | O12vi—Ni4—Se4 | 89.7 (19) |
O7—Ni1—O5 | 165 (2) | O1—Ni4—Se4 | 132.7 (17) |
O8—Ni1—O5 | 101 (2) | O8ii—Ni4—Se4 | 37.1 (8) |
O7—Ni1—O9 | 91 (2) | O6iv—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) | O1vii—Ni5—O11iii | 93 (2) |
O8—Ni1—O3 | 107.5 (14) | O1vii—Ni5—O10iii | 172 (3) |
O5—Ni1—O3 | 98 (2) | O11iii—Ni5—O10iii | 83 (3) |
O9—Ni1—O3 | 102 (2) | O1vii—Ni5—O12vi | 81.8 (15) |
O7—Ni1—Ni2ii | 125.5 (18) | O11iii—Ni5—O12vi | 101.0 (16) |
O8—Ni1—Ni2ii | 116.4 (13) | O10iii—Ni5—O12vi | 93 (2) |
O5—Ni1—Ni2ii | 41.9 (17) | O1vii—Ni5—Cl2 | 85.6 (17) |
O9—Ni1—Ni2ii | 42.7 (8) | O11iii—Ni5—Cl2 | 109.1 (13) |
O3—Ni1—Ni2ii | 123.6 (12) | O10iii—Ni5—Cl2 | 102 (2) |
O6—Ni2—O9ii | 97 (2) | O12vi—Ni5—Cl2 | 147.8 (16) |
O6—Ni2—O5ii | 171 (3) | Ni2—Cl1—Ni3 | 109.5 (14) |
O9ii—Ni2—O5ii | 78 (2) | Ni5—Cl2—Ni2 | 154.1 (18) |
O6—Ni2—O10 | 93 (3) | Se2—O1—Ni5vii | 121 (3) |
O9ii—Ni2—O10 | 166 (2) | Se2—O1—Ni4 | 98 (2) |
O5ii—Ni2—O10 | 91 (3) | Ni5vii—O1—Ni4 | 92.9 (19) |
O6—Ni2—Cl1 | 90 (2) | Se1—O2—Ni3 | 122 (2) |
O9ii—Ni2—Cl1 | 102 (2) | Se1—O2—Ni3v | 120 (2) |
O5ii—Ni2—Cl1 | 98 (2) | Ni3—O2—Ni3v | 111 (2) |
O10—Ni2—Cl1 | 88 (2) | Se3—O3—Ni1 | 129.0 (19) |
O6—Ni2—Cl2 | 92 (2) | Se3—O3—Ni3 | 95.6 (13) |
O9ii—Ni2—Cl2 | 78 (2) | Ni1—O3—Ni3 | 126.3 (17) |
O5ii—Ni2—Cl2 | 80 (2) | Se2—O4—Ni3ii | 120 (3) |
O10—Ni2—Cl2 | 92 (2) | Se2—O4—Ni4 | 103 (3) |
Cl1—Ni2—Cl2 | 178.1 (16) | Ni3ii—O4—Ni4 | 135 (3) |
O6—Ni2—Ni1ii | 126.4 (18) | Se3ii—O5—Ni1 | 135 (3) |
O9ii—Ni2—Ni1ii | 42.7 (8) | Se3ii—O5—Ni2ii | 129 (3) |
O5ii—Ni2—Ni1ii | 45.3 (18) | Ni1—O5—Ni2ii | 93 (3) |
O10—Ni2—Ni1ii | 123 (2) | Se4viii—O6—Ni2 | 124 (3) |
Cl1—Ni2—Ni1ii | 125.4 (14) | Se4viii—O6—Ni4viii | 94 (3) |
Cl2—Ni2—Ni1ii | 53.0 (6) | Ni2—O6—Ni4viii | 127 (3) |
O4ii—Ni3—O2 | 83 (3) | Se1—O7—Ni1 | 150 (3) |
O4ii—Ni3—O2v | 90 (3) | Se4ii—O8—Ni1 | 119.6 (18) |
O2—Ni3—O2v | 69 (2) | Se4ii—O8—Ni4ii | 97.0 (16) |
O4ii—Ni3—O11 | 173 (2) | Ni1—O8—Ni4ii | 123.0 (19) |
O2—Ni3—O11 | 101 (3) | Se2i—O9—Ni1 | 124 (2) |
O2v—Ni3—O11 | 97 (2) | Se2i—O9—Ni2ii | 133 (3) |
O4ii—Ni3—O3 | 98.5 (19) | Ni1—O9—Ni2ii | 94.6 (14) |
O2—Ni3—O3 | 104.0 (19) | Se4iii—O10—Ni5iii | 99 (3) |
O2v—Ni3—O3 | 169 (3) | Se4iii—O10—Ni2 | 124 (4) |
O11—Ni3—O3 | 74.8 (11) | Ni5iii—O10—Ni2 | 133 (4) |
O4ii—Ni3—Cl1 | 88.5 (19) | Se3—O11—Ni5iii | 125.8 (19) |
O2—Ni3—Cl1 | 159.5 (17) | Se3—O11—Ni3 | 96.4 (13) |
O2v—Ni3—Cl1 | 92.6 (16) | Ni5iii—O11—Ni3 | 135.9 (18) |
O11—Ni3—Cl1 | 90 (2) | Se1—O12—Ni4ii | 120 (3) |
O3—Ni3—Cl1 | 95.8 (16) | Se1—O12—Ni4ix | 119 (3) |
O12ii—Ni4—O12vi | 85 (3) | Ni4ii—O12—Ni4ix | 95 (3) |
O12ii—Ni4—O1 | 83 (2) | Se1—O12—Ni5ix | 123 (2) |
O12vi—Ni4—O1 | 106 (3) | Ni4ii—O12—Ni5ix | 100 (2) |
O12ii—Ni4—O8ii | 106 (2) | Ni4ix—O12—Ni5ix | 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. |
Crystal data top
Ni4Se4O12 | V = 2091.14 Å3 |
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 top
X-Pert diffractometer | k = ?→? |
Radiation source: X-ray tube | l = ?→? |
h = ?→? | |
Crystal data top
Ni4Se4O12 | V = 2091.14 Å3 |
Mr = 742.6 | Z = 1 |
Monoclinic, C2/c | Cu Kα radiation |
a = 15.4691 Å | µ = 0.66 mm−1 |
b = 9.8078 Å | T = 0 K |
c = 14.7312 Å | × × mm |
β = 110.6685° | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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) top
Se11—O11 | 1.7463 | Ni21—O11 | 2.141 |
Se11—O21 | 1.7444 | Ni21—O11i | 2.1911 |
Se11—O31 | 1.754 | Ni21—O21i | 2.0454 |
Se21—O41 | 1.6297 | Ni21—O31 | 2.0616 |
Se21—O51 | 1.6415 | Ni21—O61vi | 2.0114 |
Se21—O61 | 1.6991 | Ni21—O121 | 2.0872 |
Se31—O71 | 1.6713 | Ni31—O21vi | 2.1208 |
Se31—O81 | 1.751 | Ni31—O41 | 2.0435 |
Se31—O91 | 1.7613 | Ni31—O41vii | 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—O11i | 2.1471 | Ni41—O31 | 2.1764 |
Ni11—O51ii | 2.125 | Ni41—O61 | 2.1597 |
Ni11—O51iii | 2.0091 | Ni41—O81 | 2.0469 |
Ni11—O71iv | 2.0477 | Ni41—O91v | 2.1646 |
Ni11—O91v | 2.0753 | Ni41—O111 | 2.1025 |
Ni11—O111 | 2.1218 | Ni41—O121v | 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. |
Crystal data top
Cl2Ni5O12Se4 | γ = 101.948° |
Mr = 872.2 | V = 659.13 Å3 |
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 top
X-Pert diffractometer | k = ?→? |
Radiation source: X-ray tube | l = ?→? |
h = ?→? | |
Crystal data top
Cl2Ni5O12Se4 | γ = 101.948° |
Mr = 872.2 | V = 659.13 Å3 |
Triclinic, P1 | Z = 1 |
a = 9.2823 Å | Cu Kα radiation |
b = 9.3756 Å | µ = 2.18 mm−1 |
c = 8.0733 Å | T = 0 K |
α = 105.6114° | × × mm |
β = 91.8441° | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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) top
Se14—O24 | 1.7096 | Ni24—O64 | 2.0465 |
Se14—O74 | 1.665 | Ni24—O94ii | 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—O94i | 1.6564 | Ni34—O24v | 2.0513 |
Se34—O34 | 1.7244 | Ni34—O34 | 2.0751 |
Se34—O54ii | 1.719 | Ni34—O44ii | 2.0979 |
Se34—O114 | 1.6873 | Ni34—O114 | 2.1045 |
Se44—O64iii | 1.7827 | Ni44—O14 | 2.1375 |
Se44—O84ii | 1.6889 | Ni44—O44 | 2.1175 |
Se44—O104iv | 1.707 | Ni44—O64iii | 2.0484 |
Ni14—Cl24ii | 2.6184 | Ni44—O84ii | 2.0744 |
Ni14—O34 | 2.0161 | Ni44—O124vi | 2.198 |
Ni14—O54 | 1.936 | Ni44—O124ii | 2.1373 |
Ni14—O74 | 2.0311 | Ni54—Cl24 | 2.3931 |
Ni14—O84 | 2.1409 | Ni54—O14vii | 2.1028 |
Ni14—O94 | 2.1697 | Ni54—O84ii | 2.1326 |
Ni24—Cl14 | 2.3149 | Ni54—O104iv | 2.0472 |
Ni24—Cl24 | 2.5079 | Ni54—O114iv | 2.0024 |
Ni24—O54ii | 2.1011 | Ni54—O124vi | 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. |
Experimental details
| (Phase_1_NiSeO3) | (Phase_2_Ni3Se4O10Cl2) | (Phase_3_Ni5Se6O16Cl4H2) | (Phase_4_Ni5Se4O12Cl2) |
Crystal data |
Chemical formula | NiO3Se | Cl2Ni3O10Se4 | H2Cl4Ni5O16Se6 | Cl2Ni5O12Se4 |
Mr | 185.65 | 722.81 | 1167.03 | 872.19 |
Crystal system, space group | Monoclinic, C2/c | ?, C2/m | ?, C2/c | ?, P1 |
Temperature (K) | ? | ? | ? | ? |
a, b, c (Å) | 15.58, 9.96, 14.82 | 7.17, 13.70, 5.63 | 21.94, 8.38, 12.68 | 9.44, 9.44, 8.14 |
α, β, γ (°) | 90, 110.2, 90 | 90, 106.8, 90 | 90, 118.1, 90 | 105.1, 91.6, 101.6 |
V (Å3) | 2158.95 | 529.3 | 2058.3 | 684.2 |
Z | 32 | 2 | 4 | 2 |
Radiation type | Electrons, λ = 0.02510 Å | Electrons, λ = 0.02510 Å | Electrons, λ = 0.02510 Å | Electrons, λ = 0.02510 Å |
µ (mm−1) | 0.00 | 0.00 | 0.00 | 0.00 |
Crystal size (mm) | × × | × × | × × | × × |
|
Data collection |
Diffractometer | TEM diffractometer | TEM diffractometer | TEM diffractometer | TEM diffractometer |
Absorption correction | – | – | – | – |
No. of measured, independent and observed reflections | 3389, 1142, 662 [I > 2σ(I)] | 751, 248, 194 [I > 2σ(I)] | 1205, 351, 245 [I > 2σ(I)] | 2888, 1464, 425 [I > 2σ(I)] |
Rint | 0.296 | 0.283 | 0.210 | 0.228 |
θmax (°) | 0.8 | 0.7 | 0.5 | 0.8 |
(sin θ/λ)max (Å−1) | 0.528 | 0.515 | 0.369 | 0.556 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.250, 0.551, 1.75 | 0.207, 0.521, 1.96 | 0.239, 0.556, 2.27 | 0.330, 0.660, 1.47 |
No. of reflections | 1142 | 248 | 351 | 1464 |
No. of parameters | 82 | 22 | 64 | 94 |
No. of restraints | 0 | 0 | 8 | 19 |
H-atom treatment | – | – | H atoms treated by a mixture of independent and constrained refinement | – |
(Δ/σ)max | 0.188 | 0.299 | 0.006 | 0.431 |
Δρmax, Δρmin (e Å−3) | 0.85, −0.49 | 0.32, −0.55 | 0.46, −0.56 | 0.97, −0.68 |
| (Phase_1_PXRD) | (Phase_4_PXRD) |
Crystal data |
Chemical formula | Ni4Se4O12 | Cl2Ni5O12Se4 |
Mr | 742.6 | 872.2 |
Crystal system, space group | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 0 | 0 |
a, b, c (Å) | 15.4691, 9.8078, 14.7312 | 9.2823, 9.3756, 8.0733 |
α, β, γ (°) | 90, 110.6685, 90 | 105.6114, 91.8441, 101.948 |
V (Å3) | 2091.14 | 659.13 |
Z | 1 | 1 |
Radiation type | Cu Kα | Cu Kα |
µ (mm−1) | 0.66 | 2.18 |
Crystal size (mm) | × × | × × |
|
Data collection |
Diffractometer | X-Pert diffractometer | X-Pert diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed reflections | ?, ?, ? (?) | ?, ?, ? (?) |
Rint | ? | ? |
θmax (°) | ? | ? |
(sin θ/λ)max (Å−1) | – | – |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | ?, ?, ? | ?, ?, ? |
No. of reflections | ? | ? |
No. of parameters | ? | ? |
No. of restraints | ? | ? |
H-atom treatment | – | – |
(Δ/σ)max | ? | ? |
Δρmax, Δρmin (e Å−3) | ?, ? | ?, ? |