The low-temperature phase transition sequence of the Halide Perovskite Tetramethylammonium Trichlorogermanate(II) and the structure of its incommensurately modulated δ-phase
Authors:Futterer, K.; Depmeier, W.; Petricek, V.
Journal:Acta Cryst. B 51 768-779 (1995)
DOI:https://doi.org/10.1107/S0108768194013303
B-IncStrDB ID: 552EF3lwf Entry date: 2010-11-08 Last revision: 2021-12-30
GeCl3_REFRNCE
Chemical data
Structural Formula Sum: C4 H0 Cl3 Ge1 N1 [ Help ]
Formula weight: 241 Da [ Help ]
Crystallographic data and experimental details
a: 13.083(6) Å [ Help ]
b: 8.841(4) Å [ Help ]
c: 9.027(4) Å [ Help ]
α: 90 ° [ Help ]
β: 90 ° [ Help ]
γ: 90 ° [ Help ]
Volume: 1044.1(8) Å3 [ Help ]
Z: 4 [ Help ]
μ: 3.632 mm-1 [ Help ]
Cell measurement temperature: 190 K [ Help ]
Crystal system: orthorhombic [ Help ]
Space group name (H-M): P n a m [ Help ]
Space group name (Hall): -P -2yab;-2xn [ Help ]
Symmetry operations of the space group: (Show/hide table) [ Help ]
| Operation code | Operation in algebraic form |
|---|---|
| 1 | x,y,z |
| 2 | 1/2+x,1/2-y,z |
| 3 | 1/2-x,1/2+y,1/2+z |
| 4 | -x,-y,1/2+z |
| 5 | -x,-y,-z |
| 6 | 1/2-x,1/2+y,-z |
| 7 | 1/2+x,1/2-y,1/2-z |
| 8 | x,y,1/2-z |
Refinement details
Nb. of observed reflections: 410 [ Help ]
R(obs): 0.0485 [ Help ]
wR(all): 0.0635 [ Help ]
Structural Information
Average Structure: (Show/hide table) [ Help ]
| Atom site label | Atom symbol | Symmetry multiplicity | Occupancy | x | y | z | Uiso/equiv | ADP type |
|---|---|---|---|---|---|---|---|---|
| Ge | Ge | 4 | 1 | 0.2571(1) | 0.2517(1) | 0.75 | ? | Uani |
| Cl1 | Cl | 8 | 1 | 0.2701(1) | 0.0767(2) | 0.9384(2) | ? | Uani |
| Cl2 | Cl | 4 | 1 | 0.428(2) | 0.3153(3) | 0.75 | ? | Uani |
| N | N | 4 | 1 | 0.4981(4) | 0.2306(7) | 0.25 | ? | Uani |
| C1 | C | 4 | 1 | 0.4677(7) | 0.0687(9) | 0.25 | ? | Uani |
| C2 | C | 4 | 1 | 0.4035(7) | 0.33(1) | 0.25 | ? | Uani |
| C3 | C | 8 | 1 | 0.5579(9) | 0.2622(9) | 0.115(2) | ? | Uani |
ADP components: (Show/hide table) [ Help ]
| Atom site label | Atom site symbol | U11 | U22 | U33 | U12 | U13 | U23 |
|---|---|---|---|---|---|---|---|
| Ge | Ge | 0.0548(7) | 0.0479(7) | 0.181(1) | 0.012(5) | 0 | 0 |
| Cl1 | Cl | 0.066(1) | 0.072(1) | 0.128(2) | 0.0023(9) | -0.007(1) | -0.015(1) |
| Cl2 | Cl | 0.072(2) | 0.047(1) | 0.296(5) | -0.015(1) | 0 | 0 |
| N | N | 0.037(4) | 0.032(4) | 0.17(1) | 0(3) | 0 | 0 |
| C1 | C | 0.069(6) | 0.03(5) | 0.15(1) | -0.002(4) | 0 | 0 |
| C2 | C | 0.057(6) | 0.046(5) | 0.18(1) | 0.016(4) | 0 | 0 |
| C3 | C | 0.167(8) | 0.071(6) | 0.27(1) | 0.008(5) | 0.15(1) | 0.031(7) |
GeCl3_MOD
Chemical data
Structural Formula Sum: C4 H0 Cl3 Ge1 N1 [ Help ]
Formula weight: 241 Da [ Help ]
Crystallographic data and experimental details
a: 13.083(6) Å [ Help ]
b: 8.841(4) Å [ Help ]
c: 9.027(4) Å [ Help ]
α: 90 ° [ Help ]
β: 90 ° [ Help ]
γ: 90 ° [ Help ]
Volume: 1044.1(8) Å3 [ Help ]
Z: 4 [ Help ]
μ: 3.632 mm-1 [ Help ]
Cell measurement temperature: 190 K [ Help ]
Crystal system: orthorhombic [ Help ]
Superspace group name (ITC): P n a m (0 β 0) 0 0 s [ Help ]
Superspace group name: Pnam(0β0)00s [ Help ]
Symmetry operations of the superspace group: (Show/hide table) [ Help ]
| Operation code | Operation in algebraic form |
|---|---|
| 1 | x1,x2,x3,x4 |
| 2 | 1/2-x1,1/2+x2,1/2+x3,x4 |
| 3 | x1,x2,1/2-x3,1/2+x4 |
| 4 | 1/2-x1,1/2+x2,-x3,1/2+x4 |
| 5 | -x1,-x2,-x3,-x4 |
| 6 | 1/2+x1,1/2-x2,1/2-x3,-x4 |
| 7 | -x1,-x2,1/2+x3,1/2-x4 |
| 8 | 1/2+x1,1/2-x2,x3,1/2-x4 |
Space group name (H-M): P n a m [ Help ]
Modulation dimension: 1 [ Help ]
Measured independent wave vectors: (Show/hide table) [ Help ]
| Wave vector id | q_x | q_y | q_z |
|---|---|---|---|
| 1 | 0 | 0.143(1) | 0 |
Refinement details
Modulation functions description: Displacive modulation:Fourier series. Up to 2nd-order harmonics. [ Help ]
Nb. of observed reflections: 944 [ Help ]
R(obs): 0.0387 [ Help ]
wR(all): 0.052 [ Help ]
Structural Information
Average Structure: (Show/hide table) [ Help ]
| Atom site label | Atom symbol | Symmetry multiplicity | Occupancy | x | y | z | Uiso/equiv | ADP type |
|---|---|---|---|---|---|---|---|---|
| Ge | Ge | 4 | 1 | 0.2572(1) | 0.2517(1) | 0.75 | ? | Uani |
| Cl1 | Cl | 8 | 1 | 0.2701(1) | 0.0769(2) | 0.9382(2) | ? | Uani |
| Cl2 | Cl | 4 | 1 | 0.4279(1) | 0.3152(2) | 0.75 | ? | Uani |
| N | N | 4 | 1 | 0.4975(4) | 0.2309(4) | 0.25 | ? | Uani |
| C1 | C | 4 | 1 | 0.4676(4) | 0.0686(5) | 0.25 | ? | Uani |
| C2 | C | 4 | 1 | 0.4038(4) | 0.33(5) | 0.25 | ? | Uani |
| C3 | C | 8 | 1 | 0.5574(4) | 0.263(5) | 0.115(6) | ? | Uani |
Fourier Wave Vectors (explicit: q_x,q_y,q_z or coefficients: q_1,q_2,...): (Show/hide table) [ Help ]
| Wave vector code | q_x | q_y | q_z |
|---|---|---|---|
| 1 | 0 | 0.143 | 0 |
| 2 | 0 | 0.286 | 0 |
Definition of the displacive (translational) Fourier series: (Show/hide table) [ Help ]
| Modulation code | Atom site label | Displacement axis | Wave vector code |
|---|---|---|---|
| Gex2 | Ge | x | 2 |
| Gey2 | Ge | y | 2 |
| Gez1 | Ge | z | 1 |
| Cl1x1 | Cl1 | x | 1 |
| Cl1x2 | Cl1 | x | 2 |
| Cl1y1 | Cl1 | y | 1 |
| Cl1y2 | Cl1 | y | 2 |
| Cl1z1 | Cl1 | z | 1 |
| Cl1z2 | Cl1 | z | 2 |
| Cl2x2 | Cl2 | x | 2 |
| Cl2y2 | Cl2 | y | 2 |
| Cl2z1 | Cl2 | z | 1 |
| Nx2 | N | x | 2 |
| Ny2 | N | y | 2 |
| Nz1 | N | z | 1 |
| C1x2 | C1 | x | 2 |
| C1y2 | C1 | y | 2 |
| C1z1 | C1 | z | 1 |
| C2x2 | C2 | x | 2 |
| C2y2 | C2 | y | 2 |
| C2z1 | C2 | z | 1 |
| C3x1 | C3 | x | 1 |
| C3x2 | C3 | x | 2 |
| C3y1 | C3 | y | 1 |
| C3y2 | C3 | y | 2 |
| C3z1 | C3 | z | 1 |
| C3z2 | C3 | z | 2 |
Displacive (translational) Fourier coefficients: (Show/hide table) [ Help ]
| Modulation code | Cosine coefficient | Sine coefficient |
|---|---|---|
| Gex2 | -0.0004(1) | 0.0002(2) |
| Gey2 | 0.0006(2) | 0.0005(1) |
| Gez1 | 0.003(1) | 0.0464(1) |
| Cl1x1 | -0.0062(1) | -0.0019(1) |
| Cl1x2 | -0.0006(2) | -0.0006(2) |
| Cl1y1 | -0.0051(1) | -0.007(1) |
| Cl1y2 | 0.0009(3) | 0.0001(3) |
| Cl1z1 | 0.0059(1) | 0.0392(2) |
| Cl1z2 | 0.0001(2) | 0.0001(2) |
| Cl2x2 | -0.0004(4) | 0.0004(4) |
| Cl2y2 | -0.0004(3) | -0.004(4) |
| Cl2z1 | 0.0134(3) | 0.0589(3) |
| Nx2 | 0.0022(9) | -0.002(1) |
| Ny2 | 0.001(1) | 0(1) |
| Nz1 | -0.0015(7) | 0.0427(6) |
| C1x2 | -0.002(1) | 0.001(1) |
| C1y2 | -0.001(1) | -0.002(2) |
| C1z1 | -0.0075(9) | 0.0355(9) |
| C2x2 | 0.008(1) | -0.004(1) |
| C2y2 | 0.002(2) | 0.002(2) |
| C2z1 | -0.021(1) | 0.025(1) |
| C3x1 | 0.0172(7) | 0.0153(6) |
| C3x2 | 0.0003(9) | 0.001(1) |
| C3y1 | 0.0058(7) | 0.0031(8) |
| C3y2 | -0.002(1) | 0.002(1) |
| C3z1 | 0.0169(9) | 0.0592(8) |
| C3z2 | -0.0008(9) | 0.004(1) |
ADP components: (Show/hide table) [ Help ]
| Atom site label | Atom site symbol | U11 | U22 | U33 | U12 | U13 | U23 |
|---|---|---|---|---|---|---|---|
| Ge | Ge | 0.0555(3) | 0.0465(3) | 0.0705(5) | 0.0119(2) | 0 | 0 |
| Cl1 | Cl | 0.0613(6) | 0.0663(6) | 0.0535(6) | -0.0008(5) | 0.0021(5) | -0.0001(5) |
| Cl2 | Cl | 0.074(1) | 0.0454(8) | 0.104(1) | -0.0146(7) | 0 | 0 |
| N | N | 0.039(2) | 0.033(2) | 0.059(3) | -0.001(2) | 0 | 0 |
| C1 | C | 0.067(3) | 0.031(3) | 0.09(5) | -0.004(3) | 0 | 0 |
| C2 | C | 0.049(4) | 0.046(3) | 0.126(6) | 0.013(3) | 0 | 0 |
| C3 | C | 0.111(4) | 0.074(3) | 0.094(4) | 0(3) | 0.06(4) | 0.016(3) |