Tuning structural modulation and magnetic properties in metal-organic coordination polymers [CH3NH3]CoxNi1-x(HCOO)3
Authors:Geers, Madelaine; Fabelo, Oscar; Cliffe, Matthew J.; Canadillas-Delgado, Laura
Journal:IUCrJ 11 910-920 (2024)
DOI:https://doi.org/10.1107/S2052252524008583
B-IncStrDB ID: Bn1PFN5BD2w Entry date: 2024-05-08 Last revision: 2024-12-05
I
Chemical data
Full Name: ? [ Help ]
Structural Formula Sum: C4 H9 Co0.526 N1 Ni0.474 O6 [ Help ]
Formula weight: 225.9 Da [ Help ]
Absolute configuration: . [ Help ]
Crystallographic data and experimental details
Crystal system: orthorhombic [ Help ]
Superspace group name: Pnma(00γ)0s0 [ Help ]
Symmetry operations of the superspace group: (Show/hide table) [ Help ]
| Operation code | Operation in algebraic form |
|---|---|
| 1 | x1,x2,x3,x4 |
| 2 | -x1+1/2,-x2,x3+1/2,x4+1/2 |
| 3 | -x1,x2+1/2,-x3,-x4+1/2 |
| 4 | x1+1/2,-x2+1/2,-x3+1/2,-x4 |
| 5 | -x1,-x2,-x3,-x4 |
| 6 | x1+1/2,x2,-x3+1/2,-x4+1/2 |
| 7 | x1,-x2+1/2,x3,x4+1/2 |
| 8 | -x1+1/2,x2+1/2,x3+1/2,x4 |
a: 8.2052(2) Å [ Help ]
b: 11.5759(3) Å [ Help ]
c: 8.1141(2) Å [ Help ]
α: 90 ° [ Help ]
β: 90 ° [ Help ]
γ: 90 ° [ Help ]
Volume: 770.70(3) Å3 [ Help ]
Modulation dimension: 1 [ Help ]
Measured independent wave vectors: (Show/hide table) [ Help ]
| Wave vector id | q_x | q_y | q_z |
|---|---|---|---|
| 1 | 0.000000 | 0.000000 | 0.142900 |
Z: 4 [ Help ]
Cell determination reflection Nb.: 102 [ Help ]
θ(min) for cell determination: 8.92 ° [ Help ]
θ(max) for cell determination: 61.33 ° [ Help ]
Cell measurement temperature: 70 K [ Help ]
μ: 0.011 mm-1 [ Help ]
Absorption correction remarks: absorption corretion of the environment done through d19abscan program from ILL [ Help ]
Refinement details
Total nb. of reflections: 3291 [ Help ]
Nb. of observed reflections: 2152 [ Help ]
Intense reflections threshold: I>3σ(I) [ Help ]
Refinement based on: Fsqd [ Help ]
R(obs): 0.0601 [ Help ]
wR(obs): 0.2185 [ Help ]
R(all): 0.0762 [ Help ]
wR(all): 0.2321 [ Help ]
S(all): 2.0518 [ Help ]
S(obs): 2.4121 [ Help ]
Nb. of reflections: 3291 [ Help ]
Nb. of parameters: 164 [ Help ]
Number of restraints: 0 [ Help ]
Number of constraints: 9 [ Help ]
Weighting scheme: sigma [ Help ]
Weighting scheme remarks: calc w=1/[σ2(Fo2)+(0.08P)2+0.0000P] where P=(Fo2+2Fc2)/3 [ Help ]
Refinement of hydrogen atoms: refall [ Help ]
Δ/σ(max): 0.0055 [ Help ]
Δ/σ(mean): 0.0010 [ Help ]
Δρ(max): 0.77 e_Å-3 [ Help ]
Δρ(min): -1.21 e_Å-3 [ Help ]
Extinction method: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974) [ Help ]
Extinction coefficient: 17(3) [ Help ]
Structural Information
Average Structure: (Show/hide table) [ Help ]
| Atom site label | Atom symbol | x | y | z | ADP type | Uiso/equiv | Symmetry multiplicity | Occupancy | Coords from (d)iffraction or (c)alculated | Coords restraints or constraints | Disordered cluster | Disordered group |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Co1 | Co | 0.5 | 0.5 | 1 | Uani | 0.0214(5) | 4 | 0.526 | d | . | . | . |
| Ni1 | Ni | 0.5 | 0.5 | 1 | Uani | 0.0214(5) | 4 | 0.474 | d | . | . | . |
| N1 | N | 0.58533(11) | 0.75 | 0.52982(12) | Uani | 0.0260(4) | 4 | 1 | d | . | . | . |
| C1 | C | 0.41295(16) | 0.75 | 0.47604(18) | Uani | 0.0298(5) | 4 | 1 | d | . | . | . |
| C2 | C | 0.27926(11) | 0.47072(8) | 0.72152(11) | Uani | 0.0239(4) | 8 | 1 | d | . | . | . |
| C3 | C | 0.50915(15) | 0.75 | 0.94501(15) | Uani | 0.0240(5) | 4 | 1 | d | . | . | . |
| O1 | O | 0.40360(12) | 0.42963(9) | 0.78675(12) | Uani | 0.0249(4) | 8 | 1 | d | . | . | . |
| O2 | O | 0.22589(12) | 0.44111(8) | 0.58178(12) | Uani | 0.0242(4) | 8 | 1 | d | . | . | . |
| O3 | O | 0.52462(12) | 0.65490(9) | 0.87303(10) | Uani | 0.0241(4) | 8 | 1 | d | . | . | . |
| H1 | H | 0.5870(3) | 0.75 | 0.6560(4) | Uani | 0.0446(11) | 4 | 1 | d | . | . | . |
| H2 | H | 0.6468(2) | 0.82176(18) | 0.4866(2) | Uani | 0.0379(7) | 8 | 1 | d | . | . | . |
| H3 | H | 0.4091(4) | 0.75 | 0.3425(4) | Uani | 0.0532(12) | 4 | 1 | d | . | . | . |
| H4 | H | 0.3534(3) | 0.8254(2) | 0.5211(3) | Uani | 0.0555(9) | 8 | 1 | d | . | . | . |
| H5 | H | 0.2097(3) | 0.5364(2) | 0.7880(3) | Uani | 0.0478(8) | 8 | 1 | d | . | . | . |
| H6 | H | 0.4821(5) | 0.75 | 1.0787(4) | Uani | 0.0453(11) | 4 | 1 | d | . | . | . |
ADP components: (Show/hide table) [ Help ]
| Atom site label | Atom site symbol | U11 | U22 | U33 | U12 | U13 | U23 |
|---|---|---|---|---|---|---|---|
| Co1 | Co | 0.0192(8) | 0.0263(9) | 0.0188(7) | 0.0005(4) | -0.0012(5) | -0.0009(4) |
| Ni1 | Ni | 0.0192(8) | 0.0263(9) | 0.0188(7) | 0.0005(4) | -0.0012(5) | -0.0009(4) |
| N1 | N | 0.0229(6) | 0.0320(7) | 0.0229(7) | 0 | 0.0021(4) | 0 |
| C1 | C | 0.0230(8) | 0.0386(10) | 0.0279(9) | 0 | 0.0008(5) | 0 |
| C2 | C | 0.0194(6) | 0.0310(7) | 0.0212(6) | 0.0016(3) | -0.0021(3) | 0.0004(4) |
| C3 | C | 0.0202(7) | 0.0290(9) | 0.0226(8) | 0 | 0.0000(5) | 0 |
| O1 | O | 0.0205(6) | 0.0325(7) | 0.0217(6) | 0.0024(4) | -0.0020(3) | -0.0007(4) |
| O2 | O | 0.0207(6) | 0.0306(7) | 0.0212(6) | 0.0013(4) | -0.0021(3) | -0.0007(4) |
| O3 | O | 0.0246(6) | 0.0275(7) | 0.0202(6) | 0.0005(4) | 0.0005(3) | -0.0013(4) |
| H1 | H | 0.0373(16) | 0.070(2) | 0.0264(18) | 0 | -0.0007(11) | 0 |
| H2 | H | 0.0329(11) | 0.0445(15) | 0.0362(10) | -0.0058(9) | 0.0021(8) | 0.0024(9) |
| H3 | H | 0.0414(18) | 0.080(2) | 0.038(2) | 0 | -0.0040(13) | 0 |
| H4 | H | 0.0398(14) | 0.0599(17) | 0.0670(15) | 0.0109(11) | -0.0010(11) | -0.0109(12) |
| H5 | H | 0.0454(13) | 0.0604(14) | 0.0375(13) | 0.0210(10) | -0.0114(10) | -0.0137(10) |
| H6 | H | 0.064(2) | 0.0431(19) | 0.0294(15) | 0 | 0.0042(12) | 0 |
Anharmonic ADPs (C coefficients): (Show/hide table) [ Help ]
| Atom site label | Atom symbol | C111 | C112 | C113 | C122 | C123 | C133 | C222 | C223 | C233 | C333 |
|---|---|---|---|---|---|---|---|---|---|---|---|
| ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? |
Anharmonic ADPs (D coefficients): (Show/hide table) [ Help ]
| Atom site label | Atom symbol | D1111 | D1112 | D1113 | D1122 | D1123 | D1133 | D1222 | D1223 | D1233 | D1333 | D2222 | D2223 | D2233 | D2333 | D3333 |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? |
Anharmonic ADPs (E coefficients): (Show/hide table) [ Help ]
| Atom site label | Atom symbol | E11111 | E11112 | E11113 | E11122 | E11123 | E11133 | E11222 | E11223 | E11233 | E11333 | E12222 | E12223 | E12233 | E12333 | E13333 | E22222 | E22223 | E22233 | E22333 | E23333 | E33333 |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? |
Anharmonic ADPs (F coefficients): (Show/hide table) [ Help ]
| Atom site label | Atom symbol | F111111 | F111112 | F111113 | F111122 | F111123 | F111133 | F111222 | F111223 | F111233 | F111333 | F112222 | F112223 | F112233 | F112333 | F113333 | F122222 | F122223 | F122233 | F122333 | F123333 | F133333 | F222222 | F222223 | F222233 | F222333 | F223333 | F233333 | F333333 |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? | ? |
Fourier Wave Vectors (explicit: q_x,q_y,q_z or coefficients: q_1,q_2,...): (Show/hide table) [ Help ]
| Wave vector code | q_1 |
|---|---|
| 1 | 1 |
Definition of the displacive (translational) Fourier series: (Show/hide table) [ Help ]
| Modulation code | Atom site label | Displacement axis | Wave vector code |
|---|---|---|---|
| Co1x1 | Co1 | x | 1 |
| Co1y1 | Co1 | y | 1 |
| Co1z1 | Co1 | z | 1 |
| Ni1x1 | Ni1 | x | 1 |
| Ni1y1 | Ni1 | y | 1 |
| Ni1z1 | Ni1 | z | 1 |
| N1x1 | N1 | x | 1 |
| N1y1 | N1 | y | 1 |
| N1z1 | N1 | z | 1 |
| C1x1 | C1 | x | 1 |
| C1y1 | C1 | y | 1 |
| C1z1 | C1 | z | 1 |
| C2x1 | C2 | x | 1 |
| C2y1 | C2 | y | 1 |
| C2z1 | C2 | z | 1 |
| C3x1 | C3 | x | 1 |
| C3y1 | C3 | y | 1 |
| C3z1 | C3 | z | 1 |
| O1x1 | O1 | x | 1 |
| O1y1 | O1 | y | 1 |
| O1z1 | O1 | z | 1 |
| O2x1 | O2 | x | 1 |
| O2y1 | O2 | y | 1 |
| O2z1 | O2 | z | 1 |
| O3x1 | O3 | x | 1 |
| O3y1 | O3 | y | 1 |
| O3z1 | O3 | z | 1 |
| H1x1 | H1 | x | 1 |
| H1y1 | H1 | y | 1 |
| H1z1 | H1 | z | 1 |
| H2x1 | H2 | x | 1 |
| H2y1 | H2 | y | 1 |
| H2z1 | H2 | z | 1 |
| H3x1 | H3 | x | 1 |
| H3y1 | H3 | y | 1 |
| H3z1 | H3 | z | 1 |
| H4x1 | H4 | x | 1 |
| H4y1 | H4 | y | 1 |
| H4z1 | H4 | z | 1 |
| H5x1 | H5 | x | 1 |
| H5y1 | H5 | y | 1 |
| H5z1 | H5 | z | 1 |
| H6x1 | H6 | x | 1 |
| H6y1 | H6 | y | 1 |
| H6z1 | H6 | z | 1 |
Displacive (translational) Fourier coefficients: (Show/hide table) [ Help ]
| Modulation code | Cosine coefficient | Sine coefficient |
|---|---|---|
| Co1x1 | 0 | 0.00216(13) |
| Co1y1 | 0 | 0.02033(15) |
| Co1z1 | 0 | 0.00009(14) |
| Ni1x1 | 0 | 0.00216(13) |
| Ni1y1 | 0 | 0.02033(15) |
| Ni1z1 | 0 | 0.00009(14) |
| N1x1 | 0 | 0 |
| N1y1 | -0.00526(9) | 0.01924(10) |
| N1z1 | 0 | 0 |
| C1x1 | 0 | 0 |
| C1y1 | -0.00154(13) | 0.01937(15) |
| C1z1 | 0 | 0 |
| C2x1 | -0.00028(9) | 0.00191(9) |
| C2y1 | 0.00112(8) | 0.01999(10) |
| C2z1 | 0.00139(9) | 0.00037(10) |
| C3x1 | 0 | 0 |
| C3y1 | 0.00110(12) | 0.02055(14) |
| C3z1 | 0 | 0 |
| O1x1 | 0.00223(10) | 0.00187(10) |
| O1y1 | 0.00315(10) | 0.01996(12) |
| O1z1 | 0.00016(11) | 0.00049(11) |
| O2x1 | -0.00040(10) | 0.00192(10) |
| O2y1 | 0.00106(9) | 0.02027(12) |
| O2z1 | 0.00289(11) | -0.00003(11) |
| O3x1 | 0.00292(11) | 0.00170(11) |
| O3y1 | 0.00193(9) | 0.02056(11) |
| O3z1 | -0.00012(11) | 0.00023(11) |
| H1x1 | 0 | 0 |
| H1y1 | -0.0127(3) | 0.0170(3) |
| H1z1 | 0 | 0 |
| H2x1 | 0.0009(2) | -0.0005(2) |
| H2y1 | -0.00375(18) | 0.0194(2) |
| H2z1 | 0.0046(2) | 0.0005(2) |
| H3x1 | 0 | 0 |
| H3y1 | 0.0069(3) | 0.0182(4) |
| H3z1 | 0 | 0 |
| H4x1 | 0.0004(2) | -0.0003(2) |
| H4y1 | -0.0042(2) | 0.0184(3) |
| H4z1 | 0.0071(3) | 0.0013(3) |
| H5x1 | -0.0028(2) | 0.0017(2) |
| H5y1 | -0.00088(19) | 0.0196(2) |
| H5z1 | 0.0013(2) | 0.0005(2) |
| H6x1 | 0 | 0 |
| H6y1 | -0.0034(3) | 0.0205(3) |
| H6z1 | 0 | 0 |