Pressure-and Temperature Induced Phase Transitions, Piezochromism, NLC Behaviour and Pressure Controlled Jahn-Teller Switching in a Cu-based Framework
McMonagle, Charlie; Comar, Priyanka; Nichol, Gary Stephen; Allan, David Robert; Barreda-Argūeso, José A; Gonzalez, Jesus Antonio; Rodriguez, Fernando; Valiente, Rafael; Turner, Gemma; Brechin, Euan K.; Moggach, Stephen A.; Chemical Science  (2020) –; doi:10.1039/D0SC03229H

data_1558716
_publ_section_title
;
 Pressure-and Temperature Induced Phase Transitions, Piezochromism, NLC
 Behaviour and Pressure Controlled Jahn-Teller Switching in a Cu-based
 Framework
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03229H
_journal_year                    2020
_chemical_formula_moiety         'C54 H48 Cu3 N6 O12, C4 H10 O'
_chemical_formula_sum            'C58 H58 Cu3 N6 O13'
_chemical_formula_weight         1237.72
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-12-22
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_audit_update_record
;
2020-06-09 deposited with the CCDC.	2020-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                116.604(6)
_cell_angle_beta                 100.395(4)
_cell_angle_gamma                98.422(4)
_cell_formula_units_Z            1
_cell_length_a                   7.7799(3)
_cell_length_b                   15.1586(9)
_cell_length_c                   15.4901(9)
_cell_measurement_reflns_used    9584
_cell_measurement_temperature    200.0
_cell_measurement_theta_max      76.4050
_cell_measurement_theta_min      5.7750
_cell_volume                     1551.99(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.925
_diffrn_measured_fraction_theta_max 0.914
_diffrn_measurement_details
;
  1 omega  -37.00   84.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000 -120.0000 121

  2 omega  -95.00  -34.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  -30.0000 61

  3 omega  -37.00   84.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000 -180.0000 121

  4 omega  -50.00   25.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000   38.0000  -30.0000 75

  5 omega  -96.00   -2.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  125.0000 -180.0000 94

  6 omega -148.00  -79.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -99.0000   30.0000 69

  7 omega  -50.00   25.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000   38.0000   90.0000 75

  8 omega -143.00  -22.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -38.0000  -60.0000 121

  9 omega   94.00  143.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       59.0000  125.0000 -120.0000 49

 10 omega    1.00  106.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       59.0000  -99.0000  -30.0000 105

 11 omega   34.00   93.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -38.0000   60.0000 59

 12 omega  100.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  111.0000 -180.0000 78

 13 omega  100.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  111.0000   30.0000 78

 14 omega   57.00  150.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  178.0000  -60.0000 93

 15 omega   32.00  116.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000  -90.0000 84

 16 omega   32.00  116.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000   30.0000 84

 17 omega   57.00  150.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  178.0000 -180.0000 93

 18 omega  100.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  111.0000  150.0000 78

 19 omega   32.00  116.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000 -120.0000 84

 20 omega  100.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  111.0000   90.0000 78

 21 omega   81.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   63.0000  150.0000 97

 22 omega   33.00  155.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -63.0000   60.0000 122

 23 omega   34.00   93.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -38.0000 -150.0000 59

 24 omega   34.00   93.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -38.0000  150.0000 59

 25 omega   32.00  116.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000  -30.0000 84

 26 omega   32.00  116.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000  120.0000 84

 27 omega   63.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000   25.0000  -90.0000 115

 28 omega   34.00   93.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000  -38.0000  -60.0000 59

 29 omega   32.00  116.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      118.0000 -111.0000  150.0000 84

 30 omega    1.00   47.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000   60.0000 46

 31 omega    1.00   47.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -99.0000   30.0000 46

 32 omega  -39.00   92.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   77.0000    0.0000 131

 33 omega -151.00  -20.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -77.0000  -90.0000 131

 34 omega -143.00  -22.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -57.0000 -180.0000 121

 35 omega -143.00  -22.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -57.0000  120.0000 121

 36 omega -151.00  -20.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -77.0000   60.0000 131

 37 omega -151.00  -20.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -77.0000    0.0000 131

 38 omega -143.00  -22.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -57.0000   60.0000 121

 39 omega -151.00  -75.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -59.0000  -77.0000 -150.0000 76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent Technologies SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0305141000
_diffrn_orient_matrix_UB_12      0.0679958000
_diffrn_orient_matrix_UB_13      -0.0483282000
_diffrn_orient_matrix_UB_21      -0.0709540000
_diffrn_orient_matrix_UB_22      -0.0957698000
_diffrn_orient_matrix_UB_23      -0.1046274000
_diffrn_orient_matrix_UB_31      -0.1935574000
_diffrn_orient_matrix_UB_32      -0.0083973000
_diffrn_orient_matrix_UB_33      0.0112142000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0687
_diffrn_reflns_av_unetI/netI     0.0538
_diffrn_reflns_Laue_measured_fraction_full 0.925
_diffrn_reflns_Laue_measured_fraction_max 0.914
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            20345
_diffrn_reflns_point_group_measured_fraction_full 0.925
_diffrn_reflns_point_group_measured_fraction_max 0.914
_diffrn_reflns_theta_full        66.000
_diffrn_reflns_theta_max         76.540
_diffrn_reflns_theta_min         3.322
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.717
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86817
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       rod
_exptl_crystal_F_000             639
_exptl_crystal_recrystallization_method
'The material was recrystallised from diethyl ether by slow evaporation'
_exptl_crystal_size_max          0.1991
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.0449
_refine_diff_density_max         1.505
_refine_diff_density_min         -0.837
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     393
_refine_ls_number_reflns         5968
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.008
_refine_ls_R_factor_all          0.0808
_refine_ls_R_factor_gt           0.0610
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1433P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1809
_refine_ls_wR_factor_ref         0.1977
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4475
_reflns_number_total             5968
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03229h2.cif
_cod_data_source_block           CuPyrIII
_cod_original_cell_volume        1551.99(15)
_cod_database_code               1558716
_chemical_oxdiff_formula         'C30 H30 N8 O20 Cu Gd'
_chemical_oxdiff_usercomment     '@ 200 K PC1469'
_diffrn_oxdiff_twin_integration_method simultaneous
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid body (RIGU) restrains
 O7, C28, C30, C29, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Fixed Sof: O7(0.5) C28(0.5) H28A(0.5) H28B(0.5) C30(0.5) H30A(0.5) H30B(0.5)
 C29(0.5) H29A(0.5) H29B(0.5) H29C(0.5) C31(0.5) H31A(0.5) H31B(0.5) H31C(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C30(H30A,H30B)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C7(H7), C10(H10), C11(H11), C13(H13),
 C14(H14), C16(H16), C19(H19), C20(H20), C22(H22), C23(H23), C25(H25)
4.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C18(H18A,H18B,H18C), C27(H27A,H27B,H27C), C29(H29A,H29B,
 H29C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              62475
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 15/12/14
_olex2_date_sample_submission    15/12/14
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id PC1469
_olex2_submission_special_instructions 'No special instructions were received'