Observation of the influence of dipolar and spin frustration effects on the magnetocaloric properties of a trigonal prismatic {Gd7} molecular nanomagnet
Pineda, Eufemio Moreno; Lorusso, Giulia; Zangana, Karzan H.; Palacios, Elias; Schnack, Jürgen; Evangelisti, Marco; Winpenny, Richard E. P.; McInnes, Eric J. L.; Chem. Sci. 7 (2016) 4891–; doi:10.1039/C6SC01415A

data_1543194
_publ_section_title
;
 Observation of the influence of dipolar and spin frustration effects on
 the magnetocaloric properties of a trigonal prismatic {Gd7} molecular
 nanomagnet
;
_journal_issue                   8
_journal_name_full               'Chem. Sci.'
_journal_page_first              4891
_journal_paper_doi               10.1039/C6SC01415A
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety
'C66 H108 Gd7 O45, 6(C6 H16 N), 0.67(C6 H9 N3)'
_chemical_formula_sum            'C106 H210 Gd7 N8 O45'
_chemical_formula_weight         3417.56
_space_group_crystal_system      hexagonal
_space_group_IT_number           190
_space_group_name_Hall           'P -6c -2c'
_space_group_name_H-M_alt        'P -6 2 c'
_symmetry_space_group_name_Hall  'P -6c -2c'
_symmetry_space_group_name_H-M   'P -6 2 c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-03-04
_audit_creation_method
;
Olex2 1.2
(compiled Feb 16 2016 13:09:46 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-03-06 deposited with the CCDC.
2016-04-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   16.9152(2)
_cell_length_b                   16.9152(2)
_cell_length_c                   31.3646(6)
_cell_measurement_reflns_used    19955
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      28.5760
_cell_measurement_theta_min      2.9410
_cell_volume                     7771.9(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 20.7409
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega   -3.00   95.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       18.2949   77.0000   90.0000 98

  2 omega   -3.00   95.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -       18.2949   77.0000  -30.0000 98

  3 omega  -50.00   48.00   1.0000  120.0000
omega____ theta____ kappa____ phi______ frames
    -      -18.3731   77.0000 -150.0000 98
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0125463000
_diffrn_orient_matrix_UB_12      -0.0418845000
_diffrn_orient_matrix_UB_13      0.0103813000
_diffrn_orient_matrix_UB_21      -0.0045996000
_diffrn_orient_matrix_UB_22      -0.0211624000
_diffrn_orient_matrix_UB_23      -0.0200824000
_diffrn_orient_matrix_UB_31      0.0465394000
_diffrn_orient_matrix_UB_32      0.0117241000
_diffrn_orient_matrix_UB_33      0.0008152000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0198
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            43084
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.358
_diffrn_reflns_theta_min         2.736
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.013
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52155
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.460
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             3420
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.850
_refine_diff_density_min         -1.210
_refine_diff_density_rms         0.113
_refine_ls_abs_structure_details
;
 Flack x determined using 2209 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.013(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     305
_refine_ls_number_reflns         5409
_refine_ls_number_restraints     23
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0310
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0121P)^2^+34.1889P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0637
_refine_ls_wR_factor_ref         0.0672
_reflns_Friedel_coverage         0.810
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                5121
_reflns_number_total             5409
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc01415a2.cif
_cod_data_source_block           Gd7
_cod_depositor_comments          'Adding full bibliography for 1543194.cif.'
_cod_original_cell_volume        7771.9(3)
_cod_database_code               1543194
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C106 H210 Gd7 N8 O45'
_reflns_odcompleteness_completeness 99.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C12A-C11
 1.52 with sigma of 0.02
 C11-C14A
 1.52 with sigma of 0.02
 C10A-C11 = C11-C13A
 1.52 with sigma of 0.02
 C13A-C12A
 2.483 with sigma of 0.04
 C12A-C10A
 2.483 with sigma of 0.04
 C10A-C14A
 2.483 with sigma of 0.04
 C10A-C13A
 2.483 with sigma of 0.04
 C19-C18 \\sim C18-C20A \\sim C16-C15 \\sim C15-C17A \\sim C17B-C15 \\sim
C15-C16 \\sim C19-C18 \\sim C18-
 C20B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O3) = Uanis(O2) = Uanis(O1)
Uanis(O4) = Uanis(O5)
Uanis(C20A) = Uanis(C20B)
Uanis(C12B) = Uanis(C13B) = Uanis(C14B)
Uanis(C14A) = Uanis(C12A) = Uanis(C13A)
Uanis(C9) = Uanis(C10)
4. Others
 Sof(O7B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C10B)=Sof(C12B)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=Sof(C13B)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14B)=
 Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(H15A)=Sof(C17B)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(H18A)=Sof(C20B)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(O7A)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C10A)=Sof(C12A)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14A)=
 Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(H15)=Sof(C17A)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(H18)=Sof(C20A)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 Fixed Sof: O4(0.5) C2(0.5) H4A(0.5) H4B(0.5) H4C(0.5) H9B(0.5) H9C(0.5)
 H13G(0.33333) H13H(0.33333) H13I(0.33333)
 Fixed X: C5(0.61762)
 Fixed Y: C5(0.55284)
 Fixed Z: C5(0.21272)
5.a Ternary CH refined with riding coordinates:
 C15(H15), C15(H15A), C18(H18A), C18(H18)
5.b Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B)
5.c Me refined with riding coordinates:
 C9(H9A,H9B,H9C)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C),
 C12A(H12A,H12B,H12C), C12B(H12D,H12E,H12F), C13A(H13A,H13B,H13C), C13B(H13D,
 H13E,H13F), C14A(H14A,H14B,H14C), C14B(H14D,H14E,H14F), C16(H16A,H16B,H16C),
 C17A(H17A,H17B,H17C), C17B(H17D,H17E,H17F), C19(H19A,H19B,H19C), C20A(H20A,
 H20B,H20C), C20B(H20D,H20E,H20F), C13(H13G,H13H,H13I)
;
_shelx_fab_checksum              81884
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2013-10-11
_olex2_submission_special_instructions 'No special instructions were received'
_solvent_exptl_crystal_recrystallization_method Acetonitrile