Magnetic and magnetocaloric properties of an unusual family of carbonate-panelled [LnZn] cages.
Sethi, Waqas; Sanz, Sergio; Pedersen, Kasper S.; Sørensen, Mikkel A; Nichol, Gary S.; Lorusso, Giulia; Evangelisti, Marco; Brechin, Euan K.; Piligkos, Stergios; Dalton transactions (Cambridge, England : 2003) 44 (2015) 10315–10320; doi:10.1039/c5dt01240f

data_7034773
_publ_section_title
;
 Magnetic and magnetocaloric properties of an unusual family of
 carbonate-panelled [LnZn] cages.
;
_journal_issue                   22
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10315
_journal_page_last               10320
_journal_paper_doi               10.1039/c5dt01240f
_journal_volume                  44
_journal_year                    2015
_chemical_formula_moiety         'C103 H144 N14 O44 Tb6 Zn2, 31 C H4 O'
_chemical_formula_sum            'C134 H268 N14 O75 Tb6 Zn2'
_chemical_formula_weight         4359.87
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-05-06
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-05-07 deposited with the CCDC.
2015-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                75.8497(8)
_cell_angle_beta                 88.0840(9)
_cell_angle_gamma                79.2672(10)
_cell_formula_units_Z            4
_cell_length_a                   22.1510(3)
_cell_length_b                   29.0764(3)
_cell_length_c                   32.1304(3)
_cell_measurement_reflns_used    70742
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      76.0000
_cell_measurement_theta_min      3.3000
_cell_volume                     19713.7(4)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_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_temperature      120.0
_diffrn_detector_area_resol_mean 10.3147
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
  1 omega -110.00  -19.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -57.0000 -120.0000 91

  2 omega  -50.00   28.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686   38.0000  150.0000 78

  3 omega   39.00   82.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1686  -99.0000  150.0000 43

  4 omega -122.00  -90.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  -94.0000   30.0000 32

  5 omega  -88.00  -61.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000  125.0000   90.0000 27

  6 omega  -69.00   27.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.5000   61.0000   30.0000 96

  7 omega   40.00   80.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000  -90.0000 40

  8 omega   41.00   91.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000 -180.0000 50

  9 omega  117.00  151.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -15.0000   60.0000 34

 10 omega   66.00   95.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000   60.0000 29

 11 omega   43.00   95.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000  120.0000 52

 12 omega   40.00  105.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000  -30.0000 65

 13 omega   31.00   60.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000   60.0000 29

 14 omega   74.00  107.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000   60.0000 33

 15 omega   58.00  102.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000 -180.0000 44

 16 omega   92.00  121.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000 -180.0000 29

 17 omega   59.00  107.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  -30.0000 48

 18 omega   41.00  103.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  150.0000 62

 19 omega   75.00  178.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000   60.0000 103

 20 omega   40.00   96.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000 -180.0000 56

 21 omega   88.00  114.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000  120.0000 26

 22 omega  133.00  172.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000  120.0000 39

 23 omega   50.00   76.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -77.0000   30.0000 26

 24 omega   74.00  121.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000  -90.0000 47

 25 omega   62.00  114.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -61.0000   30.0000 52

 26 omega   58.00   87.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000  120.0000 29

 27 omega   86.00  112.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000  -30.0000 26

 28 omega  151.00  178.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000  -30.0000 27

 29 omega   79.00  121.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000    0.0000 42

 30 omega   40.00   65.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000    0.0000 25

 31 omega   44.00   98.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000   30.0000 54

 32 omega   96.00  178.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   30.0000   90.0000 82

 33 omega   96.00  122.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -77.0000   30.0000 26

 34 omega   33.00   75.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000    0.0000 42

 35 omega   33.00  112.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -15.0000   60.0000 79

 36 omega   56.00   88.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000  -60.0000 32

 37 omega   73.00  121.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000   90.0000 48

 38 omega   63.00   90.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  -90.0000 27

 39 omega   43.00  108.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -77.0000 -180.0000 65

 40 omega -113.00  -17.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -57.0000  150.0000 96

 41 omega -113.00  -17.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -57.0000  -30.0000 96

 42 omega -117.00  -12.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -77.0000   90.0000 105

 43 omega   87.00  178.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000  150.0000 91

 44 omega   85.00  178.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   53.0000  -46.5770 93

 45 omega   83.00  178.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   61.0000   60.0000 95

 46 omega   84.00  163.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   58.0000 -103.4799 79

 47 omega   66.00  178.00   1.0000   27.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000 -120.0000 112
;
_diffrn_measurement_device_type  'Agilent Technologies SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0544081000
_diffrn_orient_matrix_UB_12      -0.0270474000
_diffrn_orient_matrix_UB_13      0.0054207000
_diffrn_orient_matrix_UB_21      0.0429531000
_diffrn_orient_matrix_UB_22      -0.0449276000
_diffrn_orient_matrix_UB_23      -0.0083001000
_diffrn_orient_matrix_UB_31      0.0143636000
_diffrn_orient_matrix_UB_32      -0.0184366000
_diffrn_orient_matrix_UB_33      0.0484477000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0997
_diffrn_reflns_av_unetI/netI     0.0777
_diffrn_reflns_laue_measured_fraction_full 1.000
_diffrn_reflns_laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            328806
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.427
_diffrn_reflns_theta_min         3.160
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.327
_exptl_absorpt_correction_T_max  0.701
_exptl_absorpt_correction_T_min  0.262
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.469
_exptl_crystal_description       block
_exptl_crystal_F_000             8880
_exptl_crystal_size_max          0.4374
_exptl_crystal_size_mid          0.2182
_exptl_crystal_size_min          0.0689
_platon_squeeze_details          ' see _refine_special_details'
_refine_diff_density_max         1.256
_refine_diff_density_min         -1.913
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3143
_refine_ls_number_reflns         81683
_refine_ls_number_restraints     247
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0962
_refine_ls_R_factor_gt           0.0568
_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^)+(0.0851P)^2^+2.6753P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1492
_refine_ls_wR_factor_ref         0.1728
_reflns_Friedel_coverage         0.000
_reflns_number_gt                51679
_reflns_number_total             81683
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c5dt01240f2.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 7034769--7034773.cif.'
_cod_original_cell_volume        19713.8(4)
_cod_database_code               7034773
_chemical_oxdiff_formula         'C100 H200 N10 O40 Tb6 Zn2'
_chemical_oxdiff_usercomment     '@ 120 K C-1324'
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H44 of O44, H28 of O28, H27 of O27, H24 of O24, H23 of O23,
   H19 of O19, H18 of O18, H16 of O16, H14 of O14, H12 of O12, H10 of O10, H7
  of O7, H3 of O3, H53 of O53, H54 of O54, H57 of O57, H60 of O60, H62 of O62,
  H64 of O64, H66 of O66, H70 of O70, H73A of O73, H74 of O74, H78 of O78, H94
  of O94, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H202 of O202, H201 of O201, H68 of O68
2. Restrained distances
 O44-H44 = O94-H94
 0.84 with sigma of 0.01
 C179-C174 \\sim C109-C104
 with sigma of 0.02
 C155-C156 \\sim C153-C154
 with sigma of 0.02
 C156-O66 \\sim C42-O12
 with sigma of 0.02
 N1-H1 \\sim N3-H3A \\sim N9-H9 \\sim N11-H11 \\sim N13-H13
 with sigma of 0.02
 N61-H61A \\sim N63-H63 \\sim N53-H53C \\sim N55-H55 \\sim N51-H51
 with sigma of 0.02
 C65-C60 \\sim C9-C4
 with sigma of 0.02
 C68-C67 \\sim C12-C11
 with sigma of 0.02
 C142-C141 \\sim C126-C125
 with sigma of 0.02
3. Restrained planarity
 C173, C174, C175, C179
 with sigma of 0.1
 C171, C172, C173, C174, C175, C176, C179
 with sigma of 0.1
 C57, C62, C61, C60, C58, C65
 with sigma of 0.1
4. Rigid bond restraints
 O17, O18, N9, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(O66) \\sim Ueq, Uanis(C156) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
6. Rigid body (RIGU) restrains
 O66, C155, C156
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O12, C41, C42
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O71, N61, C171, C172, C173, C174, C175, C176, C177, C178, C179
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O62, C141, C142
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O59, C129, C130, C131, C132, C133, C134, C137, C138
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7.a Secondary CH2 refined with riding coordinates:
 C110(H11C,H11D), C111(H11E,H11F), C112(H11G,H11H), C113(H11I,H11J), C114(H11K,
 H11L), C124(H12I,H12J), C125(H12K,H12L), C126(H12M,H12N), C127(H12O,H12P),
 C128(H12Q,H12R), C138(H13I,H13J), C139(H13K,H13L), C140(H14C,H14D), C141(H14E,
 H14F), C142(H14G,H14H), C152(H15G,H15H), C153(H15I,H15J), C154(H15K,H15L),
 C155(H15M,H15N), C156(H15O,H15P), C166(H16G,H16H), C167(H16I,H16J), C168(H16K,
 H16L), C169(H16M,H16N), C170(H17A,H17B), C180(H18A,H18B), C181(H18C,H18D),
 C182(H18E,H18F), C183(H18G,H18H), C184(H18I,H18J), C194(H19H,H19I), C195(H19J,
 H19K), C196(H19L,H19M), C197(H19N,H19O), C198(H19P,H19Q), C10(H10A,H10B),
 C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C24(H24A,H24B),
  C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C38(H38A,
 H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B),
 C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B),
  C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,
 H70B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
 C84(H84A,H84B), C94(H94A,H94B), C95(H95A,H95B), C96(H96A,H96B), C97(H97A,H97B),
  C98(H98A,H98B)
7.b Me refined with riding coordinates:
 C137(H13F,H13G,H13H), C179(H17F,H17G,H17H), C65(H65A,H65B,H65C)
7.c Aromatic/amide H refined with riding coordinates:
 C103(H103), C105(H105), C117(H117), C119(H119), C131(H131), C133(H133),
 C145(H145), C147(H147), C159(H159), C161(H161), C173(H173), C175(H175),
 C187(H187), C189(H189), C3(H3B), C5(H5), C17(H17), C19(H19A), C31(H31),
 C33(H33), C45(H45), C47(H47), C59(H59), C61(H61), C73(H73), C75(H75), C87(H87),
  C89(H89)
7.d Tetrahedral OH refined with riding coordinates:
 O53(H53), O54(H54), O57(H57), O60(H60), O62(H62), O64(H64), O66(H66),
 O70(H70), O73(H73A), O74(H74), O78(H78), O3(H3), O7(H7), O10(H10), O12(H12),
 O14(H14), O16(H16), O18(H18), O19(H19), O23(H23), O24(H24), O27(H27), O28(H28),
  O201(H201), O202(H202)
7.e Idealised Me refined as rotating group:
 C108(H10C,H10D,H10E), C109(H10F,H10G,H10H), C122(H12C,H12D,H12E), C123(H12F,
 H12G,H12H), C136(H13C,H13D,H13E), C150(H15A,H15B,H15C), C151(H15D,H15E,H15F),
 C164(H16A,H16B,H16C), C165(H16D,H16E,H16F), C178(H17C,H17D,H17E), C192(H19B,
 H19C,H19D), C193(H19E,H19F,H19G), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C22(H22A,
 H22B,H22C), C23(H23A,H23B,H23C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C),
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C64(H64A,H64B,H64C), C78(H78A,H78B,
 H78C), C79(H79A,H79B,H79C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C),
 C201(H20A,H20B,H20C), C202(H20D,H20E,H20F)
7.f Idealised tetrahedral OH refined as rotating group:
 O68(H68)
;
_shelx_res_checksum              15591
_shelx_fab_checksum              85195
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 22/10/13
_olex2_date_sample_submission    20/10/13
_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 C-1324
_olex2_submission_special_instructions 'No special instructions were received'