Magneto-structural studies of an unusual [Mn<sup>III</sup>Mn<sup>II</sup>Gd<sup>III</sup>(OR)<sub>4</sub>]<sup>4-</sup> partial cubane from 2,2'-bis-<i>p</i>-<sup> <i>t</i> </sup>Bu-calix[4]arene.
Coletta, Marco; Sanz, Sergio; Cutler, Daniel J.; Teat, Simon J.; Gagnon, Kevin J.; Singh, Mukesh K.; Brechin, Euan K.; Dalgarno, Scott J.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 14790–14797; doi:10.1039/d0dt02731f

data_7705687
_publ_section_title
;
 Magneto-structural studies of an unusual
 [Mn<sup>III</sup>Mn<sup>II</sup>Gd<sup>III</sup>(OR)<sub>4</sub>]<sup>4-</sup>
 partial cubane from 2,2'-bis-<i>p</i>-<sup> <i>t</i>
 </sup>Bu-calix[4]arene.
;
_journal_issue                   42
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14790
_journal_page_last               14797
_journal_paper_doi               10.1039/d0dt02731f
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety
'C107 H133 Gd Mn2 N3 O15, 3(C2 H3 N), C3 H7 N O'
_chemical_formula_sum            'C116 H151 Gd Mn2 N7 O16'
_chemical_formula_weight         2166.56
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2020-07-30 deposited with the CCDC.	2020-10-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.2275(8)
_cell_length_b                   23.2275(8)
_cell_length_c                   44.2459(18)
_cell_measurement_temperature    100(2)
_cell_volume                     23871.4(15)
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.708
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Bruker D8 with PHOTON 100 detector'
_diffrn_measurement_method       '\f and \w shutterless scans'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.7749
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_unetI/netI     0.0321
_diffrn_reflns_Laue_measured_fraction_full 0.708
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            151805
_diffrn_reflns_point_group_measured_fraction_full 0.699
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        27.706
_diffrn_reflns_theta_max         24.426
_diffrn_reflns_theta_min         2.138
_diffrn_source                   'Advanced Light Source, station 11.3.1'
_exptl_absorpt_coefficient_mu    1.023
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.6157
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1524 before and 0.0757 after correction.
The Ratio of minimum to maximum transmission is 0.8263.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            Purple
_exptl_crystal_density_diffrn    1.206
_exptl_crystal_description       Plate
_exptl_crystal_F_000             9104
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.008
_refine_diff_density_min         -0.965
_refine_diff_density_rms         0.089
_refine_ls_abs_structure_details
;
 Flack x determined using 5287 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1057
_refine_ls_number_reflns         15095
_refine_ls_number_restraints     87
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0844
_refine_ls_R_factor_gt           0.0653
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0600P)^2^+141.7042P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1510
_refine_ls_wR_factor_ref         0.1718
_reflns_Friedel_coverage         0.789
_reflns_Friedel_fraction_full    0.688
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                12817
_reflns_number_total             15095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt02731f2.cif
_cod_data_source_block           bistbcmngd_a
_cod_depositor_comments          'Adding full bibliography for 7705687.cif.'
_cod_original_cell_volume        23871.4(19)
_cod_database_code               7705687
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.749
_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, All O(H) groups
2. Restrained distances
 O15-C105
 1.2 with sigma of 0.02
 N3-C105 = N3-C107 = N3-C106
 1.45 with sigma of 0.02
 O1AA-C2AA
 1.2 with sigma of 0.02
 N02J-C2AA = N02J-C031 = N02J-C02W
 1.45 with sigma of 0.02
 C78A-C77 = C78-C77 = C79A-C77 = C79-C77 = C80A-C77 = C80-C77
 1.54 with sigma of 0.02
 C74-C73 = C76-C73 = C73-C75
 1.54 with sigma of 0.02
 C86-C85 = C88-C85 = C87-C85
 1.54 with sigma of 0.02
 C32-C29 = C32A-C29 = C30A-C29 = C30-C29 = C31A-C29 = C31-C29
 1.54 with sigma of 0.02
 C43-C41 = C44-C41 = C42-C41
 1.54 with sigma of 0.02
 C02O-C029
 1.35 with sigma of 0.02
 C39-C37 = C37-C39A = C40-C37 = C40A-C37 = C38-C37 = C38A-C37
 1.54 with sigma of 0.02
 C35-C33 = C35A-C33 = C36-C33 = C36A-C33 = C34-C33 = C33-C34A
 1.54 with sigma of 0.02
 O11-H11
 0.87 with sigma of 0.01
 O10-H10
 0.87 with sigma of 0.01
 C105-C106
 2.54 with sigma of 0.04
 C106-C107
 2.54 with sigma of 0.04
 C107-C105
 2.54 with sigma of 0.04
 C02W-C031
 2.54 with sigma of 0.04
 C031-C2AA
 2.54 with sigma of 0.04
 C2AA-C02W
 2.54 with sigma of 0.04
 C78A-C79A
 2.54 with sigma of 0.04
 C79A-C80A
 2.54 with sigma of 0.04
 C80A-C78A
 2.54 with sigma of 0.04
 C78-C79
 2.54 with sigma of 0.04
 C79-C80
 2.54 with sigma of 0.04
 C80-C78
 2.54 with sigma of 0.04
 C74-C76
 2.54 with sigma of 0.04
 C76-C75
 2.54 with sigma of 0.04
 C75-C74
 2.54 with sigma of 0.04
 C86-C87
 2.54 with sigma of 0.04
 C86-C88
 2.54 with sigma of 0.04
 C88-C87
 2.54 with sigma of 0.04
 C32-C30
 2.54 with sigma of 0.04
 C30-C31
 2.54 with sigma of 0.04
 C31-C32
 2.54 with sigma of 0.04
 C30A-C31A
 2.54 with sigma of 0.04
 C31A-C32A
 2.54 with sigma of 0.04
 C32A-C30A
 2.54 with sigma of 0.04
 C43-C44
 2.54 with sigma of 0.04
 C44-C42
 2.54 with sigma of 0.04
 C42-C43
 2.54 with sigma of 0.04
 C39-C40
 2.54 with sigma of 0.04
 C40-C38
 2.54 with sigma of 0.04
 C38-C39
 2.54 with sigma of 0.04
 C38A-C39A
 2.54 with sigma of 0.04
 C39A-C40A
 2.54 with sigma of 0.04
 C40A-C38A
 2.54 with sigma of 0.04
 C35-C36
 2.54 with sigma of 0.04
 C36-C34
 2.54 with sigma of 0.04
 C34-C35
 2.54 with sigma of 0.04
 C35A-C36A
 2.54 with sigma of 0.04
 C36A-C34A
 2.54 with sigma of 0.04
 C34A-C35A
 2.54 with sigma of 0.04
 C96-H11
 1.880134 with sigma of 0.02
 Gd1-H11
 3.000508 with sigma of 0.02
 C95-H10
 1.863779 with sigma of 0.02
 Gd1-H10
 2.915276 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C105) = Uanis(C106) = Uanis(N3) = Uanis(C107)
Uanis(O1AA) = Uanis(C2AA) = Uanis(N02J) = Uanis(C031) = Uanis(C02W)
Uanis(C78A) = Uanis(C78) = Uanis(C79A) = Uanis(C79) = Uanis(C80A) = Uanis(C80)
Uanis(C84) = Uanis(C82) = Uanis(C81) = Uanis(C83)
Uanis(C86) = Uanis(C88) = Uanis(C85) = Uanis(C87)
Uanis(C32A) = Uanis(C32) = Uanis(C30A) = Uanis(C30) = Uanis(C31A) = Uanis(C31)
Uanis(C37) = Uanis(C38A) = Uanis(C38) = Uanis(C39) = Uanis(C39A) = Uanis(C40) =
Uanis(C40A)
Uanis(C35) = Uanis(C35A) = Uanis(C33) = Uanis(C36) = Uanis(C36A) = Uanis(C34) =
Uanis(C34A)
Uanis(C03U) = Uanis(N02R) = Uanis(C02V)
Uanis(N18) = Uanis(C03L) = Uanis(C01U)
Uanis(C101) = Uanis(C100) = Uanis(C99) = Uanis(C98) = Uanis(C97) = Uanis(C96) =
Uanis(O11) = Uanis(O12) = Uanis(C102) = Uanis(N2)
Uanis(C89) = Uanis(C90) = Uanis(O10) = Uanis(C95) = Uanis(C94) = Uanis(C93) =
Uanis(C92) = Uanis(C91) = Uanis(N1)
Uanis(N02C) = Uanis(C029) = Uanis(C02O)
Uanis(O14) = Uanis(C104)
Uanis(O15) = Uanis(C105) = Uanis(N3) = Uanis(C107) = Uanis(C106)
4. Others
 Fixed Sof: H10(0.5) H11(0.5) C34A(0.65) H34A(0.65) H34B(0.65) H34C(0.65)
 C40(0.8) H40A(0.8) H40B(0.8) H40C(0.8) C38(0.8) H38A(0.8) H38B(0.8) H38C(0.8)
 C31(0.55) H31A(0.55) H31B(0.55) H31C(0.55) C32(0.55) H32A(0.55) H32B(0.55)
 H32C(0.55) C36A(0.65) H36A(0.65) H36B(0.65) H36C(0.65) C35A(0.65) H35A(0.65)
 H35B(0.65) H35C(0.65) C39(0.8) H39A(0.8) H39B(0.8) H39C(0.8) C30(0.55)
 H30A(0.55) H30B(0.55) H30C(0.55) C79A(0.6) H79A(0.6) H79B(0.6) H79C(0.6)
 C78A(0.6) H78A(0.6) H78B(0.6) H78C(0.6) C80A(0.6) H80A(0.6) H80B(0.6)
 H80C(0.6) C79(0.4) H79D(0.4) H79E(0.4) H79F(0.4) C80(0.4) H80D(0.4) H80E(0.4)
 H80F(0.4) C78(0.4) H78D(0.4) H78E(0.4) H78F(0.4) C32A(0.45) H32D(0.45)
 H32E(0.45) H32F(0.45) C31A(0.45) H31D(0.45) H31E(0.45) H31F(0.45) C30A(0.45)
 H30D(0.45) H30E(0.45) H30F(0.45) C38A(0.2) H38D(0.2) H38E(0.2) H38F(0.2)
 C40A(0.2) H40D(0.2) H40E(0.2) H40F(0.2) C39A(0.2) H39D(0.2) H39E(0.2)
 H39F(0.2) C35(0.35) H35D(0.35) H35E(0.35) H35F(0.35) C36(0.35) H36D(0.35)
 H36E(0.35) H36F(0.35) C34(0.35) H34D(0.35) H34E(0.35) H34F(0.35)
5.a Ternary CH refined with riding coordinates:
 C45(H45), C28(H28)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C102(H10A,H10B), C89(H89A,H89B), C21(H21A,H21B), C52(H52A,
 H52B), C95(H95A,H95B), C7(H7A,H7B), C59(H59A,H59B), C96(H96A,H96B), C66(H66A,
 H66B)
5.c Me refined with riding coordinates:
 C34A(H34A,H34B,H34C), C40(H40A,H40B,H40C), C38(H38A,H38B,H38C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C36A(H36A,H36B,H36C), C35A(H35A,H35B,H35C),
 C39(H39A,H39B,H39C), C30(H30A,H30B,H30C), C79A(H79A,H79B,H79C), C78A(H78A,H78B,
 H78C), C80A(H80A,H80B,H80C), C79(H79D,H79E,H79F), C80(H80D,H80E,H80F),
 C78(H78D,H78E,H78F), C32A(H32D,H32E,H32F), C31A(H31D,H31E,H31F), C30A(H30D,
 H30E,H30F), C38A(H38D,H38E,H38F), C40A(H40D,H40E,H40F), C39A(H39D,H39E,H39F),
 C35(H35D,H35E,H35F), C36(H36D,H36E,H36F), C34(H34D,H34E,H34F)
5.d Aromatic/amide H refined with riding coordinates:
 C47(H47), C70(H70), C2(H2), C18(H18), C56(H56), C16(H16), C49(H49), C25(H25),
 C4(H4), C54(H54), C105(H105), C91(H91), C23(H23), C11(H11A), C68(H68),
 C93(H93), C100(H100), C98(H98), C9(H9), C99(H99), C92(H92), C61(H61),
 C2AA(H2AA), C63(H63)
5.e Idealised Me refined as rotating group:
 C01U(H01A,H01B,H01C), C43(H43A,H43B,H43C), C02O(H02D,H02E,H02F), C42(H42A,
 H42B,H42C), C103(H10C,H10D,H10E), C02W(H02A,H02B,H02C), C75(H75A,H75B,H75C),
 C031(H03A,H03B,H03C), C44(H44A,H44B,H44C), C76(H76A,H76B,H76C), C88(H88A,H88B,
 H88C), C84(H84A,H84B,H84C), C107(H10F,H10G,H10H), C74(H74A,H74B,H74C),
 C104(H10I,H10J,H10K), C83(H83A,H83B,H83C), C106(H10L,H10M,H10N), C86(H86A,H86B,
 H86C), C87(H87A,H87B,H87C), C03U(H03D,H03E,H03F), C82(H82A,H82B,H82C)
5.f Idealised tetrahedral OH refined as rotating group:
 O8(H8), O7(H7), O6(H6)
;
_shelx_fab_checksum              22285
_olex2_submission_special_instructions 'No special instructions were received'