[MIII2MII3]n+ trigonal bipyramidal cages based on diamagnetic and paramagnetic metalloligands.
Brechin, Euan K.; Sanz, Sergio; O'Connor, Helen; Martí-Centelles, Vicente; Comar, Priyanka; Pitak, Mateusz; Coles, Simon; Lorusso, Giulia; Palacios, Elias; Evangelisti, Marco; Baldansuren, Amgalanbaatar; Chilton, Nicholas F.; Weihe, Høgni; McInnes, Eric J. L.; Lusby, Paul; Piligkos, Stergios; Chem. Sci.  (2017) –; doi:10.1039/C7SC00487G

data_1546083
_publ_section_title
;
 [MIII2MII3]n+ trigonal bipyramidal cages based on diamagnetic and
 paramagnetic metalloligands.
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC00487G
_journal_year                    2017
_chemical_formula_moiety
'C135 H126 Cr2 N6 O12 P6 Pd3, 6(C F3 O3 S), 17 C H4 O'
_chemical_formula_sum            'C158 H194 Cr2 F18 N6 O47 P6 Pd3 S6'
_chemical_formula_weight         4072.56
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-09-30
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_audit_update_record
;
2017-05-01 deposited with the CCDC.
2017-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                104.146(3)
_cell_angle_beta                 109.298(4)
_cell_angle_gamma                95.522(4)
_cell_formula_units_Z            2
_cell_length_a                   18.4407(9)
_cell_length_b                   22.0037(9)
_cell_length_c                   27.1925(10)
_cell_measurement_reflns_used    15471
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      74.9620
_cell_measurement_theta_min      3.3340
_cell_volume                     9907.3(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
;
_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    'ShelXT (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -80.00   35.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686   19.0000    0.0000 115

  2 omega  -96.00   -2.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  125.0000   90.0000 94

  3 omega  -50.00   29.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686   38.0000   60.0000 79

  4 omega  -80.00   35.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686   19.0000  120.0000 115

  5 omega  -50.00   29.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686   38.0000 -120.0000 79

  6 omega   23.00   98.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1686 -125.0000   30.0000 75

  7 omega   23.00   98.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       43.1686 -125.0000 -150.0000 75

  8 omega   30.00  109.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000 -120.0000 79

  9 omega   80.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   77.0000    0.0000 98

 10 omega   40.00   98.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000  -60.0000 58

 11 omega   83.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   61.0000  -90.0000 95

 12 omega   87.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000  -30.0000 91

 13 omega   40.00   98.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000   60.0000 58

 14 omega   40.00   98.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -45.0000  120.0000 58

 15 omega   87.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000   60.0000 91

 16 omega   30.00  109.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  -30.0000 79

 17 omega   39.00  121.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000  150.0000 82

 18 omega   30.00  109.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000  -90.0000 79

 19 omega   30.00  109.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -94.0000   60.0000 79

 20 omega   36.00   91.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000  -30.0000 -120.0000 55

 21 omega   80.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   77.0000 -150.0000 98

 22 omega   39.00  121.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000 -125.0000 -150.0000 82

 23 omega -113.00  -17.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -57.0000  -30.0000 96

 24 omega -113.00  -17.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -57.0000 -120.0000 96

 25 omega -113.00  -17.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -57.0000  150.0000 96

 26 omega -117.00  -12.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -77.0000 -150.0000 105

 27 omega -117.00  -12.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -77.0000  -30.0000 105

 28 omega -113.00  -17.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.1686  -57.0000   60.0000 96

 29 omega   66.00  178.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   15.0000 -180.0000 112

 30 omega   87.00  128.00   1.0000   30.0000
omega____ theta____ kappa____ phi______ frames
    -      111.0000   45.0000   90.0000 41
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent Technologies SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0386945000
_diffrn_orient_matrix_UB_12      -0.0119060000
_diffrn_orient_matrix_UB_13      -0.0620023000
_diffrn_orient_matrix_UB_21      0.0325558000
_diffrn_orient_matrix_UB_22      0.0699653000
_diffrn_orient_matrix_UB_23      0.0068446000
_diffrn_orient_matrix_UB_31      0.0747137000
_diffrn_orient_matrix_UB_32      -0.0194672000
_diffrn_orient_matrix_UB_33      -0.0072796000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0871
_diffrn_reflns_av_unetI/netI     0.0523
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            66752
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        39.973
_diffrn_reflns_theta_max         39.973
_diffrn_reflns_theta_min         3.153
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.843
_exptl_absorpt_correction_T_max  0.946
_exptl_absorpt_correction_T_min  0.684
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34k (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,16:31:05)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       rod
_exptl_crystal_F_000             4188
_exptl_crystal_recrystallization_method
'The material was recrystallised from methanol by slow evaporation'
_exptl_crystal_size_max          0.5466
_exptl_crystal_size_mid          0.1073
_exptl_crystal_size_min          0.0443
_refine_diff_density_max         1.292
_refine_diff_density_min         -0.560
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1484
_refine_ls_number_reflns         12021
_refine_ls_number_restraints     697
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.1050
_refine_ls_R_factor_gt           0.0806
_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^)+(0.1305P)^2^+60.9034P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2197
_refine_ls_wR_factor_ref         0.2423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8644
_reflns_number_total             12021
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc00487g2.cif
_cod_data_source_block           eb4197
_cod_database_code               1546083
_chemical_oxdiff_formula         'C50 H200 O20 N10 Cr6 Pd6 F3 S P'
_chemical_oxdiff_usercomment     '@ 120 K C-1908'
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     39.93
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C110-C9' \\sim C110-C109
 with sigma of 0.02
 P5-C118 \\sim P6-C130
 with sigma of 0.02
 P6'-C24' \\sim P6-C124
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 N4, C28, C29, C30, C31, C32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C76, C77, C78, C79, C80, C81
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C70, C71, C72, C73, C74, C75
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C58, C59, C60, C61, C62, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, C1A, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6, O1, C7, C8, O2, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N2, C11, C10, C12, C13, C14
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15, O3, C16, C17, O4, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N3, C19, C20, C21, C22, C23
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, C24, C25, C26, O6, C27
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C103, C108, C107, C106, C105, C104
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C98, C99, C100, C101, C102, C97
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C137, S2, O23, O22, O24, F6, F5, F4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C45, C44, O10, C43, C42, O9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N5, C41, C40, C39, C38, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N6, C46, C48, C47, C49, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C51, O11, C52, C53, C54, O12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C85, C90, C89, C88, C87, C86
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C91, C92, C93, C94, C95, C96
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{S1, F2, F1, F3, O20, O21, O19, C136}
as
{S2, F6, F5, F4, O23, O22, O24, C137}
5. Others
 Sof(P5')=Sof(P6')=Sof(H11C)=Sof(H11D)=Sof(H11G)=Sof(H11H)=Sof(C9')=Sof(H9'A)=
 Sof(H9'B)=Sof(C12')=Sof(C17')=Sof(H17')=Sof(C16')=Sof(H16')=Sof(C15')=
 Sof(H15')=Sof(C14')=Sof(H14')=Sof(C13')=Sof(H13')=Sof(C18')=Sof(C19')=
 Sof(H19')=Sof(C20')=Sof(H20')=Sof(C21')=Sof(H21')=Sof(C22')=Sof(H22')=
 Sof(C23')=Sof(H23')=Sof(C24')=Sof(C25')=Sof(H25')=Sof(C26')=Sof(H26')=
 Sof(C27')=Sof(H27')=Sof(C28')=Sof(H28')=Sof(C29')=Sof(H29')=Sof(C30')=
 Sof(C35')=Sof(H35')=Sof(C34')=Sof(H34')=Sof(C33')=Sof(H33')=Sof(C32')=
 Sof(H32')=Sof(C31')=Sof(H31')=1-FVAR(1)
 Sof(P6)=Sof(P5)=Sof(H11A)=Sof(H11B)=Sof(H11E)=Sof(H11F)=Sof(C109)=Sof(H10A)=
 Sof(H10B)=Sof(C112)=Sof(C117)=Sof(H117)=Sof(C116)=Sof(H116)=Sof(C115)=
 Sof(H115)=Sof(C114)=Sof(H114)=Sof(C113)=Sof(H113)=Sof(C118)=Sof(C123)=
 Sof(H123)=Sof(C122)=Sof(H122)=Sof(C121)=Sof(H121)=Sof(C120)=Sof(H120)=
 Sof(C119)=Sof(H119)=Sof(C124)=Sof(C125)=Sof(H125)=Sof(C126)=Sof(H126)=
 Sof(C127)=Sof(H127)=Sof(C128)=Sof(H128)=Sof(C129)=Sof(H129)=Sof(C130)=
 Sof(C131)=Sof(H131)=Sof(C132)=Sof(H132)=Sof(C133)=Sof(H133)=Sof(C134)=
 Sof(H134)=Sof(C135)=Sof(H135)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C82(H82A,H82B), C83(H83A,
 H83B), C84(H84A,H84B), C110(H11A,H11B), C110(H11C,H11D), C111(H11E,H11F),
 C111(H11G,H11H), C109(H10A,H10B), C9'(H9'A,H9'B)
6.b Aromatic/amide H refined with riding coordinates:
 C1A(H1A), 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), C28(H28),
  C29(H29), C31(H31), C32(H32), C34(H34), C37(H37), C38(H38), C40(H40),
 C41(H41), C43(H43), C46(H46), C47(H47), C49(H49), C50(H50), C52(H52), C59(H59),
  C60(H60), C61(H61), C62(H62), C63(H63), C65(H65), C66(H66), C67(H67),
 C68(H68), C69(H69), C71(H71), C72(H72), C73(H73), C74(H74), C75(H75), C77(H77),
  C78(H78), C79(H79), C80(H80), C81(H81), C86(H86), C87(H87), C88(H88),
 C89(H89), C90(H90), C92(H92), C93(H93), C94(H94), C95(H95), C96(H96), C98(H98),
  C99(H99), C100(H100), C101(H101), C102(H102), C108(H108), C107(H107),
 C106(H106), C105(H105), C104(H104), C117(H117), C116(H116), C115(H115),
 C114(H114), C113(H113), C123(H123), C122(H122), C121(H121), C120(H120),
 C119(H119), C125(H125), C126(H126), C127(H127), C128(H128), C129(H129),
 C131(H131), C132(H132), C133(H133), C134(H134), C135(H135), C17'(H17'),
 C16'(H16'), C15'(H15'), C14'(H14'), C13'(H13'), C19'(H19'), C20'(H20'),
 C21'(H21'), C22'(H22'), C23'(H23'), C25'(H25'), C26'(H26'), C27'(H27'),
 C28'(H28'), C29'(H29'), C35'(H35'), C34'(H34'), C33'(H33'), C32'(H32'),
 C31'(H31')
6.c Fitted hexagon refined as free rotating group:
 C58(C59,C60,C61,C62,C63), C70(C71,C72,C73,C74,C75), C103(C108,C107,C106,C105,
 C104), C112(C117,C116,C115,C114,C113), C118(C123,C122,C121,C120,C119),
 C124(C125,C126,C127,C128,C129), C130(C131,C132,C133,C134,C135), C12'(C17',C16',
 C15',C14',C13'), C18'(C19',C20',C21',C22',C23'), C24'(C25',C26',C27',C28',
 C29'), C30'(C35',C34',C33',C32',C31')
6.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C18(H18A,H18B,H18C), C27(H27A,H27B,H27C), C36(H36A,H36B,
 H36C), C45(H45A,H45B,H45C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              75148
_shelx_fab_checksum              49395
_shelx_shelxl_version_number     2014/7
_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-1908
_olex2_submission_special_instructions 'No special instructions were received'