With complements of the ligands: an unusual S-shaped [Mn<sub>7</sub>]<sub>2</sub> assembly from tethered calixarenes.
Coletta, Marco; Sanz, Sergio; Brechin, Euan K.; Dalgarno, Scott J.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 9882–9887; doi:10.1039/d0dt01766c

data_7704802
_publ_section_title
;
 With complements of the ligands: an unusual S-shaped
 [Mn<sub>7</sub>]<sub>2</sub> assembly from tethered calixarenes.
;
_journal_issue                   28
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9882
_journal_page_last               9887
_journal_paper_doi               10.1039/d0dt01766c
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety
'C155 H192 Mn7 N5 O22, 2(C3 H7 N O), 1[C12H28N4O4]'
_chemical_formula_sum            'C322 H412 Mn14 N14 O48'
_chemical_formula_weight         6015.79
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-05-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.01.31 svn.r88ba2a32 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2020-05-15 deposited with the CCDC.	2020-06-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.498(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   59.816(8)
_cell_length_b                   18.706(2)
_cell_length_c                   30.329(4)
_cell_measurement_reflns_used    2623
_cell_measurement_temperature    100(5)
_cell_measurement_theta_max      15.84
_cell_measurement_theta_min      2.23
_cell_volume                     32855(7)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1609
_diffrn_reflns_av_unetI/netI     0.1430
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_h_min       -54
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            59504
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        19.026
_diffrn_reflns_theta_max         19.026
_diffrn_reflns_theta_min         0.703
_diffrn_source_current           35.0
_diffrn_source_power             1.75
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.585
_exptl_absorpt_correction_T_max  0.7445
_exptl_absorpt_correction_T_min  0.6030
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0808 before and 0.0702 after correction.
The Ratio of minimum to maximum transmission is 0.8099.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_description       block
_exptl_crystal_F_000             12704
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.074
_refine_diff_density_min         -0.909
_refine_diff_density_rms         0.228
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1296
_refine_ls_number_reflns         13262
_refine_ls_number_restraints     176
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1661
_refine_ls_R_factor_gt           0.0919
_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^)+(0.1980P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2566
_refine_ls_wR_factor_ref         0.3161
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7298
_reflns_number_total             13262
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt01766c2.cif
_cod_data_source_block           Mn14BisCalix
_cod_depositor_comments          'Adding full bibliography for 7704802.cif.'
_cod_original_cell_volume        32856(7)
_cod_database_code               7704802
_shelx_shelxl_version_number     2014/7
_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. Restrained distances
 C79A-C77 = C80-C77 = C80A-C77 = C78-C77 = C78A-C77 = C79-C77
 1.54 with sigma of 0.02
 C81-C83A = C84-C81 = C84A-C81 = C82-C81 = C82A-C81 = C83-C81
 1.54 with sigma of 0.02
 C85-C86 = C87-C85 = C88-C85
 1.54 with sigma of 0.02
 C76-C73 = C74-C73 = C75-C73
 1.54 with sigma of 0.02
 O18-C145 = O18-C1A
 1.2 with sigma of 0.02
 N3-C145 = N3-C1A = N3-C146 = N3-C1C = N3-C147 = N3-C1B
 1.45 with sigma of 0.02
 N5-C151 = N5-C153 = N5-C152
 1.45 with sigma of 0.02
 N5-C153 = N5-C151 = N5-C152
 1.45 with sigma of 0.02
 O19-C148
 1.2 with sigma of 0.02
 N4-C149 = N4-C150 = N4-C148
 1.45 with sigma of 0.02
 C30-C29 = C31-C29 = C32-C29
 1.54 with sigma of 0.02
 C36-C33 = C35-C33 = C34-C33
 1.54 with sigma of 0.02
 C38-C37 = C38A-C37 = C39-C37 = C39A-C37 = C40A-C37 = C40-C37
 1.54 with sigma of 0.02
 C42-C41 = C44-C41 = C43-C41
 1.54 with sigma of 0.02
 O22-C155 = O21-C154
 1.45 with sigma of 0.02
 C118-C117 = C119-C117 = C120-C117
 1.54 with sigma of 0.02
 C124-C121 = C121-C122 = C121-C123
 1.54 with sigma of 0.02
 C128-C125 = C126-C125 = C127-C125
 1.54 with sigma of 0.02
 C140-C139 = C141-C140 = C142-C141 = C142-C143 = C143-C144
 1.54 with sigma of 0.02
 N2-C140 = N2-C144
 1.4 with sigma of 0.02
 O17-C139
 1.2 with sigma of 0.02
 O16-C133
 1.2 with sigma of 0.02
 N1-C138 = N1-C134
 1.4 with sigma of 0.02
 C133-C134 = C135-C134 = C135-C136 = C137-C136 = C137-C138
 1.54 with sigma of 0.02
 N01E-C05B = N01E-C04R = N01E-C050
 1.45 with sigma of 0.02
 O044-C050
 1.2 with sigma of 0.02
 O01O-C04Y
 1.2 with sigma of 0.02
 N01H-C055 = N01H-C04U = N01H-C04Y
 1.45 with sigma of 0.02
 C1G-C129 = C130-C129 = C129-C1H = C129-C131 = C129-C1I = C129-C132
 1.54 with sigma of 0.02
 C12C-C125 = C12B-C125 = C12A-C125
 1.54 with sigma of 0.02
 C79A-C80A
 2.54 with sigma of 0.04
 C80A-C78A
 2.54 with sigma of 0.04
 C78A-C79A
 2.54 with sigma of 0.04
 C80-C78
 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
 C83A-C84A
 2.54 with sigma of 0.04
 C84A-C82A
 2.54 with sigma of 0.04
 C82A-C83A
 2.54 with sigma of 0.04
 C84-C82
 2.54 with sigma of 0.04
 C82-C83
 2.54 with sigma of 0.04
 C83-C84
 2.54 with sigma of 0.04
 C87-C88
 2.54 with sigma of 0.04
 C88-C86
 2.54 with sigma of 0.04
 C86-C87
 2.54 with sigma of 0.04
 C76-C74
 2.54 with sigma of 0.04
 C74-C75
 2.54 with sigma of 0.04
 C75-C76
 2.54 with sigma of 0.04
 C145-C147
 2.54 with sigma of 0.04
 C147-C146
 2.54 with sigma of 0.04
 C146-C145
 2.54 with sigma of 0.04
 C1A-C1B
 2.54 with sigma of 0.04
 C1B-C1C
 2.54 with sigma of 0.04
 C1C-C1A
 2.54 with sigma of 0.04
 C152-C153
 2.54 with sigma of 0.04
 C153-C151
 2.54 with sigma of 0.04
 C151-C152
 2.54 with sigma of 0.04
 C149-C148
 2.54 with sigma of 0.04
 C148-C150
 2.54 with sigma of 0.04
 C150-C149
 2.54 with sigma of 0.04
 C31-C32
 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
 C34-C35
 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
 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
 C44-C42
 2.54 with sigma of 0.04
 C42-C43
 2.54 with sigma of 0.04
 C43-C44
 2.54 with sigma of 0.04
 C120-C118
 2.54 with sigma of 0.04
 C118-C119
 2.54 with sigma of 0.04
 C119-C120
 2.54 with sigma of 0.04
 C123-C122
 2.54 with sigma of 0.04
 C122-C124
 2.54 with sigma of 0.04
 C124-C123
 2.54 with sigma of 0.04
 C05B-C04R
 2.54 with sigma of 0.04
 C04R-C050
 2.54 with sigma of 0.04
 C050-C05B
 2.54 with sigma of 0.04
 C055-C04U
 2.54 with sigma of 0.04
 C04U-C04Y
 2.54 with sigma of 0.04
 C04Y-C055
 2.54 with sigma of 0.04
 C130-C131
 2.54 with sigma of 0.04
 C131-C132
 2.54 with sigma of 0.04
 C132-C130
 2.54 with sigma of 0.04
 C1H-C1I
 2.54 with sigma of 0.04
 C1I-C1G
 2.54 with sigma of 0.04
 C1G-C1H
 2.54 with sigma of 0.04
 C126-C128
 2.54 with sigma of 0.04
 C12C-C12A
 2.54 with sigma of 0.04
 C128-C127
 2.54 with sigma of 0.04
 C12B-C12A
 2.54 with sigma of 0.04
 C127-C126
 2.54 with sigma of 0.04
 C12B-C12C
 2.54 with sigma of 0.04
 C3-C2 \\sim C1-C6 \\sim C5-C4
 with sigma of 0.02
 C9-C10 \\sim C11-C12 \\sim C13-C8
 with sigma of 0.02
 C16-C17 \\sim C18-C19 \\sim C20-C15
 with sigma of 0.02
 C22-C23 \\sim C24-C25 \\sim C26-C27
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C80) = Uanis(C79A) = Uanis(C79) = Uanis(C78A) = Uanis(C78) = Uanis(C80A)
= Uanis(C77)
Uanis(C84A) = Uanis(C84) = Uanis(C83A) = Uanis(C83) = Uanis(C82A) = Uanis(C82)
= Uanis(C81)
Uanis(O18) = Uanis(C1A) = Uanis(C145) = Uanis(N3) = Uanis(C147) = Uanis(C1C) =
Uanis(C146) = Uanis(C1B)
Uanis(C152) = Uanis(N5) = Uanis(C151) = Uanis(O20) = Uanis(C153)
Uanis(O19) = Uanis(C148) = Uanis(N4) = Uanis(C150) = Uanis(C149)
Uanis(C39A) = Uanis(C39) = Uanis(C40) = Uanis(C40A) = Uanis(C37) = Uanis(C38A)
= Uanis(C38)
Uanis(N01E) = Uanis(C04R) = Uanis(C05B) = Uanis(C050) = Uanis(O044)
Uanis(O01O) = Uanis(C04Y) = Uanis(N01H) = Uanis(C055) = Uanis(C04U)
Uanis(C130) = Uanis(C1G) = Uanis(C132) = Uanis(C129) = Uanis(C1H) = Uanis(C131)
= Uanis(C1I)
Uanis(C46) = Uanis(C48) = Uanis(C47) = Uanis(C49) = Uanis(C50) = Uanis(C51)
Uanis(C58) = Uanis(C53) = Uanis(C54) = Uanis(C55) = Uanis(C56) = Uanis(C57)
Uanis(C65) = Uanis(C60) = Uanis(C61) = Uanis(C62) = Uanis(C63) = Uanis(C64)
Uanis(C45) = Uanis(C28)
Uanis(C1) = Uanis(C6) = Uanis(C5) = Uanis(C2) = Uanis(C4) = Uanis(C3)
Uanis(C10) = Uanis(C13) = Uanis(C8) = Uanis(C9) = Uanis(C12) = Uanis(C11) =
Uanis(O2)
Uanis(N2) = Uanis(C144) = Uanis(C140) = Uanis(C143) = Uanis(C142) = Uanis(C141)
Uanis(C114) = Uanis(C113) = Uanis(C110) = Uanis(C112) = Uanis(C111) =
Uanis(C116) = Uanis(C115) = Uanis(C109)
Uanis(O22) = Uanis(C155)
Uanis(C89) = Uanis(C92) = Uanis(C93) = Uanis(C91) = Uanis(C90) = Uanis(C94)
Uanis(C125) = Uanis(C127) = Uanis(C128) = Uanis(C126) = Uanis(C12A) =
Uanis(C12B) = Uanis(C12C)
Uanis(C108) = Uanis(C107) = Uanis(C105) = Uanis(C106) = Uanis(C103) =
Uanis(C104)
Uanis(C15) = Uanis(C16) = Uanis(C17) = Uanis(C18) = Uanis(C19) = Uanis(C20)
Uanis(C22) = Uanis(C23) = Uanis(C24) = Uanis(C25) = Uanis(C27) = Uanis(C26)
4. Others
 Fixed Sof: C38(0.9) H38A(0.9) H38B(0.9) H38C(0.9) C39(0.9) H39A(0.9)
 H39B(0.9) H39C(0.9) C40(0.9) H40A(0.9) H40B(0.9) H40C(0.9) C78(0.8) H78A(0.8)
 H78B(0.8) H78C(0.8) C79(0.8) H79A(0.8) H79B(0.8) H79C(0.8) C80(0.8) H80A(0.8)
 H80B(0.8) H80C(0.8) C82(0.85) H82A(0.85) H82B(0.85) H82C(0.85) C83(0.85)
 H83A(0.85) H83B(0.85) H83C(0.85) C84(0.85) H84A(0.85) H84B(0.85) H84C(0.85)
 C126(0.75) H12M(0.75) H12N(0.75) H12O(0.75) C127(0.75) H12P(0.75) H12Q(0.75)
 H12R(0.75) C128(0.75) H12S(0.75) H12T(0.75) H12U(0.75) C130(0.7) H13E(0.7)
 H13F(0.7) H13G(0.7) C131(0.7) H13H(0.7) H13I(0.7) H13J(0.7) C132(0.7)
 H13K(0.7) H13L(0.7) H13M(0.7) C145(0.75) H145(0.75) C146(0.75) H14F(0.75)
 H14G(0.75) H14H(0.75) C147(0.75) H14I(0.75) H14J(0.75) H14K(0.75) C1A(0.25)
 H1A(0.25) C1B(0.25) H1BA(0.25) H1BB(0.25) H1BC(0.25) C1C(0.25) H1CA(0.25)
 H1CB(0.25) H1CC(0.25) C1G(0.3) H1GA(0.3) H1GB(0.3) H1GC(0.3) C1H(0.3)
 H1HA(0.3) H1HB(0.3) H1HC(0.3) C1I(0.3) H1IA(0.3) H1IB(0.3) H1IC(0.3)
 C12A(0.25) H12V(0.25) H12W(0.25) H12X(0.25) C12B(0.25) H12Y(0.25) H(0.25)
 HA(0.25) C12C(0.25) H12Z(0.25) HB(0.25) HC(0.25) C38A(0.1) H38D(0.1) H38E(0.1)
 H38F(0.1) C39A(0.1) H39D(0.1) H39E(0.1) H39F(0.1) C40A(0.1) H40D(0.1)
 H40E(0.1) H40F(0.1) C78A(0.2) H78D(0.2) H78E(0.2) H78F(0.2) C79A(0.2)
 H79D(0.2) H79E(0.2) H79F(0.2) C80A(0.2) H80D(0.2) H80E(0.2) H80F(0.2)
 C82A(0.15) H82D(0.15) H82E(0.15) H82F(0.15) C83A(0.15) H83D(0.15) H83E(0.15)
 H83F(0.15) C84A(0.15) H84D(0.15) H84E(0.15) H84F(0.15)
5.a Ternary CH refined with riding coordinates:
 C28(H28), C45(H45), C116(H116)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B), C21(H21A,H21B), C52(H52A,H52B), C59(H59A,H59B),
 C66(H66A,H66B), C95(H95A,H95B), C102(H10A,H10B), C109(H10C,H10D), C133(H13A,
 H13B), C139(H13C,H13D)
5.c Me refined with riding coordinates:
 C04U(H04A,H04B,H04C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C), C055(H05A,H05B,H05C), C149(H14C,H14D,H14E), C150(H15A,H15B,H15C),
 C152(H15D,H15E,H15F), C153(H15G,H15H,H15I), C38(H38A,H38B,H38C), C39(H39A,H39B,
 H39C), C40(H40A,H40B,H40C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,
 H80B,H80C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C),
 C126(H12M,H12N,H12O), C127(H12P,H12Q,H12R), C128(H12S,H12T,H12U), C130(H13E,
 H13F,H13G), C131(H13H,H13I,H13J), C132(H13K,H13L,H13M), C146(H14F,H14G,H14H),
 C147(H14I,H14J,H14K), C1B(H1BA,H1BB,H1BC), C1C(H1CA,H1CB,H1CC), C1G(H1GA,H1GB,
 H1GC), C1H(H1HA,H1HB,H1HC), C1I(H1IA,H1IB,H1IC), C12A(H12V,H12W,H12X),
 C12B(H12Y,H,HA), C12C(H12Z,HB,HC), C38A(H38D,H38E,H38F), C39A(H39D,H39E,H39F),
 C40A(H40D,H40E,H40F), C78A(H78D,H78E,H78F), C79A(H79D,H79E,H79F), C80A(H80D,
 H80E,H80F), C82A(H82D,H82E,H82F), C83A(H83D,H83E,H83F), C84A(H84D,H84E,H84F),
 C04R(H04D,H04E,H04F), C05B(H05D,H05E,H05F)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C04Y(H04Y), C9(H9), C11(H11), C16(H16), C18(H18), C23(H23),
 C25(H25), C47(H47), C49(H49), C54(H54), C56(H56), C61(H61), C63(H63), C68(H68),
  C70(H70), C90(H90), C92(H92), C97(H97), C99(H99), C104(H104), C106(H106),
 C111(H111), C113(H113), C135(H135), C136(H136), C137(H137), C138(H138),
 C141(H141), C142(H142), C143(H143), C144(H144), C148(H148), C151(H151),
 C145(H145), C1A(H1A), C050(H050)
5.e Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C42(H42A,H42B,
 H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C74(H74A,H74B,H74C), C75(H75A,
 H75B,H75C), C76(H76A,H76B,H76C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C),
 C88(H88A,H88B,H88C), C118(H11A,H11B,H11C), C119(H11D,H11E,H11F), C120(H12A,
 H12B,H12C), C122(H12D,H12E,H12F), C123(H12G,H12H,H12I), C124(H12J,H12K,H12L),
 C154(H15J,H15K,H15L), C155(H15M,H15N,H15O)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              1610
_shelx_fab_checksum              66976
_olex2_submission_special_instructions 'No special instructions were received'