Helicity inversion and redox chemistry of chiral manganese(ii) cubanes.
Deville, Claire; Granelli, Matteo; Downward, Alan M.; Besnard, Céline; Guenée, Laure; Williams, Alan F.; Dalton transactions (Cambridge, England : 2003) 43 (2014) 12917–; doi:10.1039/c4dt01590h

data_7031891
_publ_section_title
;
 Helicity inversion and redox chemistry of chiral manganese(ii) cubanes.
;
_journal_issue                   34
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12917
_journal_paper_doi               10.1039/c4dt01590h
_journal_volume                  43
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C96 H88 Mn4 N16 O8 P2, 2(Cl O4), 0.7(H2 O)'
_chemical_formula_sum            'C96 H89.4 Cl2 Mn4 N16 O16.7 P2'
_chemical_formula_weight         2087.03
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-06-30
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.06.26 svn.r2951 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.418(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.444(2)
_cell_length_b                   23.205(3)
_cell_length_c                   14.665(2)
_cell_measurement_temperature    180(2)
_cell_volume                     4818.0(11)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      180.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.927
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0423
_diffrn_reflns_av_unetI/netI     0.0869
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.927
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            27762
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.926
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         76.279
_diffrn_reflns_theta_min         3.074
_exptl_absorpt_coefficient_mu    5.611
_exptl_absorpt_correction_T_max  0.7537
_exptl_absorpt_correction_T_min  0.5369
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 numerical followed by a multi scan (ABSPACK)
crysalis
;
_exptl_crystal_density_diffrn    1.439
_exptl_crystal_F_000             2150
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.709
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.069
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.

Two 2 ClO~4~^-^ ions compensates the charge of the complexe. One is disordered 
and was modelled using two component
with geometrical restraints and restraints on anisotropic dispacement parameters. 

DFIX 1.44 Cl1L O4L Cl1L O3L Cl1L O5L Cl1L O2L
DFIX 1.44 0.005 Cl1K O5K Cl1K O2K Cl1K O4K Cl1K O3K
DFIX 2.35 0.04 O4L O5L O5L O2L O2L O3L O3L O4L O3L O5L O4L O2L
DFIX 2.35 0.01 O2K O5K O4K O5K O3K O4K O3K O2K O2K O4K O3K O5K
SIMU 0.02 0.04 1 O2K O5K Cl1K O3K O4K Cl1L O4L O5L O2L O3L

RIGU Cl1L O3L O2L O5L O4L
RIGU Cl1K O2K O5K O3K O4K

A small void with some electronic density was also found in the model. No
other molecules than disordered water could fit the electronic density so
that four disordered water molecules were added to the model. Their
occupancies were refined fisrt with Uiso fixed to 0.05 and then fixed.
REstraints were used for anisotropic displacement parameters.

SIMU 0.04 0.08 1 O2W O1W O3W O4W
ISOR O4W O2W O3W
;
_refine_ls_abs_structure_Flack   0.002(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1315
_refine_ls_number_reflns         15014
_refine_ls_number_restraints     123
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.0638
_refine_ls_R_factor_gt           0.0504
_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^)+(0.0473P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1199
_refine_ls_wR_factor_ref         0.1283
_reflns_Friedel_coverage         0.949
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.926
_reflns_number_gt                12201
_reflns_number_total             15014
_reflns_threshold_expression     'I > 2\s(I)'
_cod_duplicate_entry             7031637
_cod_data_source_file            c4dt01590h2.cif
_cod_data_source_block           7
_cod_original_formula_sum        'C96 H89.40 Cl2 Mn4 N16 O16.70 P2'
_cod_database_code               7031891
_shelxl_version_number           2013-4
_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
 Cl1L-O4L = Cl1L-O3L = Cl1L-O5L = Cl1L-O2L
 1.44 with sigma of 0.02
 Cl1K-O5K = Cl1K-O2K = Cl1K-O4K = Cl1K-O3K
 1.44 with sigma of 0.005
 O4L-O5L = O5L-O2L = O2L-O3L = O3L-O4L = O3L-O5L = O4L-O2L
 2.35 with sigma of 0.04
 O2K-O5K = O4K-O5K = O3K-O4K = O3K-O2K = O2K-O4K = O3K-O5K
 2.35 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O2K \\sim O5K \\sim Cl1K \\sim O3K \\sim O4K \\sim Cl1L \\sim O4L \\sim O5L
\\sim O2L \\sim O3L: within 1A with sigma of 0.02 and sigma for terminal atoms
of 0.04
O2W \\sim O1W \\sim O3W \\sim O4W: within 1A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(O4W) \\sim Ueq, Uanis(O2W) \\sim Ueq, Uanis(O3W) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 Cl1L, O3L, O2L, O5L, O4L
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1K, O2K, O5K, O3K, O4K
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: Cl1L(0.65) O4L(0.65) O5L(0.65) Cl1K(0.35) O2K(0.35) O3K(0.35)
 O4K(0.35) O5K(0.35) O2L(0.65) O2W(0.2) O3W(0.2) O3L(0.65) O4W(0.15) O1W(0.15)
6.a Ternary CH refined with riding coordinates:
 C2A(H2A), C2C(H2C), C2B(H2B), C2D(H2D)
6.b Secondary CH2 refined with riding coordinates:
 C12C(H12A,H12B), C12A(H12C,H12D), C12D(H12G,H12H), C12B(H12I,H12J)
6.c Aromatic/amide H refined with riding coordinates:
 C7E(H7E), C13E(H13E), C13F(H13F), C12F(H12F), C15F(H15F), C14F(H14F),
 C6A(H6A), C7B(H7B), C11F(H11F), C11E(H11E), C12E(H12E), C14E(H14E), C16D(H16D),
  C18B(H18B), C19B(H19B), C6B(H6B), C17D(H17D), C16B(H16B), C6C(H6C),
 C16A(H16A), C8B(H8B), C19D(H19D), C6F(H6F), C16C(H16C), C6E(H6E), C17B(H17B),
 C18A(H18A), C15E(H15E), C19A(H19A), C7A(H7A), C8E(H8E), C9D(H9D), C9F(H9F),
 C6D(H6D), C7F(H7F), C7C(H7C), C8C(H8C), C19C(H19C), C5E(H5E), C5F(H5F),
 C9E(H9E), C9C(H9C), C9A(H9A), C8A(H8A), C9B(H9B), C8F(H8F), C18D(H18D),
 C8D(H8D), C17C(H17C), C18C(H18C), C17A(H17A), C7D(H7D)
6.d Idealised Me refined as rotating group:
 C22D(H22A,H22B,H22C), C22B(H22D,H22E,H22F), C22A(H22G,H22H,H22I), C23D(H23A,
 H23B,H23C), C22C(H22J,H22K,H22L), C23B(H23D,H23E,H23F), C23C(H23G,H23H,H23I),
 C23A(H23J,H23K,H23L)
;
_olex2_submission_special_instructions 'No special instructions were received'