Reactive Pendant Mn═O in a Synthetic Structural Model of a Proposed S4 State in the Photosynthetic Oxygen Evolving Complex.
Vaddypally, Shivaiah; Kondaveeti, Sandeep K.; Karki, Santosh; Van Vliet, Megan M.; Levis, Robert J.; Zdilla, Michael J.; Journal of the American Chemical Society 139 (2017) 4675–4681; doi:10.1021/jacs.6b05906

data_4126154
_publ_section_title
;
 Reactive Pendant Mn&#x2550;O in a Synthetic Structural Model of a
 Proposed S4 State in the Photosynthetic Oxygen Evolving Complex.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4675
_journal_page_last               4681
_journal_paper_doi               10.1021/jacs.6b05906
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         Mn4(NC4H9)7.6105(NMnO3)0.3895
_chemical_formula_sum            'C30.44 H68.49 Mn4.39 N8 O1.17'
_chemical_formula_weight         806.60
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_symmetry_space_group_name_Hall  'C 2c -2'
_symmetry_space_group_name_H-M   'C m c 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-04-28
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.2315(15)
_cell_length_b                   12.7392(11)
_cell_length_c                   19.4043(16)
_cell_measurement_reflns_used    9917
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.971
_cell_measurement_theta_min      2.890
_cell_volume                     4259.5(6)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       'COSMO (Bruker AXS, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.04
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker KAPPA APEX II DUO'
_diffrn_measurement_method       '\f \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0142
_diffrn_reflns_av_unetI/netI     0.0293
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            10830
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.969
_diffrn_reflns_theta_min         1.988
_exptl_absorpt_coefficient_mu    1.300
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6579
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0489 before and 0.0397 after correction.
The Ratio of minimum to maximum transmission is 0.8824.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.258
_exptl_crystal_description       plate
_exptl_crystal_F_000             1705
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.501
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 2121 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.047(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     284
_refine_ls_number_reflns         4973
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.211
_refine_ls_R_factor_all          0.0285
_refine_ls_R_factor_gt           0.0267
_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^)+(0.0244P)^2^+5.0314P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0645
_refine_ls_wR_factor_ref         0.0662
_reflns_Friedel_coverage         0.832
_reflns_Friedel_fraction_full    0.914
_reflns_Friedel_fraction_max     0.880
_reflns_number_gt                4825
_reflns_number_total             4973
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b05906_si_002.cif
_cod_data_source_block           2_3
_cod_database_code               4126154
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.624
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H) groups, All C(H,H,H) groups
2. Shared sites
{C1, Mn4}
{C11, O11}
{C12, O12}
{C13, O13}
{C2, Mn5}
{C21, O21}
{C22, O22}
3. Restrained distances
 C5-C51 = C5-C52 = C5-C53 = C5-C51' = C5-C52' = C5-C53'
 1.54 with sigma of 0.005
 C51-C52 = C52-C53 = C53-C51
 2.52 with sigma of 0.01
 C51'-C52' = C52'-C53' = C53'-C51'
 2.52 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(Mn4)
Uanis(C11) = Uanis(O11)
Uanis(C12) = Uanis(O12)
Uanis(C13) = Uanis(O13)
Uanis(C2) = Uanis(Mn5)
Uanis(C21) = Uanis(O21)
Uanis(C22) = Uanis(O22)
5. Others
 Sof(C51')=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C52')=Sof(H52D)=Sof(H52E)=
 Sof(H52F)=Sof(C53')=Sof(H53D)=Sof(H53E)=Sof(H53F)=1-FVAR(1)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=FVAR(1)
 Sof(Mn4)=Sof(O11)=Sof(O12)=Sof(O13)=1-FVAR(2)
 Sof(C1)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C12)=Sof(H12A)=Sof(H12B)=
 Sof(H12C)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(2)
 Sof(O22)=1-FVAR(3)
 Sof(Mn5)=Sof(O21)=0.5*(1-FVAR(4))
 Sof(C2)=Sof(C21)=Sof(H21A)=0.5*FVAR(4)
 Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=FVAR(3)
 Fixed Sof: C41(0.5) H41A(0.5) H41B(0.5) H41C(0.5) C42(0.5) H42A(0.5)
 H42B(0.5) H42C(0.5) C43(0.5) H43A(0.5) H43B(0.5) H43C(0.5) C61(0.5) H61A(0.5)
 H61B(0.5) H61C(0.5) C62(0.5) H62A(0.5) H62B(0.5) H62C(0.5) C63(0.5) H63A(0.5)
 H63B(0.5) H63C(0.5)
6.a Me refined with riding coordinates:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C22(H22A,H22B,
 H22C), C32(H32A,H32B,H32C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,
 H43B,H43C), C51(H51A,H51B,H51C), C51'(H51D,H51E,H51F), C52(H52A,H52B,H52C),
 C52'(H52D,H52E,H52F), C53(H53A,H53B,H53C), C53'(H53D,H53E,H53F), C61(H61A,H61B,
 H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C)
;
_shelx_res_checksum              26163
_shelx_hkl_checksum              53924
_olex2_submission_special_instructions 'No special instructions were received'