Bisphosphine phenol and phenolate complexes of Mn(i): manganese(i) catalyzed Tishchenko reaction.
Kadassery, Karthika J.; MacMillan, Samantha N.; Lacy, David C.; Dalton transactions (Cambridge, England : 2003) 47 (2018) 12652–12655; doi:10.1039/c8dt02933d

data_7047254
_publ_section_title
;
 Bisphosphine phenol and phenolate complexes of Mn(i): manganese(i)
 catalyzed Tishchenko reaction.
;
_journal_issue                   36
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12652
_journal_page_last               12655
_journal_paper_doi               10.1039/c8dt02933d
_journal_volume                  47
_journal_year                    2018
_chemical_formula_moiety
'2(C72 H59 Mn2 O8 P4), 2(C F3 O3 S), 13(C4 H8 O)'
_chemical_formula_sum            'C198 H222 F6 Mn4 O35 P8 S2'
_chemical_formula_weight         3807.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-08-07 deposited with the CCDC.
2018-08-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.9700(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.1073(2)
_cell_length_b                   15.52110(10)
_cell_length_c                   43.2805(3)
_cell_measurement_reflns_used    54931
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4740
_cell_measurement_theta_min      3.0190
_cell_volume                     18779.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45g (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -56.00   9.00   0.50    2.51    --  -48.30  97.00-117.00  130
  2  \w    -73.00 -48.00   0.50   10.02    --  -86.25  97.00-117.00   50
  3  \w    -67.00 -18.00   0.50   10.02    --  -86.25  30.00  90.00   98
  4  \w   -117.00 -72.00   0.50    2.51    --  -48.30-125.00  30.00   90
  5  \w   -117.00 -71.00   0.50    2.51    --  -48.30-125.00 -60.00   92
  6  \w   -108.00 -72.00   0.50    2.51    --  -48.30-125.00-150.00   72
  7  \w   -101.00 -76.00   0.50    2.51    --  -48.30-125.00-180.00   50
  8  \w     43.00  81.00   0.50    2.51    --   48.30-125.00-120.00   76
  9  \w     38.00 109.00   0.50   10.02    --  107.75 -94.00-120.00  142
 10  \w     87.00 113.00   0.50   10.02    --  107.75 -61.00 -90.00   52
 11  \w     84.00 109.00   0.50   10.02    --  107.75 -94.00 -30.00   50
 12  \w     97.00 122.00   0.50   10.02    --  107.75 -61.00   0.00   50
 13  \w     89.00 116.00   0.50   10.02    --  107.75 -15.00  60.00   54
 14  \w    106.00 132.00   0.50   10.02    --  107.75  15.00  90.00   52
 15  \w    118.00 144.00   0.50   10.02    --  107.75  15.00  60.00   52
 16  \w    151.00 178.00   0.50   10.02    --  107.75  15.00  60.00   54
 17  \w    142.00 171.00   0.50   10.02    --  107.75  45.00 120.00   58
 18  \w    144.00 174.00   0.50   10.02    --  107.75 125.00  60.00   60
 19  \w    107.00 132.00   0.50   10.02    --  107.75  45.00 120.00   50
 20  \w    100.00 127.00   0.50   10.02    --  107.75  30.00   0.00   54
 21  \w    130.00 156.00   0.50   10.02    --  107.75  30.00 -60.00   52
 22  \w    115.00 142.00   0.50   10.02    --  107.75  97.00-117.00   54
 23  \w    133.00 160.00   0.50   10.02    --  107.75  15.00-150.00   54
 24  \w    149.00 176.00   0.50   10.02    --  107.75  15.00-180.00   54
 25  \w     98.00 125.00   0.50   10.02    --  107.75  15.00-180.00   54
 26  \w     46.00  73.00   0.50   10.02    --  107.75 -24.00-165.94   54
 27  \w     53.00  79.00   0.50   10.02    --  107.75 -56.00-157.26   52
 28  \w     37.00  76.00   0.50   10.02    --  107.75 -45.00-150.00   78
 29  \w     45.00  71.00   0.50   10.02    --  107.75 -15.00-180.00   52
 30  \w     36.00  69.00   0.50   10.02    --  107.75 -30.00-120.00   66
 31  \w     38.00  63.00   0.50   10.02    --  107.75 -61.00 -90.00   50
 32  \w     35.00  61.00   0.50   10.02    --  107.75 -30.00 -30.00   52
 33  \w     39.00  75.00   0.50   10.02    --  107.75 -61.00   0.00   72
 34  \w     64.00  90.00   0.50   10.02    --  107.75 -94.00 -60.00   52
 35  \w     66.00  92.00   0.50   10.02    --  107.75 -94.00 -90.00   52
 36  \w     63.00  97.00   0.50   10.02    --  107.75-125.00 -30.00   68
 37  \w     68.00  94.00   0.50   10.02    --  107.75-125.00   0.00   52
 38  \w     39.00  75.00   0.50   10.02    --  107.75 -94.00 -30.00   72
 39  \w     37.00  76.00   0.50   10.02    --  107.75 -45.00 -60.00   78
 40  \w     37.00  62.00   0.50   10.02    --  107.75 -94.00 -60.00   50
 41  \w     37.00  69.00   0.50   10.02    --  107.75 -30.00 -60.00   64
 42  \w     36.00  62.00   0.50   10.02    --  107.75 -30.00  30.00   52
 43  \w     35.00  66.00   0.50   10.02    --  107.75 -15.00  60.00   62
 44  \w     42.00  69.00   0.50   10.02    --  107.75 -45.00  60.00   54
 45  \w     42.00  68.00   0.50   10.02    --  107.75 -45.00 120.00   52
 46  \w     39.00  67.00   0.50   10.02    --  107.75 -30.00 150.00   56
 47  \w     46.00  76.00   0.50   10.02    --  107.75 -45.00 150.00   60
 48  \w     48.00  73.00   0.50   10.02    --  107.75 -97.00 134.00   50
 49  \w     42.00 106.00   0.50   10.02    --  107.75 -94.00 150.00  128
 50  \w     70.00 114.00   0.50   10.02    --  107.75-125.00 120.00   88
 51  \w     36.00  61.00   0.50   10.02    --  107.75 -30.00 120.00   50
 52  \w     -6.00  20.00   0.50    2.51    --   48.30 -97.00 134.00   52
 53  \w     24.00  50.00   0.50    2.51    --   48.30 -97.00 134.00   52
 54  \w     57.00  83.00   0.50   10.02    --  107.75-125.00-150.00   52
 55  \w   -144.00-119.00   0.50   10.02    --  -86.25 -97.00 134.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0051006000
_diffrn_orient_matrix_UB_12      0.0310992000
_diffrn_orient_matrix_UB_13      0.0332965000
_diffrn_orient_matrix_UB_21      -0.0329095000
_diffrn_orient_matrix_UB_22      -0.0771356000
_diffrn_orient_matrix_UB_23      0.0048370000
_diffrn_orient_matrix_UB_31      0.0439194000
_diffrn_orient_matrix_UB_32      -0.0542024000
_diffrn_orient_matrix_UB_33      0.0121647000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            109043
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.070
_diffrn_reflns_theta_min         3.027
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.641
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.568
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45g (Rigaku Oxford Diffraction, 2018)
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            'clear yellow'
_exptl_crystal_density_diffrn    1.347
_exptl_crystal_description       block
_exptl_crystal_F_000             7984
_exptl_crystal_size_max          0.167
_exptl_crystal_size_mid          0.162
_exptl_crystal_size_min          0.102
_refine_diff_density_max         1.566
_refine_diff_density_min         -1.772
_refine_diff_density_rms         0.086
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1169
_refine_ls_number_reflns         17815
_refine_ls_number_restraints     572
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0626
_refine_ls_R_factor_gt           0.0591
_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^)+(0.1089P)^2^+42.3627P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1744
_refine_ls_wR_factor_ref         0.1776
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16201
_reflns_number_total             17815
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt02933d2.cif
_cod_data_source_block           rlacy18_abs
_cod_depositor_comments
'Adding full bibliography for 7047253--7047256.cif.'
_cod_database_code               7047254
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C97H58F3Mn2O17P4S
_chemical_oxdiff_usercomment     'Crystallized from THF'
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O5-H5
 0.84 with sigma of 0.02
 C1_1-C2_1 \\sim C2_1-C3_1 \\sim C3_1-C4_1
 C1_2-C2_2 \\sim C2_2-C3_2 \\sim C3_2-C4_2
 C1_3-C2_3 \\sim C2_3-C3_3 \\sim C3_3-C4_3
 C1_4-C2_4 \\sim C2_4-C3_4 \\sim C3_4-C4_4
 C1_5-C2_5 \\sim C2_5-C3_5 \\sim C3_5-C4_5
 C1_6-C2_6 \\sim C2_6-C3_6 \\sim C3_6-C4_6
 C1_7-C2_7 \\sim C2_7-C3_7 \\sim C3_7-C4_7
 C1_8-C2_8 \\sim C2_8-C3_8 \\sim C3_8-C4_8
 with sigma of 0.02
 O1_1-C1_1 \\sim O1_1-C4_1
 O1_2-C1_2 \\sim O1_2-C4_2
 O1_3-C1_3 \\sim O1_3-C4_3
 O1_4-C1_4 \\sim O1_4-C4_4
 O1_5-C1_5 \\sim O1_5-C4_5
 O1_6-C1_6 \\sim O1_6-C4_6
 O1_7-C1_7 \\sim O1_7-C4_7
 O1_8-C1_8 \\sim O1_8-C4_8
 with sigma of 0.02
 O1_1-C2_1 \\sim O1_1-C3_1
 O1_2-C2_2 \\sim O1_2-C3_2
 O1_3-C2_3 \\sim O1_3-C3_3
 O1_4-C2_4 \\sim O1_4-C3_4
 O1_5-C2_5 \\sim O1_5-C3_5
 O1_6-C2_6 \\sim O1_6-C3_6
 O1_7-C2_7 \\sim O1_7-C3_7
 O1_8-C2_8 \\sim O1_8-C3_8
 with sigma of 0.04
 C2_1-C4_1 \\sim C1_1-C3_1
 C2_2-C4_2 \\sim C1_2-C3_2
 C2_3-C4_3 \\sim C1_3-C3_3
 C2_4-C4_4 \\sim C1_4-C3_4
 C2_5-C4_5 \\sim C1_5-C3_5
 C2_6-C4_6 \\sim C1_6-C3_6
 C2_7-C4_7 \\sim C1_7-C3_7
 C2_8-C4_8 \\sim C1_8-C3_8
 with sigma of 0.04
 C4_3-C3_3 \\sim C4_3-C3A_3 \\sim C3_3-C2_3 \\sim C3A_3-C2_3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1_1 \\sim C1_1 \\sim C2_1 \\sim C3_1 \\sim C4_1 \\sim O1_2 \\sim C1_2 \\sim
C2_2 \\sim C3_2 \\sim C4_2 \\sim O1_3 \\sim C1_3 \\sim C2_3 \\sim C3_3 \\sim
C4_3 \\sim O1_4 \\sim C1_4 \\sim C2_4 \\sim C3_4 \\sim C4_4 \\sim O1_5 \\sim
C1_5 \\sim C2_5 \\sim C3_5 \\sim C4_5 \\sim O1_6 \\sim C1_6 \\sim C2_6 \\sim
C3_6 \\sim C4_6 \\sim O1_7 \\sim C1_7 \\sim C2_7 \\sim C3_7 \\sim C4_7 \\sim
O1_8 \\sim C1_8 \\sim C2_8 \\sim C3_8 \\sim C4_8: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
Uanis(O1_1) = Uanis(O1_8)
Uanis(C1_1) = Uanis(C1_8) = Uanis(C4_8) = Uanis(C1_6) = Uanis(C4_6)
Uanis(C2_1) = Uanis(C2_8) = Uanis(C3_8) = Uanis(C2_6) = Uanis(C3_6)
4. Rigid body (RIGU) restrains
 O1_1, C1_1, C2_1, C3_1, C4_1
 O1_2, C1_2, C2_2, C3_2, C4_2
 O1_3, C1_3, C2_3, C3_3, C4_3
 O1_4, C1_4, C2_4, C3_4, C4_4
 O1_5, C1_5, C2_5, C3_5, C4_5
 O1_6, C1_6, C2_6, C3_6, C4_6
 O1_7, C1_7, C2_7, C3_7, C4_7
 O1_8, C1_8, C2_8, C3_8, C4_8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O1_6, C1_6, C2_6, C3_6, C4_6} sigma for 1-2: 0.02, 1-3: 0.02
as
{O1_5, C1_5, C2_5, C3_5, C4_5}
{O1_2, C1_2, C2_2, C3_2, C4_2} sigma for 1-2: 0.02, 1-3: 0.02
as
{O1_8, C1_8, C2_8, C3_8, C4_8}
6. Others
 Sof(H2BC)=Sof(H2BD)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H4BC)=Sof(H4BD)=1-FVAR(1)
 Sof(H2AA)=Sof(H2AB)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H4AA)=Sof(H4AB)=FVAR(1)
 Sof(O1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=1-FVAR(2)
 Sof(O1)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=FVAR(2)
 Fixed Sof: O1(0.5) C1(0.5) H1A(0.5) H1B(0.5) C2(0.5) H2A(0.5) H2B(0.5)
 C3(0.5) H3A(0.5) H3B(0.5) C4(0.5) H4A(0.5) H4B(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C24(H24A,H24B), C49(H49A,H49B), C57(H57A,H57B), C1(H1A,H1B),
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B),
 C4(H4A,H4B), C1(H1A,H1B), C2(H2BC,H2BD), C2(H2AA,H2AB), C3(H3A,H3B), C3A(H3AA,
 H3AB), C4(H4BC,H4BD), C4(H4AA,H4AB), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B),
 C4(H4A,H4B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C1(H1A,H1B),
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B),
 C4(H4A,H4B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B)
7.b Aromatic/amide H refined with riding coordinates:
 C5(H5A), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C18(H18), C20(H20), C26(H26), C27(H27), C28(H28), C29(H29),
  C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38),
 C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
  C48(H48), C51(H51), C53(H53), C59(H59), C60(H60), C61(H61), C62(H62),
 C63(H63), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69)
7.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C56(H56A,H56B,H56C)
;
_shelx_res_checksum              76509
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.207
_oxdiff_exptl_absorpt_empirical_full_min 0.786