Alkaline Earth-centered CO Homologation, Reduction and Amine Carbonylation.
Anker, Mathew D.; Kefalidis, Christos E.; Yang, Yan; Fang, Jian; Hill, Michael S.; Mahon, Mary F.; Maron, Laurent; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b04926

data_4126277
_publ_section_title
;
 Alkaline Earth-centered CO Homologation, Reduction and Amine
 Carbonylation.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b04926
_journal_year                    2017
_chemical_formula_moiety         'C74 H108 B Ca2 N5 O5, 1.8(C6 H14)'
_chemical_formula_sum            'C84.8 H133.2 B Ca2 N5 O5'
_chemical_formula_weight         1393.73
_chemical_name_systematic
;
 ?
;
_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     iterative
_audit_creation_date             2016-11-04
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                85.931(3)
_cell_angle_beta                 76.247(3)
_cell_angle_gamma                72.926(4)
_cell_formula_units_Z            2
_cell_length_a                   15.3517(7)
_cell_length_b                   15.5044(6)
_cell_length_c                   19.1840(6)
_cell_measurement_reflns_used    9650
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      72.8350
_cell_measurement_theta_min      2.9730
_cell_volume                     4239.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0687
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            33340
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.484
_diffrn_reflns_theta_min         2.982
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.544
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58180
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.092
_exptl_crystal_description       plate
_exptl_crystal_F_000             1524
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.126
_exptl_crystal_size_min          0.051
_refine_diff_density_max         1.029
_refine_diff_density_min         -0.591
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1028
_refine_ls_number_reflns         16638
_refine_ls_number_restraints     130
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0932
_refine_ls_R_factor_gt           0.0675
_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^)+(0.1033P)^2^+1.2472P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1795
_refine_ls_wR_factor_ref         0.1999
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12075
_reflns_number_total             16638
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b04926_si_002.cif
_cod_data_source_block           s16msh90-cpd-27
_cod_original_formula_sum        'C84.80 H133.20 B Ca2 N5 O5'
_cod_database_code               4126277
_shelxl_version_number           2014-3
_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
 Ca2-O4A \\sim Ca2-O4
 with sigma of 0.005
 Ca2-B1A \\sim Ca2-B1
 with sigma of 0.005
 O4A-B1A \\sim O4-B1 \\sim O5A-B1A \\sim O5-B1
 with sigma of 0.005
 O4-C70 \\sim O4A-C70A \\sim O5A-C69A \\sim O5-C69
 with sigma of 0.005
 C70-C69 \\sim C70A-C69A
 with sigma of 0.005
 C71-C69 \\sim C72A-C69A \\sim C71A-C69A \\sim C72-C69 \\sim C74-C70 \\sim
C74A-C70A \\sim C73-C70 
 C73A-C70A
 with sigma of 0.005
 C82-C81 \\sim C83-C82 \\sim C84-C83 \\sim C85-C84 \\sim C85-C86 \\sim
C85A-C86A \\sim C86A-C84
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C85A \\sim C86A \\sim C86:
within 2A with sigma of 0.005 and sigma for terminal atoms of 0.005
4. Others
 Fixed Sof: O4(0.65) O5(0.65) O4A(0.35) O5A(0.35) C69(0.65) C70(0.65)
 C71(0.65) H71A(0.65) H71B(0.65) H71C(0.65) C72(0.65) H72A(0.65) H72B(0.65)
 H72C(0.65) C73(0.65) H73A(0.65) H73B(0.65) H73C(0.65) C74(0.65) H74A(0.65)
 H74B(0.65) H74C(0.65) C69A(0.35) C70A(0.35) C72A(0.35) H72D(0.35) H72E(0.35)
 H72F(0.35) C73A(0.35) H73D(0.35) H73E(0.35) H73F(0.35) C74A(0.35) H74D(0.35)
 H74E(0.35) H74F(0.35) C71A(0.35) H71D(0.35) H71E(0.35) H71F(0.35) B1(0.65)
 H1(0.65) B1A(0.35) H1AA(0.35) C81(0.8) H81A(0.8) H81B(0.8) H81C(0.8) C82(0.8)
 H82A(0.8) H82B(0.8) C83(0.8) H83A(0.8) H83B(0.8) C84(0.8) H84A(0.4) H84B(0.4)
 H84C(0.4) H84D(0.4) C86(0.4) H86A(0.4) H86B(0.4) H86C(0.4) C85(0.4) H85A(0.4)
 H85B(0.4) C85A(0.4) H85C(0.4) H85D(0.4) H85E(0.4) C86A(0.4) H86D(0.4) H86E(0.4)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C37(H37), C40(H40), C50(H50),
 C53(H53), C63(H63), C66(H66), B1(H1), B1A(H1AA)
5.b Secondary CH2 refined with riding coordinates:
 C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C82(H82A,
 H82B), C83(H83A,H83B), C84(H84A,H84B), C84(H84C,H84D), C85(H85A,H85B),
 C86A(H86D,H86E)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C30(H30),
 C33(H33), C34(H34), C35(H35), C43(H43), C46(H46), C47(H47), C48(H48), C56(H56),
  C59(H59), C60(H60), C61(H61)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C64(H64A,H64B,
 H64C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C),
 C72A(H72D,H72E,H72F), C73A(H73D,H73E,H73F), C74A(H74D,H74E,H74F), C71A(H71D,
 H71E,H71F), C75(H75A,H75B,H75C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C),
 C86(H86A,H86B,H86C), C85A(H85C,H85D,H85E)
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