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_4126275
_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         'C76 H110 Ca2 N5 O5, C3 H7'
_chemical_formula_sum            'C82 H129 Ca2 N5 O5'
_chemical_formula_weight         1345.05
_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             2016-10-14
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                100.966(2)
_cell_angle_beta                 91.498(2)
_cell_angle_gamma                110.918(2)
_cell_formula_units_Z            2
_cell_length_a                   12.3369(3)
_cell_length_b                   14.1438(3)
_cell_length_c                   24.9534(6)
_cell_measurement_reflns_used    10764
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.3430
_cell_measurement_theta_min      3.4240
_cell_volume                     3971.84(17)
_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 1.000
_diffrn_measured_fraction_theta_max 0.978
_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           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0457
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            31950
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.519
_diffrn_reflns_theta_min         3.424
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.634
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83313
_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    1.125
_exptl_crystal_description       plate
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.161
_exptl_crystal_size_mid          0.078
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.502
_refine_diff_density_min         -0.457
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     852
_refine_ls_number_reflns         15669
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0637
_refine_ls_R_factor_gt           0.0460
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0594P)^2^+0.9988P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1146
_refine_ls_wR_factor_ref         0.1258
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12174
_reflns_number_total             15669
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b04926_si_002.cif
_cod_data_source_block           s16msh84_sq-cpd-25
_cod_database_code               4126275
_shelxl_version_number           2014-3
_chemical_oxdiff_usercomment     'Colourless Plates'
_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
 C70-C69 \\sim C70A-C69 \\sim C71-C70 \\sim C71-C70A
 with sigma of 0.005
 C74-C73 \\sim C75-C74
 with sigma of 0.005
3. Others
 Fixed Sof: H69A(0.75) H69B(0.75) H69C(0.25) H69D(0.25) C70(0.75) H70A(0.75)
 H70B(0.75) H71A(0.75) H71B(0.75) H71C(0.25) H71D(0.25) H73A(0.75) H73B(0.75)
 H75A(0.75) H75B(0.75) C70A(0.25) H70C(0.25) H70D(0.25)
4.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)
4.b Secondary CH2 refined with riding coordinates:
 C69(H69A,H69B), C69(H69C,H69D), C70(H70A,H70B), C71(H71A,H71B), C71(H71C,
 H71D), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B),
 C76(H76A,H76B), C70A(H70C,H70D), C79(H79A,H79B), C78(H78A,H78B)
4.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)
4.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), C77(H77A,
 H77B,H77C)
;
_shelx_fab_checksum              56603