Synthesis of tetra-pincer nickel(ii) and palladium(ii) complexes of resorcin[4]arene-octophosphinite [Res(OPR<sub>2</sub>)<sub>8</sub>] and rhodium-catalyzed regioselective hydroformylation reaction.
Ananthnag, Guddekoppa S.; Mondal, Dipanjan; Mague, Joel T.; Balakrishna, Maravanji S.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 14632–14641; doi:10.1039/c9dt02499a

data_7700830
_publ_section_title
;
 Synthesis of tetra-pincer nickel(ii) and palladium(ii) complexes of
 resorcin[4]arene-octophosphinite [Res(OPR<sub>2</sub>)<sub>8</sub>] and
 rhodium-catalyzed regioselective hydroformylation reaction.
;
_journal_issue                   39
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              14632
_journal_page_last               14641
_journal_paper_doi               10.1039/c9dt02499a
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C140 H122 Br4 Ni4 O8 P8, 2(C H2 Cl2)'
_chemical_formula_sum            'C142 H126 Br4 Cl4 Ni4 O8 P8'
_chemical_formula_weight         2904.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-25 deposited with the CCDC.    2019-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.0480(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.0679(15)
_cell_length_b                   21.8228(12)
_cell_length_c                   25.4931(14)
_cell_measurement_reflns_used    9629
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.2730
_cell_measurement_theta_min      2.3705
_cell_volume                     14259.7(13)
_computing_cell_refinement       '<i>SAINT</i> (Bruker, 2016)'
_computing_data_collection       '<i>APEX3</i> (Bruker, 2016)'
_computing_data_reduction        '<i>SAINT</i> (Bruker, 2016)'
_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    '<i>SHELXT</i> (Sheldrick, 2015<i>a</i>)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 8.3660
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Smart APEX CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0512
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            90638
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.385
_diffrn_reflns_theta_min         1.852
_exptl_absorpt_coefficient_mu    1.858
_exptl_absorpt_correction_T_max  0.78
_exptl_absorpt_correction_T_min  0.52
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   '<i>SADABS</i> (Bruker, 2016)'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.353
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       column
_exptl_crystal_F_000             5928
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_refine_diff_density_max         3.316
_refine_diff_density_min         -1.054
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     850
_refine_ls_number_reflns         14592
_refine_ls_number_restraints     599
_refine_ls_restrained_S_all      1.131
_refine_ls_R_factor_all          0.0992
_refine_ls_R_factor_gt           0.0800
_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^)+(0.1598P)^2^+42.2649P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2393
_refine_ls_wR_factor_ref         0.2558
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10776
_reflns_number_total             14592
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt02499a2.cif
_cod_data_source_block           msb622_0m
_cod_depositor_comments
'Adding full bibliography for 7700830--7700831.cif.'
_cod_database_code               7700830
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.781
_shelx_estimated_absorpt_t_min   0.606
_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
 Ni2-Br2 \\sim Ni2-Br2A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C33-C34 \\sim C33-C34A
 with sigma of 0.02
 P1-C7 \\sim P1-C7A
 with sigma of 0.02
 P3-C47 \\sim P3-C47A
 with sigma of 0.02
 P4-C0AA \\sim P4-C0AB
 with sigma of 0.02
 C1AA-C0AA \\sim C1AB-C0AB
 with sigma of 0.02
 C1AA-C2AA \\sim C1AB-C2AB
 with sigma of 0.02
 C0AA-C5AA \\sim C0AB-C5AB
 with sigma of 0.02
 C2AA-C3AA \\sim C2AB-C3AB
 with sigma of 0.02
 C3AA-C4AA \\sim C3AB-C4AB
 with sigma of 0.02
 C5AA-C4AA \\sim C5AB-C4AB
 with sigma of 0.02
 P4-C1AA \\sim P4-C1AB
 with sigma of 0.04
 P4-C5AA \\sim P4-C5AB
 with sigma of 0.04
 C1AA-C3AA \\sim C1AB-C3AB
 with sigma of 0.04
 C1AA-C5AA \\sim C1AB-C5AB
 with sigma of 0.04
 C0AA-C2AA \\sim C0AB-C2AB
 with sigma of 0.04
 C0AA-C4AA \\sim C0AB-C4AB
 with sigma of 0.04
 C2AA-C4AA \\sim C2AB-C4AB
 with sigma of 0.04
 C3AA-C5AA \\sim C3AB-C5AB
 with sigma of 0.04
 Cl1-C6AA \\sim Cl1A-C6AB
 with sigma of 0.02
 Cl2-C6AA \\sim Cl2A-C6AB
 with sigma of 0.02
 Cl1-Cl2 \\sim Cl1A-Cl2A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl2A) \\sim Ueq, Uanis(Cl1A)
\\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C9A)
\\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C12A) \\sim Ueq,
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C34A) \\sim Ueq, Uanis(C35A)
\\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq,
Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq,
Uanis(C47A) \\sim Ueq, Uanis(C48A) \\sim Ueq, Uanis(C49A) \\sim Ueq,
Uanis(C50A) \\sim Ueq, Uanis(C51A) \\sim Ueq, Uanis(C52A) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq,
Uanis(C57) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C69) \\sim Ueq,
Uanis(C70) \\sim Ueq, Uanis(C1AA) \\sim Ueq, Uanis(C0AA) \\sim Ueq, Uanis(C2AA)
\\sim Ueq, Uanis(C3AA) \\sim Ueq, Uanis(C5AA) \\sim Ueq, Uanis(C4AA) \\sim Ueq,
Uanis(C0AB) \\sim Ueq, Uanis(C1AB) \\sim Ueq, Uanis(C2AB) \\sim Ueq,
Uanis(C3AB) \\sim Ueq, Uanis(C4AB) \\sim Ueq, Uanis(C5AB) \\sim Ueq,
Uanis(C6AA) \\sim Ueq, Uanis(C6AB) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C7) = Uanis(C7A)
Uanis(C8) = Uanis(C8A)
Uanis(C9) = Uanis(C9A)
Uanis(C10) = Uanis(C10A)
Uanis(C11) = Uanis(C11A)
Uanis(C12) = Uanis(C12A)
Uanis(C35) = Uanis(C35A)
Uanis(C34) = Uanis(C34A)
Uanis(C47) = Uanis(C47A)
Uanis(C48) = Uanis(C48A)
Uanis(C49) = Uanis(C49A)
Uanis(C50) = Uanis(C50A)
Uanis(C51) = Uanis(C51A)
Uanis(C52) = Uanis(C52A)
Uanis(Br2) = Uanis(Br2A)
4. Others
 Sof(Br2A)=1-FVAR(1)
 Sof(Br2)=FVAR(1)
 Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=
 Sof(H11A)=Sof(C12A)=Sof(H12A)=1-FVAR(2)
 Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=
 Sof(C12)=Sof(H12)=FVAR(2)
 Sof(H33C)=Sof(H33D)=Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=1-FVAR(3)
 Sof(H33A)=Sof(H33B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(3)
 Fixed Sof: C34(0.5) H34A(0.5) H34B(0.5) C34A(0.5) C47(0.6) C48(0.6) H48(0.6)
 C49(0.6) H49(0.6) C50(0.6) H50(0.6) C51(0.6) H51(0.6) C52(0.6) H52(0.6)
 C47A(0.4) C48A(0.4) H48A(0.4) C49A(0.4) H49A(0.4) C50A(0.4) H50A(0.4)
 C51A(0.4) H51A(0.4) C52A(0.4) H52A(0.4) C1AA(0.65) H1AA(0.65) C0AA(0.65)
 C2AA(0.65) H2AA(0.65) C3AA(0.65) H3AA(0.65) C5AA(0.65) H5AA(0.65) C4AA(0.65)
 H4AA(0.65) C0AB(0.35) C1AB(0.35) H1AB(0.35) C2AB(0.35) H2AB(0.35) C3AB(0.35)
 H3AB(0.35) C4AB(0.35) H4AB(0.35) C5AB(0.35) H5AB(0.35) Cl1(0.6) Cl2(0.6)
 C6AA(0.6) H6AA(0.6) H6AB(0.6) Cl2A(0.4) C6AB(0.4) H6AC(0.4) H6AD(0.4) Cl1A(0.4)
5.a Ternary CH refined with riding coordinates:
 C31(H31), C42(H42)
5.b Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C33(H33A,H33B), C33(H33C,H33D), C34(H34A,H34B), C43(H43A,
 H43B), C44(H44A,H44B), C45(H45A,H45B), C6AA(H6AA,H6AB), C6AB(H6AC,H6AD)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A), C12A(H12A), C15(H15),
 C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28),
  C29(H29), C30(H30), C41(H41), C48(H48), C49(H49), C50(H50), C51(H51),
 C52(H52), C48A(H48A), C49A(H49A), C50A(H50A), C51A(H51A), C52A(H52A), C54(H54),
  C55(H55), C56(H56), C57(H57), C58(H58), C66(H66), C67(H67), C68(H68),
 C69(H69), C70(H70), C1AA(H1AA), C2AA(H2AA), C3AA(H3AA), C5AA(H5AA), C4AA(H4AA),
  C1AB(H1AB), C2AB(H2AB), C3AB(H3AB), C4AB(H4AB), C5AB(H5AB)
5.d Fitted hexagon refined as free rotating group:
 C7(C8,C9,C10,C11,C12), C7A(C8A,C9A,C10A,C11A,C12A), C47(C48,C49,C50,C51,C52),
 C47A(C48A,C49A,C50A,C51A,C52A)
5.e Idealised Me refined as rotating group:
 C35(H35A,H35B,H35C), C35A(H35D,H35E,H35F), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              91206
_shelx_fab_checksum              78065
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'