Oxidative Coupling with Zr(IV) Supported by a Noninnocent Anthracene-Based Ligand: Application to the Catalytic Cotrimerization of Alkynes and Nitriles to Pyrimidines.
Low, Choon Heng; Rosenberg, Jeffrey N.; Lopez, Marco A.; Agapie, Theodor; Journal of the American Chemical Society 140 (2018) 11906–11910; doi:10.1021/jacs.8b07418

data_4132927
_publ_section_title
;
 Oxidative Coupling with Zr(IV) Supported by a Noninnocent
 Anthracene-Based Ligand: Application to the Catalytic Cotrimerization of
 Alkynes and Nitriles to Pyrimidines.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11906
_journal_page_last               11910
_journal_paper_doi               10.1021/jacs.8b07418
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety
'C64 H76 O5 Zr, C4 H7.78 O, 0.56(C4 H8 O1), 0.44(C5 H12)'
_chemical_formula_sum            'C72.44 H93.74 O6.57 Zr'
_chemical_formula_weight         1160.69
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                93.281(3)
_cell_angle_beta                 103.293(4)
_cell_angle_gamma                99.373(3)
_cell_formula_units_Z            2
_cell_length_a                   12.4092(6)
_cell_length_b                   12.7750(8)
_cell_length_c                   20.5948(17)
_cell_measurement_reflns_used    9105
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      36.37
_cell_measurement_theta_min      2.26
_cell_volume                     3119.7(4)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker Apex III'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.98
_diffrn_detector                 'CMOS Area Detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'Bruker PHOTON 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'multilayer mirrors'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0517
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            216734
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         36.828
_diffrn_reflns_theta_min         2.199
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\mS HB'
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.229
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9693
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1607 before and 0.0696 after correction. The Ratio of minimum to maximum transmission is 0.9126. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.236
_exptl_crystal_description       block
_exptl_crystal_F_000             1242
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.11
_exptl_transmission_factor_max   1.0000
_exptl_transmission_factor_min   0.9693
_refine_diff_density_max         0.711
_refine_diff_density_min         -0.476
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     786
_refine_ls_number_reflns         30044
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0671
_refine_ls_R_factor_gt           0.0423
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0425P)^2^+1.2868P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0902
_refine_ls_wR_factor_ref         0.0986
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23599
_reflns_number_total             30044
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07418_si_001.cif
_cod_data_source_block           2
_cod_database_code               4132927
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H75A,H75B,H75} of C75, All C(H,H) groups, All C(H,H,H,H)
  groups
 At 1.5 times of:
  {H52A,H52B,H52C} of C52, {H51A,H51B,H51C} of C51, {H69A,H69B,H69C} of C69,
  {H33A,H33B,H33C} of C33, {H28A,H28B,H28C} of C28, {H32A,H32B,H32C} of C32,
  {H46A,H46B,H46C} of C46, {H27A,H27B,H27C} of C27, {H48A,H48B,H48C} of C48,
  {H31A,H31B,H31C} of C31, {H29A,H29B,H29C} of C29, {H47A,H47B,H47C} of C47,
  {H50A,H50B,H50C} of C50, {H73A,H73B,H73C} of C73
2. Others
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(C71)=
 Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=Sof(H73B)=
 Sof(H73C)=1-FVAR(1)
 Sof(O6)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(C67)=
 Sof(H67A)=Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=FVAR(1)
 Sof(H75)=Sof(H77C)=Sof(H77D)=Sof(C76B)=Sof(H76C)=1-FVAR(2)
 Sof(H75A)=Sof(H75B)=Sof(H77A)=Sof(H77B)=Sof(C76A)=Sof(H76A)=Sof(H76B)=FVAR(2)
3.a Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,
 H57B), C58(H58A,H58B), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B),
 C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C74(H74A,H74B), C75(H75A,H75B),
  C77(H77A,H77B), C77(H77C,H77D), C76A(H76A,H76B), C65(H65A,H65B), C66(H66A,
 H66B), C67(H67A,H67B), C68(H68A,H68B), C70(H70A,H70B), C71(H71A,H71B),
 C72(H72A,H72B)
3.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13),
 C18(H18), C20(H20), C23(H23), C25(H25), C37(H37), C39(H39), C42(H42), C44(H44),
  C75(H75), C76B(H76C)
3.c Idealised Me refined as rotating group:
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C69(H69A,H69B,H69C), C73(H73A,H73B,H73C)
;
_shelx_res_checksum              59722
_shelx_hkl_checksum              28772
_olex2_submission_special_instructions 'No special instructions were received'