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_4132928
_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
'C83.92 H80.49 O3 Zr, 0.5(C12 H20), 0.5(C5 H12)'
_chemical_formula_sum            'C92.42 H96.49 O3 Zr'
_chemical_formula_weight         1346.44
_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             2018-07-11
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                78.961(7)
_cell_angle_beta                 80.374(5)
_cell_angle_gamma                63.052(12)
_cell_formula_units_Z            2
_cell_length_a                   12.350(2)
_cell_length_b                   12.845(2)
_cell_length_c                   27.404(4)
_cell_measurement_reflns_used    9224
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.367
_cell_measurement_theta_min      2.290
_cell_volume                     3787.4(11)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'Bruker Apex III'
_computing_data_reduction        'SAINT V8.38A (?, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'CPAD Area Detector'
_diffrn_detector_area_resol_mean 7.69
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.933
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            232796
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         34.959
_diffrn_reflns_theta_min         2.290
_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    0.195
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9405
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0897 before and 0.0510 after correction. The Ratio of minimum to maximum transmission is 0.9405. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_description       plate
_exptl_crystal_F_000             1430
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.09
_exptl_transmission_factor_max   0.7461
_exptl_transmission_factor_min   0.6809
_refine_diff_density_max         2.414
_refine_diff_density_min         -2.123
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1042
_refine_ls_number_reflns         31035
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      1.148
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0661
_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^)+(0.0751P)^2^+4.0074P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1712
_refine_ls_wR_factor_ref         0.1768
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27728
_reflns_number_total             31035
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07418_si_001.cif
_cod_data_source_block           3a
_cod_original_cell_volume        3787.6(11)
_cod_database_code               4132928
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.953
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2CA-C01Q \\sim C8DA-C2CA \\sim C8DA-C6AA \\sim C9DA-C6AA
 with sigma of 0.02
 C51A-C52A \\sim C51B-C52B \\sim C52B-C53B \\sim C52A-C53A \\sim C53A-C51A
\\sim C53B-C51B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1S \\sim C2S \\sim C3S \\sim C4S \\sim C5S \\sim C6S \\sim C7S: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08
Uiso(C5S) = Uiso(C3S)
4. Rigid body (RIGU) restrains
 C1S, C2S, C3S, C4S, C5S, C6S, C7S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C81A)=Sof(H81A)=Sof(C82A)=Sof(H82A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=
 Sof(H84A)=Sof(C85A)=Sof(H85A)=Sof(C69B)=Sof(H69B)=Sof(C70B)=Sof(H70B)=
 Sof(C71B)=Sof(H71B)=Sof(C72B)=Sof(H72B)=Sof(C73B)=Sof(H73B)=Sof(C75A)=
 Sof(H75A)=Sof(C76A)=Sof(H76A)=Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78A)=
 Sof(C79A)=Sof(H79C)=1-FVAR(1)
 Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70A)=Sof(C71A)=Sof(H71A)=Sof(C72A)=
 Sof(H72A)=Sof(C73A)=Sof(H73A)=Sof(C75B)=Sof(H75B)=Sof(C76B)=Sof(H76B)=
 Sof(C77B)=Sof(H77B)=Sof(C78B)=Sof(H78B)=Sof(C79B)=Sof(H79A)=Sof(H79B)=
 Sof(C81B)=Sof(H81B)=Sof(C82B)=Sof(H82B)=Sof(C83B)=Sof(H83B)=Sof(C84B)=
 Sof(H84B)=Sof(C85B)=Sof(H85B)=FVAR(1)
 Sof(C51B)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C52B)=Sof(H52D)=Sof(H52E)=
 Sof(H52F)=Sof(C53B)=Sof(H53D)=Sof(H53E)=Sof(H53F)=1-FVAR(2)
 Sof(C50)=Sof(C51A)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52A)=Sof(H52A)=
 Sof(H52B)=Sof(H52C)=Sof(C53A)=Sof(H53A)=Sof(H53B)=Sof(H53C)=FVAR(2)
 Sof(C32B)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33B)=Sof(H33D)=Sof(H33E)=
 Sof(H33F)=Sof(C34B)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(3)
 Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C33A)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(3)
 Fixed Sof: C0BA(0.5) H(0.5) HA(0.5) C5S(0.5) HB(0.5) C6S(0.5) HC(0.5)
 C1S(0.5) C2S(0.5) HD(0.5) C3S(0.5) HE(0.5) C4S(0.5) HF(0.5) C6BA(0.5) HG(0.5)
 HH(0.5) C7AA(0.5) HI(0.5) HJ(0.5) HK(0.5) C7S(0.5) HL(0.5) HM(0.5) HO(0.5)
 C9AA(0.5) HP(0.5) HN(0.5) HQ(0.5) C9BA(0.5) HR(0.5) HS(0.5) C01Q(0.5) HT(0.5)
 HU(0.5) HV(0.5) C2CA(0.5) HW(0.5) HX(0.5) C6AA(0.5) HY(0.5) HZ(0.5) C8DA(0.5)
 H0AA(0.5) H1AA(0.5) C9DA(0.5) H2AA(0.5) H3AA(0.5) H4AA(0.5)
 Fixed Uiso: C5S(0.05) C6S(0.05) C1S(0.05) C2S(0.05) C3S(0.05) C4S(0.05)
 C7S(0.05)
6.a Secondary CH2 refined with riding coordinates:
 C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C79B(H79A,
 H79B), C0BA(H,HA), C6BA(HG,HH), C9BA(HR,HS), C2CA(HW,HX), C6AA(HY,HZ),
 C8DA(H0AA,H1AA)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13),
 C19(H19), C21(H21), C24(H24), C26(H26), C38(H38), C40(H40), C43(H43), C45(H45),
  C63(H63), C64(H64), C65(H65), C66(H66), C67(H67), C69A(H69A), C70A(H70A),
 C71A(H71A), C72A(H72A), C73A(H73A), C75B(H75B), C76B(H76B), C77B(H77B),
 C78B(H78B), C81A(H81A), C82A(H82A), C83A(H83A), C84A(H84A), C85A(H85A),
 C69B(H69B), C70B(H70B), C71B(H71B), C72B(H72B), C73B(H73B), C75A(H75A),
 C76A(H76A), C77A(H77A), C78A(H78A), C79A(H79C), C81B(H81B), C82B(H82B),
 C83B(H83B), C84B(H84B), C85B(H85B), C5S(HB), C6S(HC), C2S(HD), C3S(HE), C4S(HF)
6.c Fitted hexagon refined as free rotating group:
 C5S(C6S,C1S,C2S,C3S,C4S)
6.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C47(H47A,H47B,
 H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C32A(H32A,H32B,H32C),
 C33A(H33A,H33B,H33C), C34A(H34A,H34B,H34C), C51A(H51A,H51B,H51C), C52A(H52A,
 H52B,H52C), C53A(H53A,H53B,H53C), C32B(H32D,H32E,H32F), C33B(H33D,H33E,H33F),
 C34B(H34D,H34E,H34F), C51B(H51D,H51E,H51F), C52B(H52D,H52E,H52F), C53B(H53D,
 H53E,H53F), C7AA(HI,HJ,HK), C7S(HL,HM,HO), C9AA(HP,HN,HQ), C01Q(HT,HU,HV),
 C9DA(H2AA,H3AA,H4AA)
;
_shelx_res_checksum              86819
_shelx_hkl_checksum              90567
_olex2_submission_special_instructions 'No special instructions were received'