Bimetallic Zirconium Amine Bis(phenolate) Polymerization Catalysts: Enhanced Activity and Tacticity Control for Polyolefin Synthesis.
Radlauer, Madalyn R.; Agapie, Theodor; Organometallics 33 (2014) 3247–3250; doi:10.1021/om500608j

data_4089670
_publ_section_title
;
 Bimetallic Zirconium Amine Bis(phenolate) Polymerization Catalysts:
 Enhanced Activity and Tacticity Control for Polyolefin Synthesis.
;
_journal_issue                   13
_journal_name_full               Organometallics
_journal_page_first              3247
_journal_page_last               3250
_journal_paper_doi               10.1021/om500608j
_journal_volume                  33
_journal_year                    2014
_chemical_formula_moiety         'C82 H94 Cl4 N4 O4 Zr2, 4(C7 H8), C5 H12'
_chemical_formula_sum            'C115 H138 Cl4 N4 O4 Zr2'
_chemical_formula_weight         1964.53
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2013-12-19
_audit_creation_method
;
Olex2 1.2
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601),
 SHELXL-2013,
 and manual edit
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.1035(15)
_cell_length_b                   25.847(3)
_cell_length_c                   26.584(3)
_cell_measurement_reflns_used    9822
_cell_measurement_temperature    100
_cell_measurement_theta_max      26.20
_cell_measurement_theta_min      2.19
_cell_volume                     10378(2)
_computing_cell_refinement       'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_data_collection       'APEX2 2013.10-0 (Bruker-AXS, 2007)'
_computing_data_reduction        'SAINT V8.34A (Bruker-AXS, 2007)'
_computing_molecular_graphics    'DIAMOND 3 (Crystal Impact, 1999)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2013/2 (Sheldrick, 2013)'
_computing_structure_solution    'XT (Sheldrick, 2012)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 8.33
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1543
_diffrn_reflns_av_unetI/netI     0.0925
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       42
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            302799
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         35.695
_diffrn_reflns_theta_min         1.532
_diffrn_source_current           30
_diffrn_source_power             1.5
_diffrn_source_target            Mo
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    0.357
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8763
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0657 before and 0.0604 after correction.
The Ratio of minimum to maximum transmission is 0.8763.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       plate
_exptl_crystal_F_000             4144
_exptl_crystal_size_max          0.43
_exptl_crystal_size_mid          0.37
_exptl_crystal_size_min          0.31
_refine_diff_density_max         2.443
_refine_diff_density_min         -0.946
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     752
_refine_ls_number_reflns         23481
_refine_ls_number_restraints     325
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.1762
_refine_ls_R_factor_gt           0.0839
_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^)+(0.0621P)^2^+24.7850P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1805
_refine_ls_wR_factor_ref         0.2182
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12405
_reflns_number_total             23481
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om500608j_si_002.cif
_cod_data_source_block           mrr36
_cod_original_cell_volume        10377.7(18)
_cod_database_code               4089670
_shelx_estimated_absorpt_t_max   0.897
_shelx_estimated_absorpt_t_min   0.862
_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
 C1U-C2U \\sim C2U-C3U \\sim C3U-C4U \\sim C4U-C5U \\sim C1V-C2V \\sim C2V-C3V
\\sim C3V-C4V \\sim C4V-C5V
 with sigma of 0.02
3. Restrained planarity
 C7T, C1T, C2T, C3T, C4T, C5T, C6T
 with sigma of 0.02
4. Rigid bond restraints
 C7S, C1S, C2S, C3S, C4S, C5S, C6S, C7T, C1T, C2T, C3T, C4T, C5T, C6T, C1U,
 C2U, C3U, C4U, C5U, C1V, C2V, C3V, C4V, C5V
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C7S \\sim C1S \\sim C2S \\sim C3S \\sim C4S \\sim C5S \\sim C6S \\sim C7T \\sim
C1T \\sim C2T \\sim C3T \\sim C4T \\sim C5T \\sim C6T \\sim C1U \\sim C2U \\sim
C3U \\sim C4U \\sim C5U \\sim C1V \\sim C2V \\sim C3V \\sim C4V \\sim C5V:
within 1.7A with sigma of 0.02 and sigma for terminal atoms of 0.04
6. Same fragment restrains
{C7S, C1S, C6S, C5S, C4S, C3S, C2S}
{C7T, C1T, C2T, C3T, C4T, C5T, C6T}
as
{C7S, C1S, C2S, C3S, C4S, C5S, C6S}
7. Others
 Sof(H19C)=Sof(H19D)=Sof(C26B)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C20B)=
 Sof(H20C)=Sof(H20D)=Sof(C27B)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(1)
 Sof(H19A)=Sof(H19B)=Sof(C20C)=Sof(H20A)=Sof(H20B)=Sof(C26C)=Sof(H26A)=
 Sof(H26B)=Sof(H26C)=Sof(C27C)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(1)
 Sof(C1V)=Sof(H1V1)=Sof(H1V2)=Sof(H1V3)=Sof(C2V)=Sof(H2V1)=Sof(H2V2)=Sof(C3V)=
 Sof(H3V1)=Sof(H3V2)=Sof(C4V)=Sof(H4V1)=Sof(H4V2)=Sof(C5V)=Sof(H5V1)=Sof(H5V2)=
 Sof(H5V3)=0.5*(1-FVAR(3))
 Sof(C1U)=Sof(H1U1)=Sof(H1U2)=Sof(H1U3)=Sof(C2U)=Sof(H2U1)=Sof(H2U2)=Sof(C3U)=
 Sof(H3U1)=Sof(H3U2)=Sof(C4U)=Sof(H4U1)=Sof(H4U2)=Sof(C5U)=Sof(H5U1)=Sof(H5U2)=
 Sof(H5U3)=0.5*FVAR(3)
 Fixed Sof: C7S(0.5) H7SA(0.5) H7SB(0.5) H7SC(0.5) C1S(0.5) C2S(0.5) H2S(0.5)
 C3S(0.5) H3S(0.5) C4S(0.5) H4S(0.5) C5S(0.5) H5S(0.5) C6S(0.5) H6S(0.5)
 C7T(0.5) H7T1(0.5) H7T2(0.5) H7T3(0.5) C1T(0.5) C2T(0.5) H2T(0.5) C3T(0.5)
 H3T(0.5) C4T(0.5) H4T(0.5) C5T(0.5) H5T(0.5) C6T(0.5) H6T(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B), C19(H19A,H19B), C19(H19C,H19D), C28(H28A,H28B),
 C35(H35A,H35B), C20C(H20A,H20B), C20B(H20C,H20D), C2U(H2U1,H2U2), C3U(H3U1,
 H3U2), C4U(H4U1,H4U2), C2V(H2V1,H2V2), C3V(H3V1,H3V2), C4V(H4V1,H4V2)
8.b Me refined with riding coordinates:
 C1U(H1U1,H1U2,H1U3), C5U(H5U1,H5U2,H5U3), C1V(H1V1,H1V2,H1V3), C5V(H5V1,H5V2,
 H5V3)
8.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C10(H10), C12(H12), C30(H30), C31(H31), C32(H32), C33(H33),
 C34(H34), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C44(H44),
  C45(H45), C46(H46), C47(H47), C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S),
 C6S(H6S), C2T(H2T), C3T(H3T), C4T(H4T), C5T(H5T), C6T(H6T)
8.d Idealised Me refined with riding coordinates:
 C7T(H7T1,H7T2,H7T3)
8.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C48(H48A,H48B,H48C), C26C(H26A,H26B,H26C),
 C27C(H27A,H27B,H27C), C26B(H26D,H26E,H26F), C27B(H27D,H27E,H27F), C7S(H7SA,
 H7SB,H7SC)
;