Phosphanyl Methanimine (PCN) Ligands for the Selective Trimerization/Tetramerization of Ethylene with Chromium
Radcliffe, James E.; Batsanov, Andrei S.; Smith, David M.; Scott, John A.; Dyer, Philip W.; Hanton, Martin J.; ACS Catalysis 5 (2015) 7095–; doi:10.1021/acscatal.5b02106

data_4513677
_publ_section_title
;
 Phosphanyl Methanimine (PCN) Ligands for the Selective
 Trimerization/Tetramerization of Ethylene with Chromium
;
_journal_issue                   12
_journal_name_full               'ACS Catalysis'
_journal_page_first              7095
_journal_paper_doi               10.1021/acscatal.5b02106
_journal_volume                  5
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H28 Cr N O4 P'
_chemical_formula_sum            'C25 H28 Cr N O4 P'
_chemical_formula_weight         489.45
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-09-07
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.08.17 svn.r3210 for OlexSys, GUI svn.r5083)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.0194(8)
_cell_length_b                   14.8755(12)
_cell_length_c                   33.308(2)
_cell_measurement_reflns_used    5083
_cell_measurement_temperature    120
_cell_measurement_theta_max      25.20
_cell_measurement_theta_min      2.45
_cell_volume                     4964.3(6)
_computing_cell_refinement       'SAINT v7.46A (Bruker, 2008)'
_computing_data_collection       'SMART v5.625 (Bruker, 2001)'
_computing_data_reduction        'SAINT v7.46A (Bruker, 2008)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement
'SHELXL 2014/7 multi-CPU version (Sheldrick, 2008, 2015)'
_computing_structure_solution    'SHELXS 2013/1 (Sheldrick, 2008, 2015)'
_diffrn_ambient_temperature      120
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 5.6
_diffrn_detector_type            'Bruker SMART CCD 6000 area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 6000 area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  'Parallel, graphite'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0876
_diffrn_reflns_av_unetI/netI     0.0701
_diffrn_reflns_laue_measured_fraction_full 0.995
_diffrn_reflns_laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            41354
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.836
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           35.0
_diffrn_source_power             1.75
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.555
_exptl_absorpt_correction_T_max  0.7347
_exptl_absorpt_correction_T_min  0.6229
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2009/1 (Bruker,2010) was used for absorption correction.
wR2(int) was 0.0794 before and 0.0669 after correction.
The Ratio of minimum to maximum transmission is 0.8478.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.664
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 2426 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
 By classical fit to all intensities, x = 0.008(33). 
 Hooft parameter y = 0.009(14). 
;
_refine_ls_abs_structure_Flack   0.026(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     573
_refine_ls_number_reflns         8695
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0790
_refine_ls_R_factor_gt           0.0527
_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^)+(0.0560P)^2^+4.0370P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1137
_refine_ls_wR_factor_ref         0.1274
_reflns_Friedel_coverage         0.785
_reflns_friedel_fraction_full    0.995
_reflns_friedel_fraction_max     0.995
_reflns_number_gt                6725
_reflns_number_total             8695
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs5b02106_si_002.cif
_cod_data_source_block           9
_cod_depositor_comments
'Adding full bibliography for 4513677--4513678.cif.'
_cod_original_cell_volume        4964.3(7)
_cod_database_code               4513677
_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
 C24"-C26" \\sim C24'-C26'
 with sigma of 0.02
 C25'-C20' \\sim C25"-C20"
 with sigma of 0.02
 C8"-C6' \\sim C8'-C6'
 with sigma of 0.02
3. Restrained planarity
 C18', C17', C16", C15", C14", C13'
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uiso(C19") = Uiso(C19')
Uiso(C24") = Uiso(C24')
Uiso(C23") = Uiso(C23')
Uanis(C22") = Uanis(C22')
Uiso(C21") = Uiso(C21')
Uiso(C20") = Uiso(C20')
Uiso(C26") = Uiso(C26')
Uiso(C25') = Uiso(C25")
Uanis(C8') = Uanis(C8")
Uiso(C9") = Uiso(C9')
Uanis(C10") = Uanis(C10')
Uanis(C11') = Uanis(C11")
5. Others
 Uiso(H7A)=Uiso(H7B)=Uiso(H7C)=FVAR(1)
 Uiso(H10G)=Uiso(H10H)=Uiso(H10I)=FVAR(2)
 Uiso(H11G)=Uiso(H11H)=Uiso(H11I)=FVAR(3)
 Uiso(H25G)=Uiso(H25H)=Uiso(H25I)=FVAR(4)
 Uiso(H26G)=Uiso(H26H)=Uiso(H26I)=FVAR(5)
 Uiso(H8AA)=Uiso(H8AB)=Uiso(H8AC)=Uiso(H8BD)=Uiso(H8BE)=Uiso(H8BF)=FVAR(6)
 Sof(C22")=Sof(H22")=Sof(C23")=Sof(H23")=Sof(C24")=Sof(C19")=Sof(C20")=
 Sof(C21")=Sof(H21")=Sof(C25")=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26")=
 Sof(H26D)=Sof(H26E)=Sof(H26F)=1-FVAR(7)
 Sof(C22')=Sof(H22')=Sof(C23')=Sof(H23')=Sof(C24')=Sof(C19')=Sof(C20')=
 Sof(C21')=Sof(H21')=Sof(C25')=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26')=
 Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(7)
 Fixed Sof: H8AA(0.5) H8AB(0.5) H8AC(0.5) H8BD(0.5) H8BE(0.5) H8BF(0.5)
 H6'A(0.4) H6'(0.6) H17A(0.25) H17'(0.75) C8'(0.6) H8'A(0.6) H8'B(0.6)
 H8'C(0.6) C9'(0.6) H9'(0.6) C10'(0.6) H10A(0.6) H10B(0.6) H10C(0.6) C11'(0.6)
 H11A(0.6) H11B(0.6) H11C(0.6) C14"(0.25) H14"(0.25) C15"(0.25) H15"(0.25)
 C16"(0.25) H16"(0.25) C8"(0.4) H8"A(0.4) H8"B(0.4) H8"C(0.4) C9"(0.4) H9"(0.4)
 C10"(0.4) H10D(0.4) H10E(0.4) H10F(0.4) C11"(0.4) H11D(0.4) H11E(0.4)
 H11F(0.4) C14'(0.75) H14'(0.75) C15'(0.75) H15'(0.75) C16'(0.75) H16'(0.75)
6.a Riding coordinates:
 C8(H8AA,H8AB,H8AC,H8BD,H8BE,H8BF)
6.b Ternary CH refined with riding coordinates:
 C6(H6), C9(H9), C6'(H6'A), C6'(H6'), C9'(H9'), C9"(H9")
6.c Me refined with riding coordinates:
 C7'(H7'A,H7'B,H7'C), C8'(H8'A,H8'B,H8'C), C10'(H10A,H10B,H10C), C11'(H11A,
 H11B,H11C), C25'(H25A,H25B,H25C), C26'(H26A,H26B,H26C), C8"(H8"A,H8"B,H8"C),
 C10"(H10D,H10E,H10F), C11"(H11D,H11E,H11F), C25"(H25D,H25E,H25F), C26"(H26D,
 H26E,H26F)
6.d Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C21(H21), C22(H22),
 C23(H23), C17'(H17A), C17'(H17'), C18'(H18'), C14"(H14"), C15"(H15"),
 C16"(H16"), C22'(H22'), C23'(H23'), C21'(H21'), C14'(H14'), C15'(H15'),
 C16'(H16'), C22"(H22"), C23"(H23"), C21"(H21")
6.e Fitted hexagon refined as free rotating group:
 C22'(C23',C24',C19',C20',C21'), C22"(C23",C24",C19",C20",C21")
6.f Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C10(H10G,H10H,H10I), C11(H11G,H11H,H11I), C25(H25G,H25H,
 H25I), C26(H26G,H26H,H26I)
;
_shelx_shelxl_version_number     2014/7