Diels-Alder reactions of 1-phosphabutadienes: a highly selective route to P[double bond, length as m-dash]C-substituted phosphacyclohexenes.
Ohtsuki, Kazuaki; Walsgrove, Henry T. G.; Hayashi, Yoshihiro; Kawauchi, Susumu; Patrick, Brian O.; Gates, Derek P.; Ito, Shigekazu; Chemical communications (Cambridge, England) 56 (2020) 774–777; doi:10.1039/c9cc08997g

data_7125800
_publ_section_title
;
 Diels-Alder reactions of 1-phosphabutadienes: a highly selective route to
 P[double bond, length as m-dash]C-substituted phosphacyclohexenes.
;
_journal_issue                   5
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              774
_journal_page_last               777
_journal_paper_doi               10.1039/c9cc08997g
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C44 H70 Cl2 P2 Pd, 2(C H2 Cl2)'
_chemical_formula_sum            'C46 H74 Cl6 P2 Pd'
_chemical_formula_weight         1008.09
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-18
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5924)
;
_audit_update_record
;
2019-09-18 deposited with the CCDC.	2019-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.0020(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4889(5)
_cell_length_b                   22.8642(11)
_cell_length_c                   23.9461(11)
_cell_measurement_reflns_used    9942
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      28.70
_cell_measurement_theta_min      2.19
_cell_volume                     5099.8(4)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL n/a (Sheldrick, 2008)'
_computing_structure_solution    'XT n/a (Sheldrick, 2015)'
_diffrn_ambient_temperature      90(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'Bruker D8 Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'TRIUMPH curved-crystal'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0762
_diffrn_reflns_av_unetI/netI     0.0749
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            59508
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.712
_diffrn_reflns_theta_min         1.242
_diffrn_source                   'sealed X-ray tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.770
_exptl_absorpt_correction_T_max  0.926
_exptl_absorpt_correction_T_min  0.871
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker, 2016/2) was used for absorption correction. wR2(int) was 0.0594 before and 0.0551 after correction. The ratio of minimum to maximum transmission is 0.9407. The \l/2 correction factor is not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2112
_exptl_crystal_recrystallization_method
'The material was recrystallised from DCM by slow evaporation'
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.839
_refine_diff_density_min         -0.672
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     544
_refine_ls_number_reflns         13116
_refine_ls_number_restraints     878
_refine_ls_restrained_S_all      0.982
_refine_ls_R_factor_all          0.0834
_refine_ls_R_factor_gt           0.0469
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0333P)^2^+4.7581P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0856
_refine_ls_wR_factor_ref         0.0972
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9172
_reflns_number_total             13116
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc08997g2.cif
_cod_data_source_block           dg570
_cod_depositor_comments
'Adding full bibliography for 7125799--7125801.cif.'
_cod_database_code               7125800
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.927
_shelx_estimated_absorpt_t_min   0.906
_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
 C40-C37 \\sim C40A-C37A \\sim C39-C37 \\sim C39A-C37A \\sim C38-C37 \\sim
C38A-C37A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C37) = Uanis(C37A)
Uanis(C38) = Uanis(C38A)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C40A)=Sof(H40D)=Sof(H40E)=
 Sof(H40F)=Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C37A)=1-FVAR(1)
 Sof(C37)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39)=Sof(H39A)=Sof(H39B)=
 Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C6(H6)
6.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C45(H45A,H45B), C46(H46A,H46B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C11(H11), C13(H13), C29(H29), C31(H31)
6.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C34(H34A,
 H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C39A(H39D,H39E,H39F), C40A(H40D,H40E,H40F),
 C38A(H38D,H38E,H38F)
;
_shelx_res_checksum              65507
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in oil'
_olex2_submission_original_sample_id HW177
_olex2_submission_special_instructions 'No special instructions were received'