Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons
Grasruck, Alexander; Parla, Giorgio; Heineman, Frank W.; Langer, Jens; Herrera, Alberto; Frieß, Sybille; Schmid, Günter; Dorta, Romano; New Journal of Chemistry 47 (2023) 2307–2323; doi:10.1039/D2NJ05222A

data_7062150
_publ_section_title
;
 Developing bulky P-alkene ligands: stabilization of copper complexes with
 14 valence electrons
;
_journal_issue                   5
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              2307
_journal_page_last               2323
_journal_paper_doi               10.1039/D2NJ05222A
_journal_volume                  47
_journal_year                    2023
_chemical_formula_moiety
'C84 H60 Cl Cu2 N6 P2, C32 H12 B F24, 1.5(C6 H6)'
_chemical_formula_sum            'C125 H81 B Cl Cu2 F24 N6 P2'
_chemical_formula_weight         2358.23
_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             2022-06-03
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-06-03 deposited with the CCDC.	2022-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                106.5840(10)
_cell_angle_beta                 103.4260(10)
_cell_angle_gamma                110.9710(10)
_cell_formula_units_Z            2
_cell_length_a                   16.9539(2)
_cell_length_b                   18.4799(3)
_cell_length_c                   20.4231(3)
_cell_measurement_reflns_used    41940
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.7790
_cell_measurement_theta_min      3.8640
_cell_volume                     5311.67(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -116.00 -17.00   1.00    2.00    --  -41.44 -38.00-180.00   99
  2  \w    -74.00  35.00   1.00    2.00    --  -41.44  77.00  90.00  109
  3  \w    -66.00  33.00   1.00    2.00    --  -41.44  38.00   0.00   99
  4  \w      8.00  42.00   1.00    2.00    --   41.44  80.00-163.79   34
  5  \w     97.00 178.00   1.00    8.00    --  104.37 125.00  60.00   81
  6  \w     28.00 133.00   1.00    8.00    --  104.37 -30.00-120.00  105
  7  \w     79.00 177.00   1.00    8.00    --  104.37  45.00-150.00   98
  8  \w     22.00 106.00   1.00    8.00    --  104.37 -94.00  60.00   84
  9  \w     28.00 137.00   1.00    8.00    --  104.37 -77.00  60.00  109
 10  \w     28.00 133.00   1.00    8.00    --  104.37 -30.00  30.00  105
 11  \w     31.00 112.00   1.00    8.00    --  104.37-125.00 -90.00   81
 12  \w    103.00 178.00   1.00    8.00    --  104.37  77.00  60.00   75
 13  \w     97.00 178.00   1.00    8.00    --  104.37 125.00  30.00   81
 14  \w     26.00 108.00   1.00    8.00    --  104.37-105.00  15.57   82
 15  \w   -116.00 -17.00   1.00    2.00    --  -41.44 -38.00  30.00   99
 16  \w   -116.00 -17.00   1.00    2.00    --  -41.44 -38.00 -60.00   99
 17  \w      7.00  33.00   1.00    2.00    --   41.44  84.00 -37.38   26
 18  \w      8.00  42.00   1.00    2.00    --   41.44  81.00   2.19   34
 19  \w     52.00 178.00   1.00    8.00    --  104.37  15.00 120.00  126
 20  \w     75.00 156.00   1.00    8.00    --  104.37  61.00 -90.00   81
 21  \w     76.00 178.00   1.00    8.00    --  104.37  30.00   0.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0560460000
_diffrn_orient_matrix_UB_12      0.0967631000
_diffrn_orient_matrix_UB_13      0.0282881000
_diffrn_orient_matrix_UB_21      -0.0344545000
_diffrn_orient_matrix_UB_22      0.0127653000
_diffrn_orient_matrix_UB_23      0.0638364000
_diffrn_orient_matrix_UB_31      0.0817181000
_diffrn_orient_matrix_UB_32      -0.0039232000
_diffrn_orient_matrix_UB_33      0.0482111000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            60142
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.913
_diffrn_reflns_theta_min         3.887
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.855
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.525
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.474
_exptl_crystal_description       block
_exptl_crystal_F_000             2398
_exptl_crystal_size_max          0.264
_exptl_crystal_size_mid          0.237
_exptl_crystal_size_min          0.178
_refine_diff_density_max         1.032
_refine_diff_density_min         -0.489
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1759
_refine_ls_number_reflns         20605
_refine_ls_number_restraints     2654
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0374
_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^)+(0.0561P)^2^+3.7422P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1003
_refine_ls_wR_factor_ref         0.1024
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19220
_reflns_number_total             20605
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj05222a2.cif
_cod_data_source_block           rodo191210a
_cod_depositor_comments
'Adding full bibliography for 7062150--7062158.cif.'
_cod_original_cell_volume        5311.67(14)
_cod_database_code               7062150
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         C125H81BClCu2F24N6P2
_shelx_estimated_absorpt_t_max   0.734
_shelx_estimated_absorpt_t_min   0.640
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F10A-C129 \\sim F10-C100 \\sim F10B-C130 \\sim F11A-C129 \\sim F11-C100 \\sim
F11B-C130 \\sim F12A-
 C129 \\sim F12B-C130 \\sim F12-C100 \\sim F24-C116 \\sim F24A-C116 \\sim
F23A-C116 \\sim F23-C116 ~
 F22A-C116 \\sim F22-C116 \\sim F19A-C133 \\sim F19-C115 \\sim F20A-C133 \\sim
F20-C115 \\sim F21A-C133
 \\sim F21-C115 \\sim F18-C108 \\sim F18A-C132 \\sim F17-C108 \\sim F17A-C132
\\sim F16A-C132 \\sim F16-
 C108 \\sim F13-C107 \\sim F13A-C131 \\sim F14A-C131 \\sim F14-C107 \\sim
F15-C107 \\sim F15A-C131 ~
 F8A-C99A \\sim F8-C99 \\sim F7-C99 \\sim F7A-C99A \\sim F9-C99 \\sim F9A-C99A
 with sigma of 0.02
 C100-C97 \\sim C129-C97 \\sim C103-C131 \\sim C103-C107 \\sim C115-C111 \\sim
C133-C111 \\sim C130-
 C97 \\sim C132-C105 \\sim C108-C105
 with sigma of 0.02
 C99A-C95 \\sim C99-C95
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
F10 \\sim F11 \\sim F12 \\sim C100 \\sim F10B \\sim F11B \\sim F12B \\sim C130:
within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C111 \\sim F19 \\sim F20 \\sim F21 \\sim C115 \\sim F19A \\sim F20A \\sim F21A
\\sim C133: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 4A
C103 \\sim F13 \\sim F14 \\sim F15 \\sim C107 \\sim F13A \\sim F14A \\sim F15A
\\sim C131: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 4A
C116 \\sim F22 \\sim F23 \\sim F24 \\sim F22A \\sim F23A \\sim F24A: within 4A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138 \\sim C139: within 4A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
F16 \\sim F17 \\sim F18 \\sim C108 \\sim F16A \\sim F17A \\sim F18A \\sim C132:
within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C97 \\sim F10 \\sim F11 \\sim F12 \\sim C100 \\sim F10B \\sim F11B \\sim F12B
\\sim C130 \\sim F10A \\sim F11A \\sim F12A \\sim C129 \\sim C99 \\sim C99A
\\sim F8 \\sim F8A \\sim F9A \\sim F9 \\sim F7 \\sim F7A: within 4A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 4A
C108 \\sim C132: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(F12) \\sim Ueq, Uanis(F12B) \\sim Ueq, Uanis(F12A) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.005
Uanis(C124) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C126) \\sim Ueq,
Uanis(C127) \\sim Ueq, Uanis(C128) \\sim Ueq, Uanis(C123) \\sim Ueq: with sigma
of 0.003 and sigma for terminal atoms of 0.006
4. Rigid body (RIGU) restrains
 C97, F10, F11, F12, C100, F10B, F11B, F12B, C130
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C111, F19, F21, C115, F19A, F20A, F21A, C133
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C103, F13, F14, F15, C107, F13A, F14A, F15A, C131
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C113, C116, F22, F23, F24, F22A, F23A, F24A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C134, C135, C136, C137, C138, C139
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C123, C124, C125, C126, C127, C128
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C105, F16, F17, F18, C108, F16A, F17A, F18A, C132
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 1*[Sof(F10)+Sof(F11)+Sof(F12)+Sof(C100)]+1*[Sof(F10B)+Sof(F11B)+Sof(F12B)+
 Sof(C130)]+1*[Sof(F10A)+Sof(F11A)+Sof(F12A)+Sof(C129)]=1 with esd of 0.0001
 Sof(F10)=Sof(F11)=Sof(F12)=Sof(C100)=FVAR(1)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=Sof(C133)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F21)=Sof(C115)=FVAR(2)
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(C107)=1-FVAR(3)
 Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(C131)=FVAR(3)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(4)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(4)
 Sof(C136)=Sof(H136)=Sof(C135)=Sof(H135)=Sof(C134)=Sof(H134)=Sof(C139)=
 Sof(H139)=Sof(C138)=Sof(H138)=Sof(C137)=Sof(H137)=1-FVAR(5)
 Sof(C117)=Sof(H117)=Sof(C118)=Sof(H118)=Sof(C119)=Sof(H119)=Sof(C120)=
 Sof(H120)=Sof(C121)=Sof(H121)=Sof(C122)=Sof(H122)=FVAR(5)
 Sof(F16A)=Sof(F17A)=Sof(F18A)=Sof(C132)=1-FVAR(6)
 Sof(F16)=Sof(F17)=Sof(F18)=Sof(C108)=FVAR(6)
 Sof(F10B)=Sof(F11B)=Sof(F12B)=Sof(C130)=FVAR(7)
 Sof(F10A)=Sof(F11A)=Sof(F12A)=Sof(C129)=FVAR(8)
 Sof(F7A)=Sof(F9A)=Sof(C99A)=Sof(F8A)=1-FVAR(9)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(C99)=FVAR(9)
 Fixed Sof: C124(0.5) H124(0.5) C123(0.5) H123(0.5) C128(0.5) H128(0.5)
 C127(0.5) H127(0.5) C126(0.5) H126(0.5) C125(0.5) H125(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C10(H10), C11(H11), C12(H12),
 C13(H13), C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C24(H24),
  C25(H25), C26(H26), C27(H27), C30(H30), C31(H31), C32(H32), C33(H33),
 C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C44(H44), C45(H45),
  C46(H46), C47(H47), C49(H49), C50(H50), C52(H52), C53(H53), C54(H54),
 C55(H55), C58(H58), C59(H59), C60(H60), C61(H61), C63(H63), C64(H64), C66(H66),
  C67(H67), C68(H68), C69(H69), C72(H72), C73(H73), C74(H74), C75(H75),
 C77(H77), C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C86(H86), C88(H88),
  C90(H90), C94(H94), C96(H96), C98(H98), C102(H102), C104(H104), C106(H106),
 C110(H110), C112(H112), C114(H114), C117(H117), C118(H118), C119(H119),
 C120(H120), C121(H121), C122(H122), C136(H136), C135(H135), C134(H134),
 C139(H139), C138(H138), C137(H137), C124(H124), C123(H123), C128(H128),
 C127(H127), C126(H126), C125(H125)
6.b Fitted hexagon refined as free rotating group:
 C136(C135,C134,C139,C138,C137), C124(C123,C128,C127,C126,C125)
;
_shelx_res_checksum              42599
_olex2_date_sample_data_collection 2021-07-01
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.691
_oxdiff_exptl_absorpt_empirical_full_min 0.793