Highly selective, reversible water activation by P,N-cooperativity in pyridyl-functionalized phosphinines.
Kopp, Richard O.; Kleynemeyer, Sabrina L.; Groth, Lucie J.; Ernst, Moritz J.; Rupf, Susanne M.; Weber, Manuela; Kershaw Cook, Laurence J.; Coles, Nathan T.; Neale, Samuel E.; Müller, Christian; Chemical science 15 (2024) 5496–5506; doi:10.1039/d3sc05930h

data_1571252
_publ_section_title
;
 Highly selective, reversible water activation by P,N-cooperativity in
 pyridyl-functionalized phosphinines.
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              5496
_journal_page_last               5506
_journal_paper_doi               10.1039/d3sc05930h
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C100 H72 Li4 N16 O4 P4, 3.44(C H2 Cl2)'
_chemical_formula_sum            'C103.44 H78.88 Cl6.88 Li4 N16 O4 P4'
_chemical_formula_weight         2005.52
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      tetragonal
_space_group_IT_number           82
_space_group_name_Hall           'I -4'
_space_group_name_H-M_alt        'I -4'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-11-04
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-11-05 deposited with the CCDC.	2024-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.4512(8)
_cell_length_b                   22.4512(8)
_cell_length_c                   10.3077(5)
_cell_measurement_reflns_used    7249
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      72.68
_cell_measurement_theta_min      2.78
_cell_volume                     5195.7(4)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_detector                 'BRUKER PHOTON II'
_diffrn_detector_type            CMOS
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker Photon CMOS Detector, D8 Venture'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0999
_diffrn_reflns_av_unetI/netI     0.0748
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            20616
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        66.538
_diffrn_reflns_theta_max         66.538
_diffrn_reflns_theta_min         2.783
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.764
_exptl_absorpt_correction_T_max  0.8082
_exptl_absorpt_correction_T_min  0.5739
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1424 before and 0.1130 after correction.
The Ratio of minimum to maximum transmission is 0.7101.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       needle
_exptl_crystal_F_000             2065
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.500
_refine_diff_density_min         -0.322
_refine_diff_density_rms         0.076
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.07(3)
_refine_ls_extinction_coef       0.0008(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     334
_refine_ls_number_reflns         4550
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0686P)^2^+0.9692P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1201
_refine_ls_wR_factor_ref         0.1300
_reflns_Friedel_coverage         0.872
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                3751
_reflns_number_total             4550
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05930h2.cif
_cod_data_source_block           rok211_final_lkc
_cod_depositor_comments
'Adding full bibliography for 1571249--1571254.cif.'
_cod_database_code               1571252
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.874
_shelx_estimated_absorpt_t_min   0.682
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.93(3)
 0.07(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 Cl2-C1 = Cl1-C1
 1.77 with sigma of 0.02
 Cl1-Cl2
 2.92 with sigma of 0.04
 Cl1A-Cl2A
 2.92 with sigma of 0.04
 Cl1-Cl2 \\sim Cl1A-Cl2A
 with sigma of 0.01
 Cl1A-C1A \\sim Cl2A-C1A \\sim Cl1-C1 \\sim Cl2-C1
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Cl1A \\sim Cl2A \\sim C1A \\sim Cl1 \\sim Cl2 \\sim C1: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C1) = Uanis(C1A)
Uanis(Cl1) = Uanis(Cl1A)
5. Rigid body (RIGU) restrains
 Cl1A, Cl2A, C1A, Cl1, Cl2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Cl1A)=Sof(Cl2A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=0.86*(1-FVAR(2))
 Sof(Cl1)=Sof(Cl2)=Sof(C1)=Sof(H1A)=Sof(H1B)=0.86*FVAR(2)
7.a Everything fixed:
 H1
7.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24),
  C25(H25)
;
_shelx_res_checksum              2916
_olex2_date_sample_data_collection 2023-11-01
_olex2_submission_original_sample_id ROK211
_olex2_submission_special_instructions 'No special instructions were received'