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_1571254
_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_formula_moiety         'C58 H50 Cu4 I4 N8 P2, [C H2 Cl2]'
_chemical_formula_sum            'C59 H52 Cl2 Cu4 I4 N8 P2'
_chemical_formula_weight         1767.68
_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             2023-10-17
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-11-01 deposited with the CCDC.	2024-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.8850(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.1051(8)
_cell_length_b                   17.5837(7)
_cell_length_c                   19.9459(7)
_cell_measurement_reflns_used    9299
_cell_measurement_temperature    105
_cell_measurement_theta_max      27.46
_cell_measurement_theta_min      2.56
_cell_volume                     6601.1(4)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      105
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0515
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            169316
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_min         1.993
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.314
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6244
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0821 before and 0.0618 after correction.
The Ratio of minimum to maximum transmission is 0.8374.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.779
_exptl_crystal_description       block
_exptl_crystal_F_000             3416
_exptl_crystal_size_max          0.299
_exptl_crystal_size_mid          0.137
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.317
_refine_diff_density_min         -1.108
_refine_diff_density_rms         0.157
_refine_ls_extinction_coef       0.00029(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.148
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     694
_refine_ls_number_reflns         15131
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.149
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0152P)^2^+50.1851P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0762
_refine_ls_wR_factor_ref         0.0940
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12040
_reflns_number_total             15131
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05930h2.cif
_cod_data_source_block           rok173_mje_mp
_cod_depositor_comments
'Adding full bibliography for 1571249--1571254.cif.'
_cod_database_code               1571254
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.692
_shelx_estimated_absorpt_t_min   0.437
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C45) \\sim Ueq, Uanis(C47) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
3.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C58(H58), C25(H25), C33(H33), C10(H10), C22(H22), C20(H20),
 C3(H3), C19(H19), C13(H13), C49(H49), C28(H28), C55(H55), C52(H52), C46(H46),
 C40(H40), C56(H56), C14(H14), C37(H37), C50(H50), C16(H16), C26(H26), C43(H43),
  C44(H44), C38(H38)
3.b Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C23(H23A,H23B,H23C), C59(H59A,H59B,H59C), C11(H11A,H11B,
 H11C), C17(H17A,H17B,H17C), C47(H47A,H47B,H47C), C53(H53A,H53B,H53C), C41(H41A,
 H41B,H41C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 180 electrons were 
found in a volume of 1158\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
[+ solvents] per Asymmetric Unit 
which account for 168 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              23557
_shelx_fab_checksum              46748
_olex2_submission_special_instructions 'No special instructions were received'