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_1571251
_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         'C29 H25 N4 P, C7 H8'
_chemical_formula_sum            'C36 H33 N4 P'
_chemical_formula_weight         552.63
_chemical_name_systematic
'6,6',6'',6'''-(phosphinine-2,3,5,6-tetrayl)tetrakis(3-methylpyridine) toluene solvate'
_chemical_properties_physical    Moisture-sensitive
_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
_audit_creation_date             2023-10-31
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-31 deposited with the CCDC.	2024-03-08 downloaded from the CCDC.
;
_cell_angle_alpha                102.992(2)
_cell_angle_beta                 95.8210(10)
_cell_angle_gamma                93.2140(10)
_cell_formula_units_Z            1
_cell_length_a                   6.0439(2)
_cell_length_b                   10.8817(5)
_cell_length_c                   11.4035(5)
_cell_measurement_reflns_used    9945
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      30.56
_cell_measurement_theta_min      2.34
_cell_volume                     724.61(5)
_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_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.995
_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  0.0396
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            40058
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.591
_diffrn_reflns_theta_min         2.339
_exptl_absorpt_coefficient_mu    0.127
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9471
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0972 before and 0.0550 after correction.
The Ratio of minimum to maximum transmission is 0.9471.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       Plate
_exptl_crystal_F_000             292
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene'
_exptl_crystal_size_max          0.494
_exptl_crystal_size_mid          0.243
_exptl_crystal_size_min          0.128
_refine_diff_density_max         0.316
_refine_diff_density_min         -0.248
_refine_diff_density_rms         0.057
_refine_ls_extinction_coef       0.044(10)
_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   1.277
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         4445
_refine_ls_number_restraints     91
_refine_ls_restrained_S_all      1.267
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0735
_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^)+0.8739P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1536
_refine_ls_wR_factor_ref         0.1556
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4067
_reflns_number_total             4445
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05930h2.cif
_cod_data_source_block           skl025_lkcntc
_cod_depositor_comments
'Adding full bibliography for 1571249--1571254.cif.'
_cod_database_code               1571251
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.940
_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. Restrained planarity
 C24, C19, C20, C21, C22, C23, C18
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C23 \\sim C24 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C18: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C1) = Uanis(C2) = Uanis(C5) = Uanis(C4)
4. Rigid body (RIGU) restrains
 C24, C23, C22, C21, C20, C19, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: P1(0.5) C2(0.5) C1(0.5) C19(0.5) C24(0.5) H24(0.5) C23(0.5)
 H23(0.5) C22(0.5) H22(0.5) C21(0.5) H21(0.5) C20(0.5) H20(0.5) C18(0.5)
 H18A(0.5) H18B(0.5) H18C(0.5) C3(0.5) H3(0.5) C5(0.5) C4(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C13(H13), C10(H10), C16(H16), C7(H7), C8(H8), C24(H24), C23(H23),
 C22(H22), C21(H21), C20(H20), C3(H3)
6.b Fitted hexagon refined as free rotating group:
 C19(C24,C23,C22,C21,C20)
6.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              42755
_olex2_submission_original_sample_id SKL025
_olex2_submission_special_instructions 'No special instructions were received'