Tuning the selectivity of P<sub>4</sub> reduction at alkaline-earth metal centres.
Thum, Stefan; Townrow, Oliver P. E.; Langer, Jens; Harder, Sjoerd; Chemical science 16 (2025) 4528–4536; doi:10.1039/d4sc08502g

data_1573851
_publ_section_title
;
 Tuning the selectivity of P<sub>4</sub> reduction at alkaline-earth metal
 centres.
;
_journal_issue                   10
_journal_name_full               'Chemical science'
_journal_page_first              4528
_journal_page_last               4536
_journal_paper_doi               10.1039/d4sc08502g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C116 H164 Mg4 N8 P8, C6 H6'
_chemical_formula_sum            'C122 H170 Mg4 N8 P8'
_chemical_formula_weight         2093.65
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-04 deposited with the CCDC.	2025-02-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.570(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.4049(5)
_cell_length_b                   18.7396(2)
_cell_length_c                   27.4993(5)
_cell_measurement_reflns_used    18586
_cell_measurement_temperature    99.98(19)
_cell_measurement_theta_max      72.6050
_cell_measurement_theta_min      4.0630
_cell_volume                     11950.2(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(19)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.972
_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    -65.00 -38.00   1.00   10.00    --  -41.15 125.00   0.00   27
  2  \w   -115.00 -18.00   1.00   10.00    --  -41.15 -38.00-120.00   97
  3  \w   -110.00 -25.00   1.00   10.00    --  -41.15 -38.00 -30.00   85
  4  \w    -21.00   5.00   1.00   10.00    --   41.15 -77.00 150.00   26
  5  \w     47.00  74.00   1.00   10.00    --   41.15 -77.00 150.00   27
  6  \w     76.00 178.00   1.00   40.00    --  104.66  30.00-120.00  102
  7  \w    144.00 176.00   1.00   40.00    --  104.66 125.00 -90.00   32
  8  \w    138.00 166.00   1.00   40.00    --  104.66  30.00 -90.00   28
  9  \w     42.00 130.00   1.00   40.00    --  104.66 -45.00  60.00   88
 10  \w     36.00 100.00   1.00   40.00    --  104.66 -94.00  30.00   64
 11  \w     22.00 102.00   1.00   40.00    --  104.66 -94.00 -30.00   80
 12  \w    134.00 176.00   1.00   40.00    --  104.66  77.00 120.00   42
;
_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      -0.0649616000
_diffrn_orient_matrix_UB_12      -0.0169384000
_diffrn_orient_matrix_UB_13      -0.0280079000
_diffrn_orient_matrix_UB_21      -0.0069821000
_diffrn_orient_matrix_UB_22      0.0288851000
_diffrn_orient_matrix_UB_23      -0.0553280000
_diffrn_orient_matrix_UB_31      0.0120242000
_diffrn_orient_matrix_UB_32      -0.0751022000
_diffrn_orient_matrix_UB_33      -0.0148961000
_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  0.0293
_diffrn_reflns_av_unetI/netI     0.0400
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            48510
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.583
_diffrn_reflns_theta_min         3.660
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.672
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.528
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.106a (Rigaku Oxford Diffraction, 2024)
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    1.164
_exptl_crystal_description       block
_exptl_crystal_F_000             4504
_exptl_crystal_size_max          0.311
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.508
_refine_diff_density_min         -0.299
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.007
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1636
_refine_ls_number_reflns         23050
_refine_ls_number_restraints     3246
_refine_ls_restrained_S_all      0.965
_refine_ls_R_factor_all          0.0580
_refine_ls_R_factor_gt           0.0441
_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^)+(0.0555P)^2^+6.4649P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1072
_refine_ls_wR_factor_ref         0.1163
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18684
_reflns_number_total             23050
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08502g2.cif
_cod_data_source_block           hasj240610a
_cod_depositor_comments
'Adding full bibliography for 1573851--1573855.cif.'
_cod_database_code               1573851
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C122H170Mg4N8P8
_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 distances
 N1-C6 \\sim N1-C6A \\sim N2-C18 \\sim N2-C18A
 with sigma of 0.02
 C23-C18 \\sim C23A-C18A \\sim C19A-C18A \\sim C19-C18 \\sim C7-C6 \\sim
C7A-C6A \\sim C6-C11 \\sim C6A-C11A
 with sigma of 0.02
 C8-C7 \\sim C8A-C7A \\sim C11-C10 \\sim C11A-C10A \\sim C23-C22 \\sim
C23A-C22A \\sim C20A-C19A \\sim C20-
 C19
 with sigma of 0.02
 C9A-C8A \\sim C9-C8 \\sim C9-C10 \\sim C9A-C10A \\sim C21A-C20A \\sim C21-C20
\\sim C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C24A-C19A \\sim C24-C19 \\sim C27-C23 \\sim C27A-C23A \\sim C7A-C12A \\sim
C7-C12 \\sim C15A-C11A ~
 C15-C11 \\sim C70A-C65 \\sim C70-C65 \\sim C44-C40 \\sim C44A-C40
 with sigma of 0.02
 C25-C24 \\sim C25A-C24A \\sim C26A-C24A \\sim C26-C24 \\sim C28A-C27A \\sim
C28-C27 \\sim C29A-C27A ~
 C29-C27 \\sim C14A-C12A \\sim C14-C12 \\sim C13-C12 \\sim C13A-C12A \\sim
C17-C15 \\sim C17A-C15A ~
 C16A-C15A \\sim C16-C15 \\sim C72A-C70A \\sim C72-C70 \\sim C71-C70 \\sim
C71A-C70A \\sim C46-C44 ~
 C46A-C44A \\sim C45A-C44A \\sim C45-C44
 with sigma of 0.02
 C17A-C16A \\sim C17-C16 \\sim C13-C14 \\sim C13A-C14A \\sim C26-C25 \\sim
C26A-C25A \\sim C29A-C28A ~
 C28-C29 \\sim C71A-C72A \\sim C71-C72 \\sim C46A-C45A \\sim C46-C45
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C40 \\sim C44 \\sim C45 \\sim C46 \\sim C44A \\sim C45A \\sim C46A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim
C26 \\sim C27 \\sim C28 \\sim C29 \\sim C18A \\sim C19A \\sim C20A \\sim C21A
\\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim C28A
\\sim C29A: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 4A
C65 \\sim C70 \\sim C71 \\sim C72 \\sim C70A \\sim C71A \\sim C72A: within 4A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C117 \\sim C118 \\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim
C124 \\sim C125 \\sim C126 \\sim C127 \\sim C128: within 4A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 4A
C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14
\\sim C15 \\sim C16 \\sim C17 \\sim C6A \\sim C7A \\sim C8A \\sim C9A \\sim
C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim C16A \\sim
C17A: within 3A with sigma of 0.03 and sigma for terminal atoms of 0.06 within
3A
C70 \\sim C70A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C18A) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C40, C44A, C45A, C46A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C65, C70, C71, C72, C70A, C71A, C72A
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
 C19, C20, C21, C22, C23, C24, C25, C26, C27, C28, C29, C19A, C20A, C21A, C22A,
  C23A, C24A, C25A, C26A, C27A, C28A, C29A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C27, C28, C23
 with sigma for 1-2 distances of 0.003 and sigma for 1-3 distances of 0.003
5. Others
 Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45D)=Sof(H45E)=Sof(H45F)=Sof(C46A)=
 Sof(H46D)=Sof(H46E)=Sof(H46F)=1-FVAR(1)
 Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=Sof(H46A)=
 Sof(H46B)=Sof(H46C)=FVAR(1)
 Sof(C18A)=Sof(C19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=
 Sof(H22A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25D)=Sof(H25E)=
 Sof(H25F)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27A)=Sof(H27A)=
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=1-FVAR(2)
 Sof(C18)=Sof(C19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=
 Sof(C23)=Sof(C24)=Sof(H24)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C26)=
 Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28A)=Sof(H28B)=
 Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(2)
 Sof(C70A)=Sof(H70A)=Sof(C71A)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C72A)=
 Sof(H72D)=Sof(H72E)=Sof(H72F)=1-FVAR(3)
 Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=
 Sof(H72B)=Sof(H72C)=FVAR(3)
 Sof(C122)=Sof(H122)=Sof(C121)=Sof(H121)=Sof(C120)=Sof(H120)=Sof(C119)=
 Sof(H119)=Sof(C118)=Sof(H118)=Sof(C117)=Sof(H117)=1-FVAR(4)
 Sof(C123)=Sof(H123)=Sof(C128)=Sof(H128)=Sof(C127)=Sof(H127)=Sof(C126)=
 Sof(H126)=Sof(C125)=Sof(H125)=Sof(C124)=Sof(H124)=FVAR(4)
 Sof(C6A)=Sof(C7A)=Sof(C8A)=Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10M)=
 Sof(C11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=
 Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=1-FVAR(5)
 Sof(C6)=Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C41(H41), C53(H53), C56(H56), C73(H73), C82(H82), C85(H85), C99(H99),
 C102(H102), C111(H111), C114(H114), C12(H12), C15(H15), C24(H24), C27(H27),
 C44(H44), C70(H70), C12A(H12A), C15A(H15A), C24A(H24A), C27A(H27A), C44A(H44A),
  C70A(H70A)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C32(H32), C37(H37), C38(H38), C39(H39), C49(H49), C50(H50), C51(H51),
 C61(H61), C66(H66), C67(H67), C68(H68), C78(H78), C79(H79), C80(H80), C90(H90),
  C95(H95), C96(H96), C97(H97), C107(H107), C108(H108), C109(H109), C8(H8),
 C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C8A(H8A), C9A(H9A), C10A(H10M),
  C20A(H20A), C21A(H21A), C22A(H22A), C122(H122), C121(H121), C120(H120),
 C119(H119), C118(H118), C117(H117), C123(H123), C128(H128), C127(H127),
 C126(H126), C125(H125), C124(H124)
6.c Fitted hexagon refined as free rotating group:
 C122(C121,C120,C119,C118,C117), C123(C128,C127,C126,C125,C124)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C5(H5A,H5B,H5C), C30(H30A,H30B,H30C), C34(H34A,H34B,H34C),
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C54(H54A,H54B,H54C), C55(H55A,H55B,
 H55C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C63(H63A,
 H63B,H63C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C83(H83A,H83B,H83C),
 C84(H84A,H84B,H84C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,
 H88C), C92(H92A,H92B,H92C), C100(H10A,H10B,H10C), C101(H10D,H10E,H10F),
 C103(H10G,H10H,H10I), C104(H10J,H10K,H10L), C112(H11A,H11B,H11C), C113(H11D,
 H11E,H11F), C115(H11G,H11H,H11I), C116(H11J,H11K,H11L), C13(H13A,H13B,H13C),
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C45(H45A,
 H45B,H45C), C46(H46A,H46B,H46C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C),
 C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F), C16A(H16D,H16E,H16F), C17A(H17D,
 H17E,H17F), C25A(H25D,H25E,H25F), C26A(H26D,H26E,H26F), C28A(H28D,H28E,H28F),
 C29A(H29D,H29E,H29F), C45A(H45D,H45E,H45F), C46A(H46D,H46E,H46F), C71A(H71D,
 H71E,H71F), C72A(H72D,H72E,H72F)
;
_shelx_res_checksum              26497
_shelx_hkl_checksum              11284
_olex2_date_sample_data_collection 2024-06-10
_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 1.571
_oxdiff_exptl_absorpt_empirical_full_min 0.763