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_1573852
_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         'C74 H114 Mg2 N4 P4'
_chemical_formula_sum            'C74 H114 Mg2 N4 P4'
_chemical_formula_weight         1232.19
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.1211(5)
_cell_length_b                   21.8425(4)
_cell_length_c                   12.8482(3)
_cell_measurement_reflns_used    13157
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      71.6540
_cell_measurement_theta_min      3.7980
_cell_volume                     7330.5(3)
_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      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -68.00  31.00   1.00   10.00    --  -41.40  57.00   0.00   99
  2  \w   -111.00 -20.00   1.00   10.00    --  -41.40 -57.00-150.00   91
  3  \w    -73.00  24.00   1.00   10.00    --  -41.90  77.00 120.00   97
  4  \w     32.00 137.00   1.00   40.00    --  104.66 -77.00-150.00  105
  5  \w     54.00 133.00   1.00   40.00    --  104.66 -30.00-150.00   79
  6  \w     77.00 113.00   1.00   40.00    --  104.66-125.00-150.00   36
  7  \w     34.00 129.00   1.00   40.00    --  104.66 -61.00  60.00   95
  8  \w     90.00 176.00   1.00   40.00    --  104.66  45.00-150.00   86
  9  \w    125.00 171.00   1.00   40.00    --  104.66  77.00  30.00   46
 10  \w     33.00 113.00   1.00   40.00    --  104.66-125.00  60.00   80
 11  \w     25.00 106.00   1.00   40.00    --  104.66 -94.00  60.00   81
 12  \w     31.00 151.00   1.00   40.00    --  104.66 -15.00  30.00  120
;
_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      0.0450617000
_diffrn_orient_matrix_UB_12      0.0173070000
_diffrn_orient_matrix_UB_13      -0.0717260000
_diffrn_orient_matrix_UB_21      -0.0365128000
_diffrn_orient_matrix_UB_22      0.0014240000
_diffrn_orient_matrix_UB_23      -0.0940460000
_diffrn_orient_matrix_UB_31      -0.0105614000
_diffrn_orient_matrix_UB_32      0.0683561000
_diffrn_orient_matrix_UB_33      0.0200348000
_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  0.0311
_diffrn_reflns_av_unetI/netI     0.0144
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            45281
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.057
_diffrn_reflns_theta_min         3.834
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.427
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.398
_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    1.116
_exptl_crystal_description       block
_exptl_crystal_F_000             2680
_exptl_crystal_size_max          0.343
_exptl_crystal_size_mid          0.216
_exptl_crystal_size_min          0.126
_exptl_crystal_size_rad          0.107
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.347
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     715
_refine_ls_number_reflns         7152
_refine_ls_number_restraints     2733
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0881
_refine_ls_R_factor_gt           0.0756
_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^)+(0.1458P)^2^+2.0967P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2342
_refine_ls_wR_factor_ref         0.2547
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5588
_reflns_number_total             7152
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08502g2.cif
_cod_data_source_block           hasj240617a
_cod_depositor_comments
'Adding full bibliography for 1573851--1573855.cif.'
_cod_database_code               1573852
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C74H114Mg2N4P4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 P1-P1_$1 \\sim P5-P4
 with sigma of 0.02
 P3-P1 \\sim P3-P1_$1 \\sim P2-P1 \\sim P2-P1_$1 \\sim P6-P4 \\sim P6-P5 \\sim
P6_$1-P4 \\sim P6_$1-P5
 with sigma of 0.02
 P4-Mg2 \\sim P5-Mg2 \\sim P1_$1-Mg1 \\sim P1-Mg1
 with sigma of 0.02
 P2-Mg2 \\sim P3-Mg2 \\sim P6_$1-Mg1 \\sim P6-Mg1
 with sigma of 0.02
 N3-C41 \\sim N3-C41A \\sim N2-C22 \\sim N1-C6
 with sigma of 0.02
 C27-C22 \\sim C23-C22 \\sim C7-C6 \\sim C6-C11 \\sim C42-C41 \\sim C42A-C41A
\\sim C46-C41 \\sim C46A-C41A
 with sigma of 0.02
 C11-C10 \\sim C8-C7 \\sim C27-C26 \\sim C24-C23 \\sim C43-C42 \\sim C43A-C42A
\\sim C46-C45 \\sim C46A-C45A
 with sigma of 0.02
 C9-C10 \\sim C9-C8 \\sim C26-C25 \\sim C25-C24 \\sim C45-C44 \\sim C45A-C44A
\\sim C43-C44 \\sim C43A-C44A
 with sigma of 0.02
 C7-C12 \\sim C17-C11 \\sim C28-C23 \\sim C33-C27 \\sim C47A-C42A \\sim C47-C42
\\sim C52-C46 \\sim C52A-
 C46A
 with sigma of 0.02
 C29-C28 \\sim C31-C28 \\sim C34-C33 \\sim C36-C33 \\sim C53A-C52A \\sim
C55A-C52A \\sim C53-C52 \\sim C55-
 C52 \\sim C48A-C47A \\sim C50A-C47A \\sim C48-C47 \\sim C50-C47
 with sigma of 0.02
 C30-C29 \\sim C32-C31 \\sim C35-C34 \\sim C37-C36 \\sim C49A-C48A \\sim
C49-C48 \\sim C51A-C50A \\sim C51-
 C50 \\sim C54-C53 \\sim C54A-C53A \\sim C56A-C55A \\sim C56-C55
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
P4 \\sim P5 \\sim P6 \\sim P6 \\sim P2 \\sim P1 \\sim P1 \\sim P3: within 4A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C41A \\sim C42A \\sim C43A \\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim
C48A \\sim C49A \\sim C50A \\sim C51A \\sim C52A \\sim C53A \\sim C54A \\sim
C55A \\sim C56A \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46
\\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54
\\sim C55 \\sim C56: within 4A with sigma of 0.02 and sigma for terminal atoms
of 0.04 within 4A
C19 \\sim C15 \\sim C13 \\sim C17 \\sim C21 \\sim C14 \\sim C16 \\sim C18 \\sim
C20 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12: within
4A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
C35 \\sim C27 \\sim C23 \\sim C31 \\sim C25 \\sim C29 \\sim C33 \\sim C37 \\sim
C22 \\sim C24 \\sim C26 \\sim C28 \\sim C30 \\sim C32 \\sim C34 \\sim C36:
within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 4A
4. Others
 Sof(P6)=1-FVAR(1)
 Sof(P4)=Sof(P5)=0.5*(1-FVAR(2))
 Sof(P2)=Sof(P3)=0.5*FVAR(2)
 Sof(P1)=FVAR(1)
 Sof(C41A)=Sof(C42A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44A)=Sof(C45A)=
 Sof(H45A)=Sof(C46A)=Sof(C47A)=Sof(H47A)=Sof(C48A)=Sof(H48a)=Sof(H48b)=
 Sof(C49A)=Sof(H49a)=Sof(H49b)=Sof(H49c)=Sof(C50A)=Sof(H50a)=Sof(H50b)=
 Sof(C51A)=Sof(H51a)=Sof(H51b)=Sof(H51c)=Sof(C52A)=Sof(H52A)=Sof(C53A)=
 Sof(H53a)=Sof(H53b)=Sof(C54A)=Sof(H54a)=Sof(H54b)=Sof(H54c)=Sof(C55A)=
 Sof(H55a)=Sof(H55b)=Sof(C56A)=Sof(H56a)=Sof(H56b)=Sof(H56c)=1-FVAR(2)
 Sof(C41)=Sof(C42)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45)=
 Sof(C46)=Sof(C47)=Sof(H47)=Sof(C48)=Sof(H48c)=Sof(H48d)=Sof(C49)=Sof(H49d)=
 Sof(H49e)=Sof(H49f)=Sof(C50)=Sof(H50c)=Sof(H50d)=Sof(C51)=Sof(H51d)=Sof(H51e)=
 Sof(H51f)=Sof(C52)=Sof(H52)=Sof(C53)=Sof(H53c)=Sof(H53d)=Sof(C54)=Sof(H54d)=
 Sof(H54e)=Sof(H54f)=Sof(C55)=Sof(H55c)=Sof(H55d)=Sof(C56)=Sof(H56d)=Sof(H56e)=
 Sof(H56f)=FVAR(2)
 Fixed Sof: H1a(0.5) H1b(0.5) H1c(0.5) H5a(0.5) H5b(0.5) H5c(0.5) C19(0.5)
 H19a(0.5) H19b(0.5) H19c(0.5) C35(0.5) H35a(0.5) H35b(0.5) H35c(0.5) C15(0.5)
 H15a(0.5) H15b(0.5) C31(0.5) H31a(0.5) H31b(0.5) C13(0.5) H13a(0.5) H13b(0.5)
 C17(0.5) H17(0.5) C21(0.5) H21a(0.5) H21b(0.5) H21c(0.5) C29(0.5) H29a(0.5)
 H29b(0.5) C33(0.5) H33(0.5) C37(0.5) H37a(0.5) H37b(0.5) H37c(0.5) C14(0.5)
 H14a(0.5) H14b(0.5) H14c(0.5) C16(0.5) H16a(0.5) H16b(0.5) H16c(0.5) C18(0.5)
 H18a(0.5) H18b(0.5) C20(0.5) H20a(0.5) H20b(0.5) C22(0.5) C27(0.5) C26(0.5)
 H26(0.5) C25(0.5) H25(0.5) C24(0.5) H24(0.5) C23(0.5) C28(0.5) H28(0.5)
 C6(0.5) C30(0.5) H30a(0.5) H30b(0.5) H30c(0.5) C7(0.5) C32(0.5) H32a(0.5)
 H32b(0.5) H32c(0.5) C8(0.5) H8(0.5) C34(0.5) H34a(0.5) H34b(0.5) C9(0.5)
 H9(0.5) C36(0.5) H36a(0.5) H36b(0.5) C10(0.5) H10(0.5) C11(0.5) C12(0.5)
 H12(0.5)
5.a Ternary CH refined with riding coordinates:
 C47A(H47A), C52A(H52A), C17(H17), C47(H47), C33(H33), C52(H52), C28(H28),
 C12(H12)
5.b Secondary CH2 refined with riding coordinates:
 C48A(H48a,H48b), C50A(H50a,H50b), C53A(H53a,H53b), C55A(H55a,H55b), C15(H15a,
 H15b), C31(H31a,H31b), C13(H13a,H13b), C29(H29a,H29b), C48(H48c,H48d),
 C50(H50c,H50d), C18(H18a,H18b), C20(H20a,H20b), C53(H53c,H53d), C55(H55c,H55d),
  C34(H34a,H34b), C36(H36a,H36b)
5.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C40(H40), C43A(H43A), C44A(H44A), C45A(H45A), C43(H43), C44(H44),
 C45(H45), C26(H26), C25(H25), C24(H24), C8(H8), C9(H9), C10(H10)
5.d Fitted hexagon refined as free rotating group:
 C22(C27,C26,C25,C24,C23)
5.e Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C5(H5a,H5b,H5c), C38(H38a,H38b,H38c), C49A(H49a,H49b,H49c),
 C51A(H51a,H51b,H51c), C54A(H54a,H54b,H54c), C56A(H56a,H56b,H56c), C19(H19a,
 H19b,H19c), C35(H35a,H35b,H35c), C21(H21a,H21b,H21c), C37(H37a,H37b,H37c),
 C49(H49d,H49e,H49f), C14(H14a,H14b,H14c), C16(H16a,H16b,H16c), C51(H51d,H51e,
 H51f), C54(H54d,H54e,H54f), C56(H56d,H56e,H56f), C30(H30a,H30b,H30c), C32(H32a,
 H32b,H32c)
;
_shelx_res_checksum              75217
_shelx_hkl_checksum              987
_olex2_date_sample_data_collection 2024-06-17
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.937
_oxdiff_exptl_absorpt_empirical_full_min 0.673