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_1573855
_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         'C126 H201 Ca3 N6 O3 P7, 1(C5 H10 O)'
_chemical_formula_sum            'C131 H211 Ca3 N6 O4 P7'
_chemical_formula_weight         2271.08
_chemical_properties_physical    Air-sensitive,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   mixed
_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                70.084(2)
_cell_angle_beta                 81.755(2)
_cell_angle_gamma                64.564(3)
_cell_formula_units_Z            2
_cell_length_a                   20.4699(6)
_cell_length_b                   20.4809(5)
_cell_length_c                   21.4594(5)
_cell_measurement_reflns_used    37090
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.5740
_cell_measurement_theta_min      3.8600
_cell_volume                     7638.6(4)
_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 2018/2 (Sheldrick, 2018)'
_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 0.996
_diffrn_measured_fraction_theta_max 0.969
_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    -70.00  32.00   1.00    8.00    --  -41.40  57.00  60.00  102
  2  \w   -114.00 -13.00   1.00    8.00    --  -41.40 -57.00 -90.00  101
  3  \w    -66.00  33.00   1.00    8.00    --  -41.40  38.00-150.00   99
  4  \w    -86.00  -6.00   1.00    8.00    --  -41.40 125.00 120.00   80
  5  \w     33.00 113.00   1.00   32.00    --  104.66-125.00-180.00   80
  6  \w     33.00 113.00   1.00   32.00    --  104.66-125.00   0.00   80
  7  \w     76.00 178.00   1.00   32.00    --  104.66  30.00 120.00  102
  8  \w     28.00 133.00   1.00   32.00    --  104.66 -30.00 150.00  105
  9  \w     76.00 178.00   1.00   32.00    --  104.66  30.00-150.00  102
 10  \w     97.00 176.00   1.00   32.00    --  104.66 125.00 120.00   79
 11  \w     32.00 134.00   1.00   32.00    --  104.66 -61.00  30.00  102
 12  \w     33.00 113.00   1.00   32.00    --  104.66-125.00-180.00   80
 13  \w     22.00 106.00   1.00   32.00    --  104.66 -94.00  30.00   84
 14  \w     29.00 137.00   1.00   32.00    --  104.66 -77.00 150.00  108
 15  \w   -114.00 -13.00   1.00    8.00    --  -41.40 -57.00 150.00  101
 16  \w   -114.00 -13.00   1.00    8.00    --  -41.40 -57.00 -30.00  101
 17  \w   -114.00 -13.00   1.00    8.00    --  -41.40 -57.00  60.00  101
 18  \w      6.00  81.00   1.00    8.00    --   41.40 -99.00 -90.00   75
 19  \w     76.00 130.00   1.00   32.00    --  104.66  61.00  30.00   54
 20  \w     52.00 178.00   1.00   32.00    --  104.66  15.00 -30.00  126
;
_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      -0.0707804000
_diffrn_orient_matrix_UB_12      0.0561669000
_diffrn_orient_matrix_UB_13      0.0214925000
_diffrn_orient_matrix_UB_21      -0.0091260000
_diffrn_orient_matrix_UB_22      0.0574500000
_diffrn_orient_matrix_UB_23      -0.0702054000
_diffrn_orient_matrix_UB_31      -0.0430372000
_diffrn_orient_matrix_UB_32      -0.0350993000
_diffrn_orient_matrix_UB_33      -0.0209659000
_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     0.0296
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            85219
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.723
_diffrn_reflns_theta_min         3.817
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.970
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.464
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    0.987
_exptl_crystal_description       block
_exptl_crystal_F_000             2472
_exptl_crystal_size_max          0.297
_exptl_crystal_size_mid          0.189
_exptl_crystal_size_min          0.145
_refine_diff_density_max         0.526
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1589
_refine_ls_number_reflns         29465
_refine_ls_number_restraints     623
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0424
_refine_ls_R_factor_gt           0.0369
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0510P)^2^+1.5889P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0955
_refine_ls_wR_factor_ref         0.0991
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25778
_reflns_number_total             29465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08502g2.cif
_cod_data_source_block           hasj240506a
_cod_depositor_comments
'Adding full bibliography for 1573851--1573855.cif.'
_cod_original_cell_volume        7638.7(4)
_cod_database_code               1573855
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C131H211Ca3N6O4P7
_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
 C136-O4A \\sim O4A-C132 \\sim O4-C131 \\sim O4-C127
 with sigma of 0.02
 C127-C128 \\sim C129-C128 \\sim C129-C130 \\sim C130-C131 \\sim C133-C132
\\sim C133-C134 \\sim C135-
 C134 \\sim C136-C135
 with sigma of 0.02
 C128-O4 \\sim O4-C130 \\sim C133-O4A \\sim O4A-C135
 with sigma of 0.02
 C134-O4A \\sim O4-C129
 with sigma of 0.02
 C127-C129 \\sim C129-C131 \\sim C132-C134 \\sim C134-C136
 with sigma of 0.02
 C69-C64 \\sim C65-C64 \\sim C65A-C64
 with sigma of 0.02
 C66A-C65A \\sim C66-C65 \\sim C69-C68A \\sim C69-C68
 with sigma of 0.02
 C67-C66 \\sim C67A-C66A \\sim C68-C67 \\sim C68A-C67A
 with sigma of 0.02
 C70-C65 \\sim C70A-C65A \\sim C27-C33A \\sim C27-C33
 with sigma of 0.01
 C65-C68 \\sim C65A-C68A
 with sigma of 0.02
 C67A-C64 \\sim C64-C67
 with sigma of 0.02
 C66-C68 \\sim C66A-C68A
 with sigma of 0.02
3. Restrained planarity
 C65, C66, C67, C68, C69, C64
 with sigma of 0.1
 C65A, C64, C69, C68A, C67A, C66A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O4A \\sim C132 \\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim O4 \\sim C127
\\sim C128 \\sim C129 \\sim C130 \\sim C131: within 3A with sigma of 0.03 and
sigma for terminal atoms of 0.06 within 3A
C70 \\sim C70A \\sim C65 \\sim C65A \\sim C64 \\sim C66 \\sim C66A \\sim C67
\\sim C67A \\sim C68 \\sim C68A \\sim C69: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 O4A, C132, C133, C134, C135, C136
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C70A)=Sof(H70A)=Sof(C71A)=Sof(H71c)=Sof(H71d)=Sof(C72A)=Sof(H72d)=
 Sof(H72e)=Sof(H72f)=Sof(C73A)=Sof(H73c)=Sof(H73d)=Sof(C74A)=Sof(H74d)=
 Sof(H74e)=Sof(H74f)=Sof(C68A)=Sof(H68A)=Sof(C67A)=Sof(H67A)=Sof(C66A)=
 Sof(H66A)=Sof(C65A)=1-FVAR(1)
 Sof(C65)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68)=Sof(C70)=
 Sof(H70)=Sof(C71)=Sof(H71a)=Sof(H71b)=Sof(C72)=Sof(H72a)=Sof(H72b)=Sof(H72c)=
 Sof(C73)=Sof(H73a)=Sof(H73b)=Sof(C74)=Sof(H74a)=Sof(H74b)=Sof(H74c)=FVAR(1)
 Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34c)=Sof(H34d)=Sof(C35A)=Sof(H35d)=
 Sof(H35e)=Sof(H35f)=Sof(C36A)=Sof(H36c)=Sof(H36d)=Sof(C37A)=Sof(H37d)=
 Sof(H37e)=Sof(H37f)=1-FVAR(2)
 Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34a)=Sof(H34b)=Sof(C35)=Sof(H35a)=Sof(H35b)=
 Sof(H35c)=Sof(C36)=Sof(H36a)=Sof(H36b)=Sof(C37)=Sof(H37a)=Sof(H37b)=Sof(H37c)=
 FVAR(2)
 Sof(O4A)=Sof(C132)=Sof(H13c)=Sof(H13d)=Sof(C133)=Sof(H13e)=Sof(H13f)=
 Sof(C134)=Sof(H13g)=Sof(H13h)=Sof(C135)=Sof(H13i)=Sof(H13j)=Sof(C136)=
 Sof(H13k)=Sof(H13l)=1-FVAR(3)
 Sof(O4)=Sof(C127)=Sof(H12p)=Sof(H12q)=Sof(C128)=Sof(H12r)=Sof(H12s)=Sof(C129)=
 Sof(H12t)=Sof(H12u)=Sof(C130)=Sof(H13m)=Sof(H13n)=Sof(C131)=Sof(H13o)=
 Sof(H13p)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C12(H12), C17(H17), C28(H28), C54(H54), C59(H59), C75(H75), C96(H96),
 C101(H101), C112(H112), C117(H117), C33(H33), C70(H70), C33A(H33A), C70A(H70A)
7.b Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C15(H15a,H15b), C18(H18a,H18b), C20(H20a,H20b), C29(H29a,
 H29b), C31(H31a,H31b), C38(H38a,H38b), C39(H39a,H39b), C40(H40a,H40b),
 C41(H41a,H41b), C42(H42a,H42b), C55(H55a,H55b), C57(H57a,H57b), C60(H60a,H60b),
  C62(H62a,H62b), C76(H76a,H76b), C78(H78a,H78b), C80(H80a,H80b), C81(H81a,
 H81b), C82(H82a,H82b), C83(H83a,H83b), C84(H84a,H84b), C97(H97a,H97b),
 C99(H99a,H99b), C102(H10d,H10e), C104(H10i,H10j), C113(H11a,H11b), C115(H11f,
 H11g), C118(H11k,H11l), C120(H12a,H12b), C122(H12f,H12g), C123(H12h,H12i),
 C124(H12j,H12k), C125(H12l,H12m), C126(H12n,H12o), C34(H34a,H34b), C36(H36a,
 H36b), C71(H71a,H71b), C73(H73a,H73b), C34A(H34c,H34d), C36A(H36c,H36d),
 C71A(H71c,H71d), C73A(H73c,H73d), C132(H13c,H13d), C133(H13e,H13f), C134(H13g,
 H13h), C135(H13i,H13j), C136(H13k,H13l), C127(H12p,H12q), C128(H12r,H12s),
 C129(H12t,H12u), C130(H13m,H13n), C131(H13o,H13p)
7.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C24(H24), C25(H25), C26(H26), C50(H50), C51(H51),
 C52(H52), C66(H66), C67(H67), C68(H68), C92(H92), C93(H93), C94(H94),
 C108(H108), C109(H109), C110(H110), C68A(H68A), C67A(H67A), C66A(H66A)
7.d Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C5(H5a,H5b,H5c), C14(H14a,H14b,H14c), C16(H16a,H16b,H16c),
 C19(H19a,H19b,H19c), C21(H21a,H21b,H21c), C30(H30a,H30b,H30c), C32(H32a,H32b,
 H32c), C43(H43a,H43b,H43c), C47(H47a,H47b,H47c), C56(H56a,H56b,H56c), C58(H58a,
 H58b,H58c), C61(H61a,H61b,H61c), C63(H63a,H63b,H63c), C77(H77a,H77b,H77c),
 C79(H79a,H79b,H79c), C85(H85a,H85b,H85c), C89(H89a,H89b,H89c), C98(H98a,H98b,
 H98c), C100(H10a,H10b,H10c), C103(H10f,H10g,H10h), C105(H10k,H10l,H10m),
 C114(H11c,H11d,H11e), C116(H11h,H11i,H11j), C119(H11m,H11n,H11o), C121(H12c,
 H12d,H12e), C35(H35a,H35b,H35c), C37(H37a,H37b,H37c), C72(H72a,H72b,H72c),
 C74(H74a,H74b,H74c), C35A(H35d,H35e,H35f), C37A(H37d,H37e,H37f), C72A(H72d,
 H72e,H72f), C74A(H74d,H74e,H74f)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              87542
_shelx_hkl_checksum              33589
_shelx_fab_checksum              14664
_olex2_date_sample_data_collection 2024-05-06
_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 1.958
_oxdiff_exptl_absorpt_empirical_full_min 0.607