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_1573853
_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         'C82 H134 Ca2 N4 O2 P4, 2(C4 H10 O)'
_chemical_formula_sum            'C90 H154 Ca2 N4 O4 P4'
_chemical_formula_weight         1560.20
_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   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                90
_cell_angle_beta                 111.8607(18)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.4588(2)
_cell_length_b                   23.0603(3)
_cell_length_c                   15.7858(2)
_cell_measurement_reflns_used    18244
_cell_measurement_temperature    99.98(12)
_cell_measurement_theta_max      72.5060
_cell_measurement_theta_min      5.2000
_cell_volume                     4547.04(12)
_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(12)
_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 0.980
_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    -82.00  39.00   1.00    2.25    --  -41.40  19.00 120.00  121
  2  \w   -116.00 -17.00   1.00    2.25    --  -41.40 -38.00 -60.00   99
  3  \w     27.00  95.00   1.00    2.25    --   41.40-125.00  90.00   68
  4  \w     28.00 133.00   1.00    9.00    --  104.66 -30.00  60.00  105
  5  \w     76.00 177.00   1.00    9.00    --  104.66  61.00 120.00  101
  6  \w     76.00 178.00   1.00    9.00    --  104.66  30.00   0.00  102
  7  \w     97.00 176.00   1.00    9.00    --  104.66 125.00 150.00   79
  8  \w     97.00 176.00   1.00    9.00    --  104.66 125.00  90.00   79
  9  \w     22.00 106.00   1.00    9.00    --  104.66 -94.00  90.00   84
 10  \w     33.00 113.00   1.00    9.00    --  104.66-125.00 -90.00   80
 11  \w     28.00 133.00   1.00    9.00    --  104.66 -30.00  60.00  105
 12  \w    103.00 178.00   1.00    9.00    --  104.66  77.00-150.00   75
 13  \w   -114.00 -45.00   1.00    2.25    --  -41.40 -57.00-150.00   69
 14  \w   -114.00 -13.00   1.00    2.25    --  -41.40 -57.00  90.00  101
;
_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      -0.0801382000
_diffrn_orient_matrix_UB_12      0.0444420000
_diffrn_orient_matrix_UB_13      0.0104178000
_diffrn_orient_matrix_UB_21      0.0297112000
_diffrn_orient_matrix_UB_22      0.0427414000
_diffrn_orient_matrix_UB_23      -0.0617562000
_diffrn_orient_matrix_UB_31      -0.0886019000
_diffrn_orient_matrix_UB_32      -0.0259057000
_diffrn_orient_matrix_UB_33      -0.0845621000
_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  0.0638
_diffrn_reflns_av_unetI/netI     0.0445
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            34888
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.605
_diffrn_reflns_theta_min         3.538
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.121
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79867
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.106a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.140
_exptl_crystal_description       block
_exptl_crystal_F_000             1708
_exptl_crystal_size_max          0.272
_exptl_crystal_size_mid          0.226
_exptl_crystal_size_min          0.194
_refine_diff_density_max         0.768
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     717
_refine_ls_number_reflns         8864
_refine_ls_number_restraints     1069
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0622
_refine_ls_R_factor_gt           0.0584
_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^)+(0.0703P)^2^+3.9761P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1529
_refine_ls_wR_factor_ref         0.1569
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8169
_reflns_number_total             8864
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08502g2.cif
_cod_data_source_block           hasj240524a
_cod_depositor_comments
'Adding full bibliography for 1573851--1573855.cif.'
_cod_original_cell_volume        4547.02(13)
_cod_database_code               1573853
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C90H154Ca2N4O4P4
_shelx_estimated_absorpt_t_max   0.684
_shelx_estimated_absorpt_t_min   0.596
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H16a,H16b,H16c} of C16, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups, {H30a,H30b,H30c} of C30, {H19a,H19b,H19c} of C19,
   {H35a,H35b,H35c} of C35, {H32A,H32B,H32C} of C32A, {H1a,H1b,H1c} of C1,
  {H14a,H14b,H14c} of C14, {H5a,H5b,H5c} of C5, {H35D,H35E,H35F} of C35A, {H19D,
  H19E,H19F} of C19A, {H39D,H39E,H39F} of C39A, {H30D,H30E,H30F} of C30A, {H39a,
  H39b,H39c} of C39, {H41D,H41E,H41F} of C41A, {H41a,H41b,H41c} of C41, {H43D,
  H43E,H43F} of C43A, {H32d,H32e,H32f} of C32, {H45A,H45B,H45C} of C45, {H45D,
  H45E,H45F} of C45A, {H43A,H43B,H43C} of C43
2. Restrained distances
 O1-C40 \\sim O1A-C40A \\sim O1-C38 \\sim O1A-C38A
 with sigma of 0.02
 C40A-C41A \\sim C41-C40 \\sim C39A-C38A \\sim C39-C38
 with sigma of 0.02
 C42A-C43A \\sim C42-C43 \\sim C44A-C45A \\sim C45-C44
 with sigma of 0.02
 O2A-C42A \\sim O2-C42 \\sim O2A-C44A \\sim O2-C44
 with sigma of 0.02
 Ca1-O1 \\sim Ca1-O1A
 with sigma of 0.02
 C17-C11 \\sim C17A-C11 \\sim C28A-C23 \\sim C28-C23
 with sigma of 0.02
 C20A-C17A \\sim C20-C17 \\sim C18-C17 \\sim C18A-C17A \\sim C34-C33 \\sim
C34A-C33 \\sim C36A-C33 ~
 C36-C33 \\sim C29A-C28A \\sim C29-C28 \\sim C31-C28 \\sim C31A-C28A
 with sigma of 0.02
 C37-C36A \\sim C37-C36 \\sim C35A-C34A \\sim C35-C34 \\sim C30A-C29A \\sim
C30-C29 \\sim C32A-C31A ~
 C32-C31 \\sim C19-C18 \\sim C19A-C18A \\sim C21-C20A \\sim C21-C20
 with sigma of 0.02
 C34-C36 \\sim C34A-C36A \\sim C20-C18 \\sim C20A-C18A \\sim C31A-C29A \\sim
C29-C31
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
P1 \\sim P2 \\sim P1A \\sim P2A: within 2A with sigma of 0.03 and sigma for
terminal atoms of 0.6 within 2A
O2 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim O2A \\sim C42A \\sim C43A
\\sim C44A \\sim C45A: within 3A with sigma of 0.03 and sigma for terminal
atoms of 0.06 within 3A
O1 \\sim C38 \\sim C40 \\sim C41 \\sim O1A \\sim C38A \\sim C40A \\sim C41A:
within 3A with sigma of 0.03 and sigma for terminal atoms of 0.06 within 3A
C21 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C17A \\sim C18A \\sim C19A
\\sim C20A: within 4A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 4A
C30 \\sim C29A \\sim C29 \\sim C30A \\sim C28A \\sim C28 \\sim C31A \\sim C31
\\sim C32A \\sim C32: within 4A with sigma of 0.02 and sigma for terminal atoms
of 0.04 within 4A
4. Rigid body (RIGU) restrains
 C33, C34A, C35A, C36A, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 P1A, P2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1A, C38A, C40A, C41A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C28, C23, C31
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20A, C17A, C18A, C11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(P1A)=Sof(P2A)=1-FVAR(1)
 Sof(P1)=Sof(P2)=FVAR(1)
 Sof(O1A)=Sof(C38A)=Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39D)=Sof(H39E)=
 Sof(H39F)=Sof(C40A)=Sof(H40C)=Sof(H40D)=Sof(C41A)=Sof(H41D)=Sof(H41E)=
 Sof(H41F)=1-FVAR(2)
 Sof(O1)=Sof(C38)=Sof(H38a)=Sof(H38b)=Sof(C39)=Sof(H39a)=Sof(H39b)=Sof(H39c)=
 Sof(C40)=Sof(H40a)=Sof(H40b)=Sof(C41)=Sof(H41a)=Sof(H41b)=Sof(H41c)=FVAR(2)
 Sof(H33A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C34A)=Sof(H34C)=Sof(H34D)=
 Sof(C35A)=Sof(H35D)=Sof(H35E)=Sof(H35F)=Sof(C36A)=Sof(H36C)=Sof(H36D)=1-FVAR(3)
 Sof(H33)=Sof(H37a)=Sof(H37b)=Sof(H37c)=Sof(C34)=Sof(H34a)=Sof(H34b)=Sof(C35)=
 Sof(H35a)=Sof(H35b)=Sof(H35c)=Sof(C36)=Sof(H36a)=Sof(H36b)=FVAR(3)
 Sof(O2)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=1-FVAR(4)
 Sof(O2A)=Sof(C42A)=Sof(H42C)=Sof(H42D)=Sof(C43A)=Sof(H43D)=Sof(H43E)=
 Sof(H43F)=Sof(C44A)=Sof(H44C)=Sof(H44D)=Sof(C45A)=Sof(H45D)=Sof(H45E)=
 Sof(H45F)=FVAR(4)
 Sof(C28A)=Sof(H28A)=Sof(C31A)=Sof(H31A)=Sof(H31B)=Sof(C32A)=Sof(H32A)=
 Sof(H32B)=Sof(H32C)=Sof(C29A)=Sof(H29C)=Sof(H29D)=Sof(C30A)=Sof(H30D)=
 Sof(H30E)=Sof(H30F)=1-FVAR(5)
 Sof(C29)=Sof(H29a)=Sof(H29b)=Sof(C30)=Sof(H30a)=Sof(H30b)=Sof(H30c)=Sof(C28)=
 Sof(H28)=Sof(C31)=Sof(H31c)=Sof(H31d)=Sof(C32)=Sof(H32d)=Sof(H32e)=Sof(H32f)=
 FVAR(5)
 Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18C)=
 Sof(H18D)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20A)=Sof(H20C)=
 Sof(H20D)=1-FVAR(6)
 Sof(H21a)=Sof(H21b)=Sof(H21c)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18a)=Sof(H18b)=
 Sof(C19)=Sof(H19a)=Sof(H19b)=Sof(H19c)=Sof(C20)=Sof(H20a)=Sof(H20b)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C28A(H28A), C33(H33), C33(H33A), C17(H17), C17A(H17A), C28(H28)
6.b Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C15(H15a,H15b), C31A(H31A,H31B), C18(H18a,H18b), C20(H20a,
 H20b), C29(H29a,H29b), C34(H34a,H34b), C36(H36a,H36b), C38(H38a,H38b),
 C40(H40a,H40b), C18A(H18C,H18D), C20A(H20C,H20D), C29A(H29C,H29D), C34A(H34C,
 H34D), C36A(H36C,H36D), C38A(H38C,H38D), C40A(H40C,H40D), C42(H42A,H42B),
 C44(H44A,H44B), C42A(H42C,H42D), C44A(H44C,H44D), C31(H31c,H31d)
6.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C24(H24), C25(H25), C26(H26)
6.d Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C5(H5a,H5b,H5c), C14(H14a,H14b,H14c), C16(H16a,H16b,H16c),
 C21(H21a,H21b,H21c), C21(H21D,H21E,H21F), C32A(H32A,H32B,H32C), C37(H37a,H37b,
 H37c), C37(H37D,H37E,H37F), C19(H19a,H19b,H19c), C30(H30a,H30b,H30c), C35(H35a,
 H35b,H35c), C39(H39a,H39b,H39c), C41(H41a,H41b,H41c), C19A(H19D,H19E,H19F),
 C30A(H30D,H30E,H30F), C35A(H35D,H35E,H35F), C39A(H39D,H39E,H39F), C41A(H41D,
 H41E,H41F), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C43A(H43D,H43E,H43F),
 C45A(H45D,H45E,H45F), C32(H32d,H32e,H32f)
;
_shelx_res_checksum              38782
_shelx_hkl_checksum              20478
_olex2_date_sample_data_collection 2024-05-24
_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 1.870
_oxdiff_exptl_absorpt_empirical_full_min 0.615