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_1573854
_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         '2(C44 H64 B Ca N2), 1.5(C6 H12)'
_chemical_formula_sum            'C97 H146 B2 Ca2 N4'
_chemical_formula_weight         1469.95
_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
_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                106.025(2)
_cell_angle_beta                 90.6120(10)
_cell_angle_gamma                98.438(2)
_cell_formula_units_Z            2
_cell_length_a                   12.7375(2)
_cell_length_b                   16.5295(3)
_cell_length_c                   21.8122(3)
_cell_measurement_reflns_used    15204
_cell_measurement_temperature    99.97(16)
_cell_measurement_theta_max      72.4620
_cell_measurement_theta_min      3.9470
_cell_volume                     4359.87(13)
_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      99.97(16)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.966
_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    -66.00  29.00   1.00    3.70    --  -41.40  38.00   0.00   95
  2  \w    -70.00  30.00   1.00    3.70    --  -41.40  57.00-150.00  100
  3  \w   -113.00 -20.00   1.00    3.70    --  -41.40 -57.00  60.00   93
  4  \w     45.00  95.00   1.00    3.70    --   41.40-125.00  30.00   50
  5  \w     39.00 125.00   1.00   14.50    --  104.66 -45.00  60.00   86
  6  \w    101.00 174.00   1.00   14.50    --  104.66 125.00  60.00   73
  7  \w    120.00 171.00   1.00   14.50    --  104.66  96.00 174.00   51
  8  \w     76.00 177.00   1.00   14.50    --  104.66  30.00-120.00  101
  9  \w    103.00 176.00   1.00   14.50    --  104.66  77.00 150.00   73
 10  \w     25.00 106.00   1.00   14.50    --  104.66 -94.00  90.00   81
 11  \w     27.00 105.00   1.00   14.50    --  104.66 -94.00   0.00   78
 12  \w     33.00 113.00   1.00   14.50    --  104.66-125.00 -60.00   80
 13  \w     53.00 113.00   1.00   14.50    --  104.66-125.00-120.00   60
 14  \w    112.00 178.00   1.00   14.50    --  104.66  30.00 120.00   66
;
_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      -0.0270600000
_diffrn_orient_matrix_UB_12      0.0651693000
_diffrn_orient_matrix_UB_13      -0.0339903000
_diffrn_orient_matrix_UB_21      0.0409715000
_diffrn_orient_matrix_UB_22      0.0731953000
_diffrn_orient_matrix_UB_23      0.0599652000
_diffrn_orient_matrix_UB_31      0.1121728000
_diffrn_orient_matrix_UB_32      0.0056767000
_diffrn_orient_matrix_UB_33      -0.0257769000
_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  0.0257
_diffrn_reflns_av_unetI/netI     0.0366
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            29288
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.481
_diffrn_reflns_theta_min         3.513
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.477
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.564
_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 orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.120
_exptl_crystal_description       block
_exptl_crystal_F_000             1612
_exptl_crystal_size_max          0.325
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.118
_refine_diff_density_max         0.839
_refine_diff_density_min         -0.417
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1176
_refine_ls_number_reflns         16686
_refine_ls_number_restraints     1859
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0468
_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^)+(0.0628P)^2^+1.9961P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1191
_refine_ls_wR_factor_ref         0.1263
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14270
_reflns_number_total             16686
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08502g2.cif
_cod_data_source_block           hasj240219a
_cod_depositor_comments
'Adding full bibliography for 1573851--1573855.cif.'
_cod_database_code               1573854
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C97H146B2Ca2N4
_shelx_estimated_absorpt_t_max   0.845
_shelx_estimated_absorpt_t_min   0.645
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C92-C97 \\sim C92A-C93A \\sim C92-C93 \\sim C95A-C94A \\sim C93-C94 \\sim
C95-C94 \\sim C96-C95 ~
 C95A-C96A \\sim C92A-C97A \\sim C96-C97 \\sim C94A-C93A \\sim C92B-C97B \\sim
C92B-C93B \\sim C93B-
 C94B \\sim C94B-C95B \\sim C95B-C96B \\sim C97B-C96B
 with sigma of 0.01
 C95-C93 \\sim C94-C92 \\sim C93-C97 \\sim C92-C96 \\sim C97-C95 \\sim C96-C94
\\sim C97A-C93A \\sim C92A-
 C94A \\sim C93A-C95A \\sim C94A-C96A \\sim C95A-C97A \\sim C96A-C92A \\sim
C94B-C92B \\sim C93B-C97B ~
 C92B-C96B \\sim C97B-C95B \\sim C96B-C94B \\sim C95B-C93B
 with sigma of 0.01
 C56-C51 \\sim C56A-C51 \\sim C77A-C71 \\sim C77-C71
 with sigma of 0.02
 C57-C56 \\sim C56A-C57A \\sim C59-C56 \\sim C56A-C59A \\sim C77A-C80A \\sim
C80-C77 \\sim C78-C77 ~
 C77A-C78A
 with sigma of 0.02
 C58A-C57A \\sim C58-C57 \\sim C60A-C59A \\sim C60-C59 \\sim C81A-C80A \\sim
C81-C80 \\sim C79A-C78A ~
 C79-C78
 with sigma of 0.02
 C57-C59 \\sim C57A-C59A
 with sigma of 0.02
 C94A-C97A \\sim C92A-C95A \\sim C96A-C93A \\sim C97-C94 \\sim C95-C92 \\sim
C96-C93 \\sim C97B-C94B ~
 C96B-C93B \\sim C92B-C95B
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C92A \\sim C93A \\sim C94A \\sim C95A \\sim C96A \\sim C97A \\sim C92 \\sim C93
\\sim C94 \\sim C95 \\sim C96 \\sim C97: within 4A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 4A
C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C56A \\sim C57A \\sim C58A
\\sim C59A \\sim C60A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C77A \\sim C78A \\sim C79A
\\sim C80A \\sim C81A: within 4A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 4A
C92A \\sim C93A \\sim C94A \\sim C95A \\sim C96A \\sim C97A \\sim C92B \\sim
C93B \\sim C94B \\sim C95B \\sim C96B \\sim C97B \\sim C92 \\sim C93 \\sim C94
\\sim C95 \\sim C96 \\sim C97: within 4A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 4A
4. Rigid body (RIGU) restrains
 C51, C56, C57, C59, C56A, C57A, C59A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C71, C77A, C78A, C80A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(C92)+Sof(H92e)+Sof(H92f)+Sof(C93)+Sof(H93e)+Sof(H93f)+Sof(C94)+
 Sof(H94e)+Sof(H94f)+Sof(C95)+Sof(H95e)+Sof(H95f)+Sof(C96)+Sof(H96e)+Sof(H96f)+
 Sof(C97)+Sof(H97e)+Sof(H97f)]+1*[Sof(C92B)+Sof(H92c)+Sof(H92d)+Sof(C93B)+
 Sof(H93c)+Sof(H93d)+Sof(C94B)+Sof(H94c)+Sof(H94d)+Sof(C95B)+Sof(H95c)+
 Sof(H95d)+Sof(C96B)+Sof(H96c)+Sof(H96d)+Sof(C97B)+Sof(H97c)+Sof(H97d)]+1*
 [Sof(C92A)+Sof(H92a)+Sof(H92b)+Sof(C93A)+Sof(H93a)+Sof(H93b)+Sof(C94A)+
 Sof(H94a)+Sof(H94b)+Sof(C95A)+Sof(H95a)+Sof(H95b)+Sof(C96A)+Sof(H96a)+
 Sof(H96b)+Sof(C97A)+Sof(H97a)+Sof(H97b)]=1 with esd of 0
 Sof(C92)=Sof(H92e)=Sof(H92f)=Sof(C93)=Sof(H93e)=Sof(H93f)=Sof(C94)=Sof(H94e)=
 Sof(H94f)=Sof(C95)=Sof(H95e)=Sof(H95f)=Sof(C96)=Sof(H96e)=Sof(H96f)=Sof(C97)=
 Sof(H97e)=Sof(H97f)=FVAR(1)
 Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(H57c)=Sof(H57d)=Sof(C58A)=Sof(H58d)=
 Sof(H58e)=Sof(H58f)=Sof(C59A)=Sof(H59c)=Sof(H59d)=Sof(C60A)=Sof(H60d)=
 Sof(H60e)=Sof(H60f)=1-FVAR(2)
 Sof(C56)=Sof(H56)=Sof(C57)=Sof(H57a)=Sof(H57b)=Sof(C58)=Sof(H58a)=Sof(H58b)=
 Sof(H58c)=Sof(C59)=Sof(H59a)=Sof(H59b)=Sof(C60)=Sof(H60a)=Sof(H60b)=Sof(H60c)=
 FVAR(2)
 Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78c)=Sof(H78d)=Sof(C79A)=Sof(H79d)=
 Sof(H79e)=Sof(H79f)=Sof(C80A)=Sof(H80c)=Sof(H80d)=Sof(C81A)=Sof(H81d)=
 Sof(H81e)=Sof(H81f)=1-FVAR(3)
 Sof(C77)=Sof(H77)=Sof(C78)=Sof(H78a)=Sof(H78b)=Sof(C79)=Sof(H79a)=Sof(H79b)=
 Sof(H79c)=Sof(C80)=Sof(H80a)=Sof(H80b)=Sof(C81)=Sof(H81a)=Sof(H81b)=Sof(H81c)=
 FVAR(3)
 Sof(C92B)=Sof(H92c)=Sof(H92d)=Sof(C93B)=Sof(H93c)=Sof(H93d)=Sof(C94B)=
 Sof(H94c)=Sof(H94d)=Sof(C95B)=Sof(H95c)=Sof(H95d)=Sof(C96B)=Sof(H96c)=
 Sof(H96d)=Sof(C97B)=Sof(H97c)=Sof(H97d)=FVAR(4)
 Sof(C92A)=Sof(H92a)=Sof(H92b)=Sof(C93A)=Sof(H93a)=Sof(H93b)=Sof(C94A)=
 Sof(H94a)=Sof(H94b)=Sof(C95A)=Sof(H95a)=Sof(H95b)=Sof(C96A)=Sof(H96a)=
 Sof(H96b)=Sof(C97A)=Sof(H97a)=Sof(H97b)=FVAR(5)
 Sof(H1bd)=Sof(H1be)=Sof(H1bf)=1-FVAR(6)
 Sof(H1aa)=Sof(H1ab)=Sof(H1ac)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C12(H12), C17(H17), C28(H28), C33(H33), C61(H61), C72(H72), C56(H56),
 C77(H77), C56A(H56A), C77A(H77A)
6.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), C34(H34a,H34b), C36(H36a,H36b), C62(H62a,H62b),
 C64(H64a,H64b), C73(H73a,H73b), C75(H75a,H75b), C57(H57a,H57b), C59(H59a,H59b),
  C78(H78a,H78b), C80(H80a,H80b), C57A(H57c,H57d), C59A(H59c,H59d), C78A(H78c,
 H78d), C80A(H80c,H80d), C92A(H92a,H92b), C93A(H93a,H93b), C94A(H94a,H94b),
 C95A(H95a,H95b), C96A(H96a,H96b), C97A(H97a,H97b), C92B(H92c,H92d), C93B(H93c,
 H93d), C94B(H94c,H94d), C95B(H95c,H95d), C96B(H96c,H96d), C97B(H97c,H97d),
 C89(H89a,H89b), C90(H90a,H90b), C91(H91a,H91b), C92(H92e,H92f), C93(H93e,H93f),
  C94(H94e,H94f), C95(H95e,H95f), C96(H96e,H96f), C97(H97e,H97f)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C8(H8), C9(H9), C10(H10), C24(H24), C25(H25), C26(H26), C39(H39),
 C40(H40), C41(H41), C42(H42), C47(H47), C52(H52), C53(H53), C54(H54), C68(H68),
  C69(H69), C70(H70), C83(H83), C84(H84), C85(H85), C86(H86)
6.d Idealised Me refined as rotating group:
 C1(H1aa,H1ab,H1ac), C1(H1bd,H1be,H1bf), 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), C35(H35a,H35b,H35c), C37(H37a,H37b,H37c), C44(H44a,
 H44b,H44c), C45(H45a,H45b,H45c), C49(H49a,H49b,H49c), C63(H63a,H63b,H63c),
 C65(H65a,H65b,H65c), C74(H74a,H74b,H74c), C76(H76a,H76b,H76c), C88(H88a,H88b,
 H88c), C58(H58a,H58b,H58c), C60(H60a,H60b,H60c), C79(H79a,H79b,H79c), C81(H81a,
 H81b,H81c), C58A(H58d,H58e,H58f), C60A(H60d,H60e,H60f), C79A(H79d,H79e,H79f),
 C81A(H81d,H81e,H81f)
;
_shelx_res_checksum              73735
_shelx_hkl_checksum              84737
_olex2_date_sample_data_collection 2024-02-19
_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 1.326
_oxdiff_exptl_absorpt_empirical_full_min 0.789