Manganese-catalyzed base-free addition of saturated nitriles to unsaturated nitriles by template catalysis.
Thiyagarajan, Subramanian; Diskin-Posner, Yael; Montag, Michael; Milstein, David; Chemical science 15 (2024) 2571–2577; doi:10.1039/d3sc04935c

data_1570790
_publ_section_title
;
 Manganese-catalyzed base-free addition of saturated nitriles to
 unsaturated nitriles by template catalysis.
;
_journal_issue                   7
_journal_name_full               'Chemical science'
_journal_page_first              2571
_journal_page_last               2577
_journal_paper_doi               10.1039/d3sc04935c
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '4(C34 H49 Mn N2 O2 P2), H2 O'
_chemical_formula_sum            'C136 H198 Mn4 N8 O9 P8'
_chemical_formula_weight         2556.53
_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             2022-12-06
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.11.02 svn.ra8b101fa for OlexSys, GUI svn.r6635)
;
_audit_update_record
;
2022-12-06 deposited with the CCDC.	2024-01-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.648(2)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   10.4236(3)
_cell_length_b                   17.9728(5)
_cell_length_c                   17.9093(5)
_cell_measurement_reflns_used    21251
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      31.0390
_cell_measurement_theta_min      1.9360
_cell_volume                     3354.94(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.54a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.869
_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    -26.00  21.00   0.25    4.00    --  -16.86 -68.00  88.00  188
  2  \w    -91.00 -32.00   0.25    4.00    --  -16.86 -68.00  88.00  236
  3  \w     -2.00  51.00   0.25    4.00    --   15.45 -99.00  30.00  212
  4  \w     -1.00  63.00   0.25    4.00    --   15.45 -99.00 -60.00  256
  5  \w     -2.00  67.00   0.25    4.00    --   15.45 -99.00-180.00  276
  6  \w    -65.00  -9.00   0.25    4.00    --   15.45 -77.00  60.00  224
  7  \w     -3.00  57.00   0.25    4.00    --   15.45 -77.00  60.00  240
  8  \w      8.00  33.00   0.25    4.00    --   15.45 -99.00-150.00  100
  9  \w     34.00  60.00   0.25    4.00    --   15.45 -99.00-150.00  104
 10  \w    -21.00  42.00   0.25    4.00    --  -16.86  68.00-138.00  252
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0081093000
_diffrn_orient_matrix_UB_12      -0.0277966000
_diffrn_orient_matrix_UB_13      0.0276367000
_diffrn_orient_matrix_UB_21      -0.0633007000
_diffrn_orient_matrix_UB_22      0.0128570000
_diffrn_orient_matrix_UB_23      0.0062955000
_diffrn_orient_matrix_UB_31      -0.0236633000
_diffrn_orient_matrix_UB_32      -0.0248821000
_diffrn_orient_matrix_UB_33      -0.0276640000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0499
_diffrn_reflns_av_unetI/netI     0.0464
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.869
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            43438
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.869
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.384
_diffrn_reflns_theta_min         1.954
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.522
_exptl_absorpt_correction_T_max  0.312
_exptl_absorpt_correction_T_min  0.094
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.54a (Rigaku Oxford Diffraction, 2022)
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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.265
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1362
_exptl_crystal_size_max          0.161
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.426
_refine_diff_density_min         -0.299
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     391
_refine_ls_number_reflns         9616
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0434
_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^)+(0.0474P)^2^+0.6240P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0999
_refine_ls_wR_factor_ref         0.1057
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7542
_reflns_number_total             9616
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04935c2.cif
_cod_data_source_block           m2320_auto
_cod_depositor_comments
'Adding full bibliography for 1570790--1570791.cif.'
_cod_original_cell_volume        3354.92(17)
_cod_database_code               1570790
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H30 N2 O2 P2 Mn1'
_chemical_oxdiff_usercomment     Rajan
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_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 O(H,H) groups
2. Others
 Fixed Sof: O3(0.25) H3A(0.25) H3B(0.25)
3.a Riding coordinates:
 O3(H3A,H3B)
3.b Ternary CH refined with riding coordinates:
 C1(H1)
3.c Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
3.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30),
 C31(H31), C32(H32)
3.e Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C)
;
_shelx_res_checksum              23992
_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 1.553
_oxdiff_exptl_absorpt_empirical_full_min 0.529