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_1570791
_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_absolute_configuration unk
_chemical_formula_moiety         'C34 H49 Mn N2 O2 P2'
_chemical_formula_sum            'C34 H49 Mn N2 O2 P2'
_chemical_formula_weight         634.63
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-27
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2022.11.02 svn.ra8b101fa for OlexSys, GUI svn.r6635)
;
_audit_update_record
;
2022-12-07 deposited with the CCDC.	2024-01-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.110(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.5026(5)
_cell_length_b                   16.9110(6)
_cell_length_c                   21.3649(10)
_cell_measurement_reflns_used    8687
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      69.2220
_cell_measurement_theta_min      3.3550
_cell_volume                     3380.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.63a (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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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   -112.00 -75.00   0.25    3.50    --  -68.07 -20.00 -87.00  148
  2  \w   -108.00 -58.00   0.25    3.50    --  -68.68 -20.00 -87.00  200
  3  \w     58.00 109.00   0.25    3.50    --   68.80  20.00  79.00  204
  4  \w     91.00 117.00   0.25    3.50    --   73.16  20.00  79.00  104
  5  \w     41.00  67.00   0.25    3.50    --   34.00  76.00 170.56  104
  6  \w     66.00  94.00   0.25    3.50    --   54.00  59.00  63.12  112
  7  \w     72.00  98.00   0.25    3.50    --   62.00  71.00 -14.54  104
  8  \w    -98.00 -73.00   0.25    3.50    --  -62.00 -71.00 -60.64  100
  9  \w     73.00  99.00   0.25    3.50    --   62.00  62.00  98.62  104
 10  \w   -107.00 -78.00   0.25    3.50    --  -66.00 -56.00 142.11  116
 11  \w   -107.00 -78.00   0.25    3.50    --  -66.00 -56.00-178.52  116
 12  \w    -64.00 -33.00   0.25    3.50    --  -68.07   0.00   0.00  124
 13  \w   -102.00 -67.00   0.25    3.50    --  -68.07   0.00   0.00  140
 14  \w     54.00  93.00   0.25    3.50    --   68.80-125.00-180.00  156
 15  \w     32.00  77.00   0.25    3.50    --   68.80-125.00 -90.00  180
 16  \w   -115.00 -89.00   0.25    3.50    --  -70.00 -38.00 -93.80  104
 17  \w     36.00  83.00   0.25    3.50    --   73.16-125.00-120.00  188
 18  \w   -115.00 -89.00   0.25    3.50    --  -74.00 -39.00  -8.31  104
 19  \w    -73.00 -48.00   0.25    3.50    --  -74.00  84.00-107.36  100
 20  \w   -118.00 -92.00   0.25    3.50    --  -74.00 -37.00  48.41  104
 21  \w    -67.00 -42.00   0.25    3.50    --  -74.00  74.00 -41.93  100
 22  \w     36.00  64.00   0.25    3.50    --   77.50 -52.00 -71.76  112
 23  \w     93.00 120.00   0.25    3.50    --   77.50  37.00 -72.00  108
 24  \w     77.00 104.00   0.25    3.50    --   77.50-126.00-157.03  108
 25  \w     37.00  62.00   0.25    3.50    --   77.50 -56.00 -18.25  100
 26  \w     44.00  70.00   0.25    3.50    --   77.50-126.00-157.03  104
 27  \w     56.00 100.00   0.25    3.50    --   77.50-121.00-104.76  176
 28  \w     39.00  64.00   0.25    3.50    --   77.50 -63.00 158.93  100
 29  \w     40.00  66.00   0.25    3.50    --   77.50 -63.00 -93.73  104
 30  \w     36.00  61.00   0.25    3.50    --   77.50 -52.00 -38.48  100
 31  \w     36.00  61.00   0.25    3.50    --   77.50 -54.00  82.91  100
 32  \w     38.00  65.00   0.25    3.50    --   77.50 -56.00  33.18  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1544676000
_diffrn_orient_matrix_UB_12      -0.0238800000
_diffrn_orient_matrix_UB_13      -0.0041663000
_diffrn_orient_matrix_UB_21      -0.0374022000
_diffrn_orient_matrix_UB_22      0.0020708000
_diffrn_orient_matrix_UB_23      -0.0731737000
_diffrn_orient_matrix_UB_31      0.0427873000
_diffrn_orient_matrix_UB_32      0.0879063000
_diffrn_orient_matrix_UB_33      0.0004748000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            12804
_diffrn_reflns_point_group_measured_fraction_full 0.837
_diffrn_reflns_point_group_measured_fraction_max 0.837
_diffrn_reflns_theta_full        65.086
_diffrn_reflns_theta_max         65.086
_diffrn_reflns_theta_min         3.353
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.308
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59967
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.63a (Rigaku Oxford Diffraction, 2022)
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    1.247
_exptl_crystal_description       plate
_exptl_crystal_F_000             1352
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.809
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.096
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.481(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     683
_refine_ls_number_reflns         12804
_refine_ls_number_restraints     657
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0978
_refine_ls_R_factor_gt           0.0888
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0894P)^2^+12.8791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2071
_refine_ls_wR_factor_ref         0.2140
_reflns_Friedel_coverage         0.618
_reflns_Friedel_fraction_full    0.665
_reflns_Friedel_fraction_max     0.665
_reflns_number_gt                11471
_reflns_number_total             12804
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9773\% 
around [0.93 0.00 -0.37] (reciprocal) or [1.00 0.00 -0.00] (direct)
;
_cod_data_source_file            d3sc04935c2.cif
_cod_data_source_block           m2319_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1570790--1570791.cif.'
_cod_database_code               1570791
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H30 N2 O2 P2 Mn1'
_chemical_oxdiff_usercomment     Rajan
_shelx_estimated_absorpt_t_max   0.882
_shelx_estimated_absorpt_t_min   0.604
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.522(2)
 0.478(2)
2. 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
3. Restrained distances
 H48B-H45B
 -2.1 with sigma of 0.01
 H48B-H45C
 -2.1 with sigma of 0.01
 H45C-H48C
 -2.1 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C13) = Uanis(C18)
Uanis(C33) = Uanis(O1)
Uanis(C14) = Uanis(C17)
Uanis(C22) = Uanis(C17)
Uanis(C23) = Uanis(C18)
Uanis(C1) = Uanis(C4)
Uanis(Mn1) = Uanis(N2)
Uanis(C21) = Uanis(C19)
Uanis(P1) = Uanis(C15)
Uanis(C50) = Uanis(C54)
Uanis(C44) = Uanis(C43)
5. Rigid body (RIGU) restrains
 Mn1, P1, P2, O1, O2, N1, N2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11,
 C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27,
  C32, C31, C30, C29, C28, C33, C34
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Mn2, P3, P4, O3, O4, N3, N4, C35, C36, C37, C38, C39, C40, C42, C43, C44, C45,
  C46, C47, C48, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60,
 C61, C62, C63, C64, C65, C66, C67, C68
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6.a Ternary CH refined with riding coordinates:
 C1(H1), C35(H35)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C41(H41A,H41B)
6.c Me refined with riding coordinates:
 C19(H19A,H19B,H19C), C23(H23A,H23B,H23C), C44(H44A,H44B,H44C)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C25(H25), C26(H26), C32(H32), C31(H31), C30(H30),
 C29(H29), C28(H28), C37(H37), C38(H38), C39(H39), C59(H59), C60(H60), C62(H62),
  C63(H63), C64(H64), C65(H65), C66(H66)
6.e Fitted hexagon refined as free rotating group:
 C27(C32,C31,C30,C29,C28)
6.f 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), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C43(H43A,H43B,H43C),
 C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C55(H55A,
 H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C)
;
_shelx_res_checksum              52027
_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 1.685
_oxdiff_exptl_absorpt_empirical_full_min 0.600
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2