Solvent-Free Synthesis and Key Intermediate Isolation in Ni<sub>2</sub>Dy<sub>2</sub> Catalyst Development in the Domino Ring-Opening Electrocyclization Reaction of Furfural and Amines.
Sampani, Stavroula I.; McGown, Andrew; Vargas, Alfredo; Abdul-Sada, Alaa; Tizzard, Graham J.; Coles, Simon J.; Spencer, John; Kostakis, George E.; The Journal of organic chemistry 84 (2019) 6858–6867; doi:10.1021/acs.joc.9b00608

data_4034595
_publ_section_title
;
 Solvent-Free Synthesis and Key Intermediate Isolation in
 Ni<sub>2</sub>Dy<sub>2</sub> Catalyst Development in the Domino
 Ring-Opening Electrocyclization Reaction of Furfural and Amines.
;
_journal_issue                   11
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6858
_journal_page_last               6867
_journal_paper_doi               10.1021/acs.joc.9b00608
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety
'C74 H86 Dy2 N10 Ni2 O18, 2(C F3 O3 S), 2(C3 H7 N O)'
_chemical_formula_sum            'C82 H100 Dy2 F6 N12 Ni2 O26 S2'
_chemical_formula_weight         2290.27
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-19
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.02.24 svn.r3390 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.115(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.7112(6)
_cell_length_b                   18.8566(7)
_cell_length_c                   15.7900(6)
_cell_measurement_reflns_used    6394
_cell_measurement_temperature    173
_cell_measurement_theta_max      71.0600
_cell_measurement_theta_min      3.6490
_cell_volume                     4672.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1033
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.955
_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    -29.00  64.00   1.00    2.50    --   36.88 -77.00  60.00   93
  2  \w     47.00  84.00   1.00    7.50    --  107.00 -95.00  90.00   37
  3  \w     38.00  69.00   1.00    7.50    --  107.00 -95.00  30.00   31
  4  \w     39.00 116.00   1.00    7.50    --  107.00 -45.00 120.00   77
  5  \w     94.00 175.00   1.00    7.50    --  107.00  45.00 150.00   81
  6  \w    106.00 172.00   1.00    7.50    --  107.00  77.00-150.00   66
  7  \w     94.00 173.00   1.00    7.50    --  107.00  77.00-180.00   79
  8  \w     37.00  90.00   1.00    7.50    --  107.00-111.00-180.00   53
  9  \w     20.00 103.00   1.00    2.50    --   36.88  57.00-150.00   83
 10  \w   -109.00 -57.00   1.00    2.50    --  -36.88-178.00-120.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0331033000
_diffrn_orient_matrix_UB_12      0.0695269000
_diffrn_orient_matrix_UB_13      0.0512064000
_diffrn_orient_matrix_UB_21      0.0919553000
_diffrn_orient_matrix_UB_22      -0.0206422000
_diffrn_orient_matrix_UB_23      0.0089055000
_diffrn_orient_matrix_UB_31      -0.0110648000
_diffrn_orient_matrix_UB_32      0.0375580000
_diffrn_orient_matrix_UB_33      -0.0897773000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0708
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            14643
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.857
_diffrn_reflns_theta_min         4.690
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.071
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32845
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.628
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             2316
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.178
_refine_diff_density_min         -2.231
_refine_diff_density_rms         0.129
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     595
_refine_ls_number_reflns         8755
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0645
_refine_ls_R_factor_gt           0.0563
_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^)+(0.0911P)^2^+2.4796P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1529
_refine_ls_wR_factor_ref         0.1655
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7511
_reflns_number_total             8755
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00608_si_001.cif
_cod_data_source_block           sis541b
_cod_database_code               4034595
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C176 H212 Dy4 N24 Ni4 O52 S2 F2'
_reflns_odcompleteness_completeness 98.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Me refined with riding coordinates:
 C1(H1A,H1B,H1C), C15(H15A,H15B,H15C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,
 H37B,H37C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C8(H8), C10(H10), C11(H11), C12(H12), C13(H13),
 C17(H17), C18(H18), C19(H19), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27),
  C29(H29), C32(H32), C35(H35), C38(H38)
;
_olex2_date_sample_data_collection 2018-02-19
_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 3.585
_oxdiff_exptl_absorpt_empirical_full_min 0.447