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_4034596
_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         'Cl, C17 H17 N2 O'
_chemical_formula_sum            'C17 H17 Cl N2 O'
_chemical_formula_weight         300.77
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   21.6654(4)
_cell_length_b                   9.6032(2)
_cell_length_c                   29.9888(7)
_cell_measurement_reflns_used    9572
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      69.6660
_cell_measurement_theta_min      4.0620
_cell_volume                     6239.4(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 0.0350
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.989
_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    -89.00  -2.00   0.50    4.00    --    0.00  10.00-150.00  174
  2  \w     -6.00  19.00   0.50    4.00    --    0.00  15.00  79.00   50
  3  \w    -19.00   6.00   0.50    4.00    --    5.00  15.00  79.00   50
  4  \w   -105.00  -2.00   0.50   16.00    --  -90.00  15.00  79.00  206
  5  \w   -168.00-142.00   0.50   16.00    --  -90.00  15.00  79.00   52
  6  \w    -40.00 -14.00   0.50   16.00    --  -90.00  54.00-129.03   52
  7  \w    -49.00 -15.00   0.50   16.00    --  -90.00  59.00 132.73   68
  8  \w    -68.00  -1.00   0.50   16.00    --  -90.00  58.00 164.17  134
  9  \w   -179.00 -87.00   0.50   16.00    --  -90.00  58.00 164.17  184
 10  \w   -113.00 -68.00   0.50   16.00    --  -90.00  59.00 132.73   90
 11  \w   -176.00-131.00   0.50   16.00    --  -90.00  59.00 -81.85   90
 12  \w   -113.00 -87.00   0.50   16.00    --  -90.00  59.00 -81.85   52
 13  \w   -179.00 -97.00   0.50   16.00    --  -90.00  54.00-129.03  164
;
_diffrn_measurement_device       'CrystalLogic Kappa (4 circle)'
_diffrn_measurement_device_type  'Kappa Rigaku Saturn724+'
_diffrn_measurement_method       'omega rotation'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0183836000
_diffrn_orient_matrix_UB_12      0.1523410000
_diffrn_orient_matrix_UB_13      -0.0092413000
_diffrn_orient_matrix_UB_21      0.0035046000
_diffrn_orient_matrix_UB_22      0.0319300000
_diffrn_orient_matrix_UB_23      0.0502856000
_diffrn_orient_matrix_UB_31      0.0685932000
_diffrn_orient_matrix_UB_32      0.0389156000
_diffrn_orient_matrix_UB_33      -0.0049851000
_diffrn_radiation_collimation    '0.3 x 1.5 Double Pinhole'
_diffrn_radiation_monochromator  'Synchrotron '
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0438
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            31394
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.063
_diffrn_reflns_theta_min         3.585
_diffrn_source                   Synchrotron
_diffrn_source_type              'Undulator, I19, DLS, RAL'
_exptl_absorpt_coefficient_mu    2.162
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56098
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.281
_exptl_crystal_description       block
_exptl_crystal_F_000             2528
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.244
_refine_diff_density_min         -0.285
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.239
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     422
_refine_ls_number_reflns         5857
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.237
_refine_ls_R_factor_all          0.0851
_refine_ls_R_factor_gt           0.0754
_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^)+17.3715P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1657
_refine_ls_wR_factor_ref         0.1694
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5051
_reflns_number_total             5857
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00608_si_001.cif
_cod_data_source_block           2018ncs0894z
_cod_database_code               4034596
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C17 H16 Cl N2 O'
_chemical_oxdiff_usercomment     SIS672_03
_reflns_odcompleteness_completeness 98.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 O51A-H51A \\sim O1B-H1B \\sim O1A-H1A \\sim O51B-H51B
 with sigma of 0.02
 N51-H51 \\sim N2-H2 \\sim N1-H1 \\sim N52-H52
 with sigma of 0.02
3. Others
 Sof(H8)=Sof(H58)=Sof(O51B)=Sof(H51B)=Sof(O1B)=Sof(H1B)=1-FVAR(1)
 Sof(H10)=Sof(H60)=Sof(O1A)=Sof(H1A)=Sof(O51A)=Sof(H51A)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C58(H58), C7(H7), C10(H10), C61(H61), C59(H59), C9(H9), C57(H57),
 C60(H60), C67(H67), C6(H6), C11(H11), C56(H56), C52(H52A), C2(H2A), C13(H13),
 C55(H55), C54(H54), C66(H66), C63(H63), C53(H53), C5(H5), C15(H15), C17(H17),
 C3(H3), C65(H65), C4(H4), C14(H14), C16(H16), C64(H64)
;
_shelx_res_checksum              17425
_shelx_hkl_checksum              65781
_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 1.750
_oxdiff_exptl_absorpt_empirical_full_min 0.773