Efficient Ni(II)2Ln(III)2 Electrocyclization Catalysts for the Synthesis of trans-4,5-Diaminocyclopent-2-enones from 2-Furaldehyde and Primary or Secondary Amines.
Griffiths, Kieran; Kumar, Prashant; Mattock, James D.; Abdul-Sada, Alaa; Pitak, Mateusz B.; Coles, Simon J.; Navarro, Oscar; Vargas, Alfredo; Kostakis, George E.; Inorganic chemistry 55 (2016) 6988–6994; doi:10.1021/acs.inorgchem.6b00720

data_4347854
_publ_section_title
;
 Efficient Ni(II)2Ln(III)2 Electrocyclization Catalysts for the Synthesis
 of trans-4,5-Diaminocyclopent-2-enones from 2-Furaldehyde and Primary or
 Secondary Amines.
;
_journal_issue                   14
_journal_name_full               'Inorganic chemistry'
_journal_page_first              6988
_journal_page_last               6994
_journal_paper_doi               10.1021/acs.inorgchem.6b00720
_journal_volume                  55
_journal_year                    2016
_chemical_formula_moiety         'C84 H70 N6 O20 Sm4, 2(C2 H3 N1)'
_chemical_formula_sum            'C88 H76 N8 O20 Sm4'
_chemical_formula_weight         2166.96
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-06-18
_audit_creation_method           SHELXL-2013
_cell_angle_alpha                100.536(7)
_cell_angle_beta                 106.682(8)
_cell_angle_gamma                114.818(8)
_cell_formula_units_Z            1
_cell_length_a                   12.8651(12)
_cell_length_b                   13.5435(12)
_cell_length_c                   14.0419(12)
_cell_measurement_reflns_used    22497
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.6
_cell_measurement_theta_min      3.0
_cell_volume                     1993.6(4)
_computing_cell_refinement
;
CrystalClear-SM Expert 3.1 b27 (Rigaku, 2012)
;
_computing_data_collection
;
CrystalClear-SM Expert 3.1 b27 (Rigaku, 2012)
;
_computing_data_reduction
;
CrystalClear-SM Expert 3.1 b27 (Rigaku, 2012)
;
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100.(2)
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device
;
AFC12 (Right): Kappa 3 circle
;
_diffrn_measurement_device_type
;
Rigaku Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support MiTeGen
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0347
_diffrn_reflns_av_unetI/netI     0.0368
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            26495
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         3.010
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    2.983
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.695
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear-SM Expert 3.1 b18 (Rigaku, 2012)'
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.805
_exptl_crystal_description       block
_exptl_crystal_F_000             1068
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.700
_refine_diff_density_min         -1.043
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     578
_refine_ls_number_reflns         9143
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0303
_refine_ls_R_factor_gt           0.0246
_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^)+(0.0254P)^2^+1.7351P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0582
_refine_ls_wR_factor_ref         0.0604
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8010
_reflns_number_total             9143
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00720_si_002.cif
_cod_data_source_block           1Sm-C
_cod_original_cell_volume        1993.5(3)
_cod_database_code               4347854
_shelxl_version_number           2014-1
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.755
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 N5, C45, C46, N4, C43, C44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
N5 \\sim C45 \\sim C46 \\sim N4 \\sim C43 \\sim C44: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 N5, C45, C46, N4, C43, C44
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(N5)=Sof(C45)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=1-FVAR(1)
 Sof(N4)=Sof(C43)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 O20(H20)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5), C7(H7), C9(H9), C10(H10), C11(H11), C16(H16),
  C17(H17), C18(H18), C19(H19), C21(H21), C23(H23), C24(H24), C25(H25),
 C30(H30), C31(H31), C32(H32), C33(H33), C35(H35), C37(H37), C38(H38), C39(H39)
6.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C28(H28A,H28B,H28C), C42(H42A,H42B,H42C), C46(H46A,H46B,
 H46C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              69631
_shelx_hkl_checksum              37582
_olex2_submission_special_instructions 'No special instructions were received'