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_4347855
_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         'C105 H90 N8 Ni5 O28 Sm2'
_chemical_formula_sum            'C105 H90 N8 Ni5 O28 Sm2'
_chemical_formula_weight         2506.09
_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
_audit_creation_date             2015-11-30
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.977(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.327(18)
_cell_length_b                   14.386(15)
_cell_length_c                   47.92(5)
_cell_measurement_reflns_used    15681
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.7
_cell_measurement_theta_min      2.4
_cell_volume                     11829(2)
_computing_cell_refinement
'CrystalClear-SM Expert 2.1 b29 (Rigaku, 2013)'
_computing_data_collection
'CrystalClear-SM Expert 2.1 b29 (Rigaku, 2013)'
_computing_data_reduction
'CrystalClear-SM Expert 2.1 b29 (Rigaku, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.962
_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  0.1927
_diffrn_reflns_av_unetI/netI     0.1158
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       61
_diffrn_reflns_limit_l_min       -61
_diffrn_reflns_number            170842
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.574
_diffrn_reflns_theta_min         2.344
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           55.0
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    1.825
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.214
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrystalClear-SM Expert 2.1 b29 (Rigaku, 2013)'
_exptl_crystal_colour            Yellow
_exptl_crystal_density_diffrn    1.407
_exptl_crystal_description       needle
_exptl_crystal_F_000             5056
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.01
_refine_diff_density_max         2.667
_refine_diff_density_min         -0.739
_refine_diff_density_rms         0.167
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1346
_refine_ls_number_reflns         26360
_refine_ls_number_restraints     3266
_refine_ls_restrained_S_all      0.967
_refine_ls_R_factor_all          0.1360
_refine_ls_R_factor_gt           0.0952
_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^)+(0.1466P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2511
_refine_ls_wR_factor_ref         0.2744
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15206
_reflns_number_total             26360
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00720_si_002.cif
_cod_data_source_block           1Sm-A
_cod_original_cell_volume        11829(21)
_cod_database_code               4347855
_shelxl_version_number           2014-1
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.690
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups
2. Restrained distances
 N6-C91
 1.33 with sigma of 0.01
 C90-N6
 1.44 with sigma of 0.01
 C91-C92
 1.5 with sigma of 0.01
 O13-H13
 0.85 with sigma of 0.01
 C57-H13
 1.875448 with sigma of 0.02
 Ni5-H13
 2.738312 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Rotating group:
 O26(H26A,H26B), O27(H27A,H27B), O28(H28A,H28B)
6.b Secondary CH2 refined with riding coordinates:
 N8(H8A,H8B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), 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),
 C44(H44), C45(H45), C46(H46), C47(H47), C49(H49), C51(H51), C52(H52), C53(H53),
  C58(H58), C59(H59), C60(H60), C61(H61), C63(H63), C65(H65), C66(H66),
 C67(H67), C72(H72), C73(H73), C74(H74), C75(H75), C77(H77), C79(H79), C80(H80),
  C81(H81), C86(H86), C87(H87), C88(H88), C89(H89), C91(H91), C93(H93),
 C94(H94), C95(H95), C100(H100), C101(H101), C102(H102), C103(H103)
6.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C28(H28C,H28D,H28E), C42(H42A,H42B,H42C), C56(H56A,H56B,
 H56C), C70(H70A,H70B,H70C), C84(H84A,H84B,H84C), C98(H98A,H98B,H98C)
;
_shelx_res_checksum              87488
_shelx_hkl_checksum              93094
_olex2_submission_special_instructions 'No special instructions were received'