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_4347856
_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         'C120 H122 Eu4 N10 Ni8 O50, 4(Cl)'
_chemical_formula_sum            'C120 H122 Cl4 Eu4 N10 Ni8 O50'
_chemical_formula_weight         3723.59
_space_group_crystal_system      tetragonal
_space_group_IT_number           114
_space_group_name_Hall           'P -4 2n'
_space_group_name_H-M_alt        'P -4 21 c'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-11-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.89378(9)
_cell_length_b                   16.89378(9)
_cell_length_c                   25.8611(2)
_cell_measurement_reflns_used    110392
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.5790
_cell_measurement_theta_min      1.9450
_cell_volume                     7380.75(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrystalClear-SM Expert 3.1 b27 (Rigaku, 2013)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_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 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
  1 omega -106.00   74.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000    0.0000 -120.0000 180

  2 omega  -76.00   23.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000  -72.0000   60.0000 99

  3 omega  -70.00   23.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000  -72.0000 -150.0000 93

  4 omega  -30.00   69.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000   72.0000  -30.0000 99

  5 omega  -49.00  -33.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000  -72.0000   30.0000 16

  6 omega -106.00   30.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000  -18.0000   30.0000 136

  7 omega  -88.00   23.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000  -72.0000  -30.0000 111

  8 omega  -31.00   35.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000   54.0000 -150.0000 66

  9 omega  -60.00   23.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000  -72.0000  120.0000 83

 10 omega  -30.00   13.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.0000   72.0000 -120.0000 43
;
_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  0.0429
_diffrn_reflns_av_unetI/netI     0.0134
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            165854
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.558
_diffrn_reflns_theta_min         1.575
_diffrn_source                   'Rotating Anode'
_exptl_absorpt_coefficient_mu    2.822
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87866
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
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    1.675
_exptl_crystal_description       prism
_exptl_crystal_F_000             3712
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.156
_refine_diff_density_min         -0.787
_refine_diff_density_rms         0.238
_refine_ls_abs_structure_details
;
 Flack x determined using 3664 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.025(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.174
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     487
_refine_ls_number_reflns         8518
_refine_ls_number_restraints     1047
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0280
_refine_ls_R_factor_gt           0.0268
_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^)+(0.0603P)^2^+4.7215P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0897
_refine_ls_wR_factor_ref         0.0904
_reflns_Friedel_coverage         0.835
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                8231
_reflns_number_total             8518
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic6b00720_si_002.cif
_cod_data_source_block           1Eu-A
_cod_original_cell_volume        7380.75(10)
_cod_database_code               4347856
_shelxl_version_number           2014-1
_chemical_oxdiff_formula         'Eu2 Ni2 (C14 H11 O3 N)4 Cl2 (C2 H3 N)2'
_shelx_estimated_absorpt_t_max   0.895
_shelx_estimated_absorpt_t_min   0.895
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.50
_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, All O(H,H) groups
2. Restrained distances
 N3-C30
 1.2 with sigma of 0.02
 O10-H10A
 0.87 with sigma of 0.01
 O10-H10B
 0.87 with sigma of 0.01
 O11-H11A
 0.87 with sigma of 0.01
 O11-H11B
 0.87 with sigma of 0.01
 H10A-H10B
 1.421 with sigma of 0.02
 H11A-H11B
 1.421 with sigma of 0.02
 H11A-Eu1
 3.01 with sigma of 0.01
 Eu1-H11B
 3.07 with sigma of 0.01
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. Others
 Sof(Cl2)=1-FVAR(1)
 Sof(Cl1)=FVAR(1)
 Fixed Sof: O15(0.5) H15D(0.5) H15E(0.5) N3(0.5) C30(0.5) C31(0.5) H31A(0.5)
 H31B(0.5) H31C(0.5)
7.a Rotating group:
 O12(H12A,H12B), O15(H15D,H15E)
7.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)
7.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C15(H15A,H15B,H15C), C31(H31A,H31B,H31C)
;
_shelx_res_checksum              62842
_shelx_hkl_checksum              56902
_olex2_submission_special_instructions 'No special instructions were received'