Tetranuclear Zn/4f coordination clusters as highly efficient catalysts for Friedel-Crafts alkylation
Griffiths, Kieran; Kumar, Prashant; Akien, Geoffrey R.; Chilton, Nicholas F.; Abdul-Sada, Alaa; Tizzard, Graham J.; Coles, Simon J.; Kostakis, George E.; Chemical Communications 52 (2016) 7866–7869; doi:10.1039/c6cc03608b

data_7119379
_publ_section_title
;
 Tetranuclear Zn/4f coordination clusters as highly efficient catalysts
 for Friedel-Crafts alkylation
;
_journal_issue                   50
_journal_name_full               'Chemical Communications'
_journal_page_first              7866
_journal_page_last               7869
_journal_paper_doi               10.1039/c6cc03608b
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C62 H58 Gd2 N8 O20 Zn2'
_chemical_formula_sum            'C62 H58 Gd2 N8 O20 Zn2'
_chemical_formula_weight         1680.40
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-22
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-02-09 deposited with the CCDC.
2016-05-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.502(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.8176(6)
_cell_length_b                   14.3073(6)
_cell_length_c                   16.9982(8)
_cell_measurement_reflns_used    6766
_cell_measurement_temperature    173
_cell_measurement_theta_max      60.9420
_cell_measurement_theta_min      4.4360
_cell_volume                     3344.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      173
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1033
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.990
_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  95.00   1.00    1.00    --   36.75  57.00 -30.00   66
  2  \w     80.00 106.00   1.00    2.00    --   86.50  61.00-120.00   26
  3  \w    110.00 138.00   1.00    2.00    --   86.50  61.00-120.00   28
  4  \w    106.00 155.00   1.00    2.00    --   86.50  30.00-180.00   49
  5  \w     91.00 122.00   1.00    2.00    --   86.50  61.00-150.00   31
  6  \w     69.00 144.00   1.00    2.00    --   86.50  45.00-150.00   75
  7  \w     70.00 105.00   1.00    2.00    --   86.50 -61.00   0.00   35
  8  \w     51.00  77.00   1.00    2.00    --   86.50 -61.00 -90.00   26
  9  \w     52.00  84.00   1.00    2.00    --   86.50 -95.00-120.00   32
 10  \w     49.00  90.00   1.00    2.00    --   86.50-111.00-150.00   41
 11  \w     27.00  59.00   1.00    2.00    --   86.50 -95.00 -90.00   32
 12  \w     22.00  48.00   1.00    2.00    --   86.50 -61.00 -90.00   26
 13  \w     26.00  53.00   1.00    2.00    --   86.50 -30.00-120.00   27
 14  \w     25.00  51.00   1.00    2.00    --   86.50 -61.00   0.00   26
 15  \w     25.00  83.00   1.00    2.00    --   86.50 -95.00   0.00   58
 16  \w     19.00  78.00   1.00    2.00    --   86.50 -77.00 120.00   59
 17  \w     21.00  84.00   1.00    2.00    --   86.50 -95.00  60.00   63
 18  \w     17.00  46.00   1.00    2.00    --   86.50-111.00 -60.00   29
 19  \w    106.00 158.00   1.00    2.00    --   86.50  15.00 150.00   52
 20  \w    104.00 153.00   1.00    2.00    --   86.50  45.00  90.00   49
 21  \w    126.00 151.00   1.00    2.00    --   86.50  61.00  30.00   25
 22  \w     58.00  84.00   1.00    2.00    --   86.50  15.00 150.00   26
 23  \w     35.00  85.00   1.00    1.00    --   36.75 178.00 -30.00   50
 24  \w     41.00 109.00   1.00    1.00    --   36.75 178.00-180.00   68
 25  \w   -108.00 -80.00   1.00    1.00    --  -36.75-178.00 -90.00   28
;
_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      -0.0808953000
_diffrn_orient_matrix_UB_12      0.0465277000
_diffrn_orient_matrix_UB_13      -0.0552045000
_diffrn_orient_matrix_UB_21      0.0774461000
_diffrn_orient_matrix_UB_22      0.0482465000
_diffrn_orient_matrix_UB_23      -0.0454356000
_diffrn_orient_matrix_UB_31      -0.0003066000
_diffrn_orient_matrix_UB_32      -0.0843900000
_diffrn_orient_matrix_UB_33      -0.0562552000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0753
_diffrn_reflns_av_unetI/netI     0.0612
_diffrn_reflns_Laue_measured_fraction_full 0.958
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            18009
_diffrn_reflns_point_group_measured_fraction_full 0.958
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         61.102
_diffrn_reflns_theta_min         4.459
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.090
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32903
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.668
_exptl_crystal_F_000             1668
_refine_diff_density_max         1.735
_refine_diff_density_min         -1.727
_refine_diff_density_rms         0.166
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     428
_refine_ls_number_reflns         5079
_refine_ls_number_restraints     1148
_refine_ls_restrained_S_all      0.965
_refine_ls_R_factor_all          0.0600
_refine_ls_R_factor_gt           0.0541
_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^)+(0.1021P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1392
_refine_ls_wR_factor_ref         0.1485
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4512
_reflns_number_total             5079
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6cc03608b2.cif
_cod_data_source_block           1Gd
_cod_database_code               7119379
_shelxl_version_number           2014-1
_chemical_oxdiff_formula         Zn2Gd2C60H80N8022
_reflns_odcompleteness_completeness 85.58
_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. Rigid bond restraints
 C014, Gd01, O007, O005, O003, N00F, O00I, O00D, O00H, N00W, Zn02, C00O, C00K,
 C00G, C00P, C01C, C010, C018, O00N, N004, O00C, O009, C00V, C01A, C00M, C00X,
 C00Z, H01D, C012, H01A, H01B, H01C, C006, C011, C00R, C017, O00A, C00Q, C019,
 C00Y, C00L, H00X, H00Z, C016, H012, C01D, C013, H011, C00U, N00J, H017, C2,
 H00Q, C015, H019, H00Y, H00L, H016, H01E, H013, C00S, H00U, C00T, C8, H2A, H2B,
  H2C, H015, H014, H00S, H00A, H00B, H00C, H8A, H8B, H8C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C00S \\sim Gd01 \\sim O007 \\sim O005 \\sim O003 \\sim N00F \\sim O00I \\sim
O00D \\sim O00H \\sim N00W \\sim Zn02 \\sim C00O \\sim C00K \\sim C00G \\sim
C00P \\sim C01C \\sim C010 \\sim C018 \\sim O00N \\sim N004 \\sim O00C \\sim
O009 \\sim C00V \\sim C01A \\sim C00M \\sim C00X \\sim C00Z \\sim H01D \\sim
C012 \\sim H01A \\sim H01B \\sim H01C \\sim C006 \\sim C011 \\sim C00R \\sim
C017 \\sim O00A \\sim C00Q \\sim C019 \\sim C00Y \\sim C00L \\sim H00X \\sim
H00Z \\sim C016 \\sim H012 \\sim C01D \\sim C013 \\sim H011 \\sim C00U \\sim
N00J \\sim H017 \\sim C2 \\sim H00Q \\sim C015 \\sim H019 \\sim H00Y \\sim H00L
\\sim H016 \\sim H01E \\sim H013 \\sim C014 \\sim H00U \\sim C00T \\sim C8
\\sim H2A \\sim H2B \\sim H2C \\sim H015 \\sim H014 \\sim H00S \\sim H00A \\sim
H00B \\sim H00C \\sim H8A \\sim H8B \\sim H8C: within 1.7A with sigma of 0.04
and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 C00S, Gd01, O007, O005, O003, N00F, O00I, O00D, O00H, N00W, Zn02, C00O, C00K,
 C00G, C00P, C01C, C010, C018, O00N, N004, O00C, O009, C00V, C01A, C00M, C00X,
 C00Z, H01D, C012, H01A, H01B, H01C, C006, C011, C00R, C017, O00A, C00Q, C019,
 C00Y, C00L, H00X, H00Z, C016, H012, C01D, C013, H011, C00U, N00J, H017, C2,
 H00Q, C015, H019, H00Y, H00L, H016, H01E, H013, C014, H00U, C00T, C8, H2A, H2B,
  H2C, H015, H014, H00S, H00A, H00B, H00C, H8A, H8B, H8C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Aromatic/amide H refined with riding coordinates:
 C00L(H00L), C00Q(H00Q), C00S(H00S), C00U(H00U), C00X(H00X), C00Y(H00Y),
 C00Z(H00Z), C011(H011), C012(H012), C013(H013), C014(H014), C015(H015),
 C016(H016), C017(H017), C019(H019), C01C(H01D), C01D(H01E)
5.b Idealised Me refined as rotating group:
 C00T(H00A,H00B,H00C), C018(H01A,H01B,H01C), C2(H2A,H2B,H2C), C8(H8A,H8B,H8C)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.954
_oxdiff_exptl_absorpt_empirical_full_min 0.612