Catalyst Control of Selectivity in the C‒O Bond Alumination of Biomass Derived Furans
Hooper, Thomas; Brown, Ryan; Rekhroukh, Feriel; Garçon, Martí; White, Andrew J. P.; Costa, Paulo J.; Crimmin, Mark Richard; Chemical Science  (2020) –; doi:10.1039/D0SC01918F

data_1558545
_publ_section_title
;
 Catalyst Control of Selectivity in the C--O Bond Alumination of Biomass
 Derived Furans
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC01918F
_journal_year                    2020
_chemical_formula_moiety         '2(C34 H47 Al N2 O2), C7 H16'
_chemical_formula_sum            'C75 H110 Al2 N4 O4'
_chemical_formula_weight         1185.62
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-12-19 deposited with the CCDC.	2020-07-06 downloaded from the CCDC.
;
_cell_angle_alpha                108.504(5)
_cell_angle_beta                 93.588(5)
_cell_angle_gamma                112.988(6)
_cell_formula_units_Z            2
_cell_length_a                   13.6025(8)
_cell_length_b                   17.2522(10)
_cell_length_c                   17.7358(9)
_cell_measurement_reflns_used    4856
_cell_measurement_temperature    173.00(14)
_cell_measurement_theta_max      28.0510
_cell_measurement_theta_min      2.6490
_cell_volume                     3549.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0382
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.798
_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    -40.00  52.00   1.00   89.45    --  -13.18  77.00 -60.00   92
  2  \w    -81.00  11.00   1.00   89.45    --  -13.18 -77.00-180.00   92
  3  \w     -2.00  82.00   1.00   89.45    --   14.27  57.00  90.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0519256000
_diffrn_orient_matrix_UB_12      -0.0350493000
_diffrn_orient_matrix_UB_13      -0.0227363000
_diffrn_orient_matrix_UB_21      -0.0071964000
_diffrn_orient_matrix_UB_22      -0.0154493000
_diffrn_orient_matrix_UB_23      0.0327540000
_diffrn_orient_matrix_UB_31      -0.0247767000
_diffrn_orient_matrix_UB_32      0.0291170000
_diffrn_orient_matrix_UB_33      0.0165494000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0341
_diffrn_reflns_av_unetI/netI     0.0754
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.798
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            20817
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.798
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.253
_diffrn_reflns_theta_min         2.347
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.090
_exptl_absorpt_correction_T_max  0.992
_exptl_absorpt_correction_T_min  0.966
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.109
_exptl_crystal_description       block
_exptl_crystal_F_000             1292
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: heptane'
_exptl_crystal_size_max          0.59
_exptl_crystal_size_mid          0.221
_exptl_crystal_size_min          0.125
_refine_diff_density_max         0.963
_refine_diff_density_min         -0.431
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     884
_refine_ls_number_reflns         14007
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.1127
_refine_ls_R_factor_gt           0.0705
_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^)+(0.0685P)^2^+2.5337P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1668
_refine_ls_wR_factor_ref         0.1886
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9163
_reflns_number_total             14007
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc01918f3.cif
_cod_data_source_block           4d
_cod_database_code               1558545
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C75 H110 Al2 N4 O4'
_chemical_oxdiff_usercomment     TH479
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.949
_reflns_odcompleteness_completeness 98.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C95-C96
 1.54 with sigma of 0.01
 C96-C97
 1.54 with sigma of 0.01
 C95-C96A
 1.54 with sigma of 0.01
 C96A-C97A
 1.54 with sigma of 0.01
 Al2-O80 \\sim Al2-O80A
 with sigma of 0.02
 Al2-C84 \\sim Al2-C84A
 with sigma of 0.02
 O80-C81 \\sim O80A-C81A
 with sigma of 0.02
 O85-C84 \\sim O85A-C84A
 with sigma of 0.02
 O85-C86 \\sim O85A-C86A
 with sigma of 0.02
 C81-C82 \\sim C81A-C82A
 with sigma of 0.02
 C82-C83 \\sim C82A-C83A
 with sigma of 0.02
 C83-C84 \\sim C83A-C84A
 with sigma of 0.02
 Al2-O85 \\sim Al2-O85A
 with sigma of 0.04
 Al2-C81 \\sim Al2-C81A
 with sigma of 0.04
 Al2-C83 \\sim Al2-C83A
 with sigma of 0.04
 O80-C82 \\sim O80A-C82A
 with sigma of 0.04
 O85-C83 \\sim O85A-C83A
 with sigma of 0.04
 C81-C83 \\sim C81A-C83A
 with sigma of 0.04
 C82-C84 \\sim C82A-C84A
 with sigma of 0.04
 C84-C86 \\sim C84A-C86A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C96) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C96A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C97) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C97A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(Al2A)=Sof(O80A)=Sof(O85A)=Sof(C81A)=Sof(H81A)=Sof(C82A)=Sof(H82A)=
 Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(C86A)=Sof(H86D)=Sof(H86E)=Sof(H86F)=1-FVAR(1)
 Sof(Al2)=Sof(O80)=Sof(O85)=Sof(C81)=Sof(H81)=Sof(C82)=Sof(H82)=Sof(C83)=
 Sof(H83)=Sof(C84)=Sof(C86)=Sof(H86A)=Sof(H86B)=Sof(H86C)=FVAR(1)
 Sof(H95C)=Sof(H95D)=Sof(C96A)=Sof(H96C)=Sof(H96D)=Sof(C97A)=Sof(H97D)=
 Sof(H97E)=Sof(H97F)=1-FVAR(2)
 Sof(H95A)=Sof(H95B)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(C97)=Sof(H97A)=Sof(H97B)=
 Sof(H97C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C62(H62), C65(H65), C74(H74), C77(H77)
5.b Secondary CH2 refined with riding coordinates:
 C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B), C95(H95C,
 H95D), C96(H96A,H96B), C96A(H96C,H96D)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C31(H31),
 C32(H32), C33(H33), C52(H52), C58(H58), C59(H59), C60(H60), C70(H70), C71(H71),
  C72(H72), C81(H81), C82(H82), C83(H83), C81A(H81A), C82A(H82A), C83A(H83A)
5.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C36(H36A,H36B,H36C), C54(H54A,
 H54B,H54C), C55(H55A,H55B,H55C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C),
 C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C75(H75A,H75B,H75C), C76(H76A,H76B,
 H76C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C86(H86A,H86B,H86C),
 C86A(H86D,H86E,H86F), C91(H91A,H91B,H91C), C97(H97A,H97B,H97C), C97A(H97D,H97E,
 H97F)
;
_shelx_res_checksum              95767
_olex2_date_sample_data_collection 2019-07-23
_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 1.056
_oxdiff_exptl_absorpt_empirical_full_min 0.953