Specific Localization of Aluminum Sites Favors Ethene-to-Propene Conversion on (Al)MCM-41-Supported Ni(II) Single Sites
Moroz, Ilia B.; Lund, Alicia; Kaushik, Monu; Severy, Laurent; Gajan, David; Fedorov, Alexey; Lesage, Anne; Copéret, Christophe; ACS Catalysis 9 (2019) 7476–; doi:10.1021/acscatal.9b01903

data_4514643
_publ_section_title
;
 Specific Localization of Aluminum Sites Favors Ethene-to-Propene
 Conversion on (Al)MCM-41-Supported Ni(II) Single Sites
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              7476
_journal_paper_doi               10.1021/acscatal.9b01903
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         '2(C48 H108 Ni2 O16 Si4), C7 H8'
_chemical_formula_sum            'C103 H224 Ni4 O32 Si8'
_chemical_formula_weight         2434.37
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.288(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.2076(4)
_cell_length_b                   27.0780(3)
_cell_length_c                   21.5320(3)
_cell_measurement_reflns_used    36197
_cell_measurement_temperature    103(1)
_cell_measurement_theta_max      32.1090
_cell_measurement_theta_min      1.7610
_cell_volume                     13547.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.16b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.16b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.16b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      103(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0839
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.915
_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    -38.00   8.00   1.00    7.00    --  -26.54 -87.00  78.00   46
  2  \w    -86.00  -8.00   1.00    7.00    --  -26.54 -57.00 150.00   78
  3  \w    -87.00  36.00   1.00    7.00    --  -26.54   0.00   0.00  123
  4  \w    -42.00  89.00   1.00    7.00    --   27.01   0.00  60.00  131
  5  \w    -95.00 -43.00   1.00    7.00    --  -26.54 -57.00-120.00   52
  6  \w   -103.00 -32.00   1.00    7.00    --  -26.54 179.00 -60.00   71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0087459000
_diffrn_orient_matrix_UB_12      -0.0170517000
_diffrn_orient_matrix_UB_13      0.0204148000
_diffrn_orient_matrix_UB_21      -0.0227078000
_diffrn_orient_matrix_UB_22      0.0160707000
_diffrn_orient_matrix_UB_23      0.0015812000
_diffrn_orient_matrix_UB_31      -0.0184385000
_diffrn_orient_matrix_UB_32      -0.0116847000
_diffrn_orient_matrix_UB_33      -0.0275485000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.915
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            170290
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.915
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.601
_diffrn_reflns_theta_min         1.670
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.683
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82549
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.16b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.194
_exptl_crystal_description       block
_exptl_crystal_F_000             5288
_exptl_crystal_size_max          0.9728
_exptl_crystal_size_mid          0.8217
_exptl_crystal_size_min          0.6536
_refine_diff_density_max         0.823
_refine_diff_density_min         -0.477
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1472
_refine_ls_number_reflns         45223
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0764
_refine_ls_R_factor_gt           0.0443
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0351P)^2^+5.5285P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0847
_refine_ls_wR_factor_ref         0.0948
_reflns_Friedel_coverage         0.000
_reflns_number_gt                32559
_reflns_number_total             45223
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01903_si_002.cif
_cod_data_source_block           af-i-092
_cod_database_code               4514643
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ni2 Si4 O16 C55 H116'
_shelx_estimated_absorpt_t_max   0.664
_shelx_estimated_absorpt_t_min   0.556
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_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 body (RIGU) restrains
 C1A, C2A, C3A, C4A, C5A, C6A, C7A, C1, C2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=
 Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=1-FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=
 Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=FVAR(1)
 Sof(C104)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C105)=Sof(C106)=Sof(H10G)=
 Sof(H10H)=Sof(H10I)=Sof(C107)=Sof(H10J)=Sof(H10K)=Sof(H10L)=1-FVAR(2)
 Sof(C52)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(H54C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=FVAR(2)
4.a Free rotating group:
 C1A(C2A,C3A,C4A,C5A,C6A,C7A), C1(C2,C3,C4,C5,C6,C7)
4.b Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C7A(H7A), C3(H3), C4(H4), C5(H5),
 C6(H6), C7(H7)
4.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,
 H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C),
 C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,
 H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C),
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C104(H10D,H10E,
 H10F), C106(H10G,H10H,H10I), C107(H10J,H10K,H10L), C1A(H1AA,H1AB,H1AC), C1(H1A,
 H1B,H1C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C),
 C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C65(H65A,H65B,
 H65C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C), C70(H70A,
 H70B,H70C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C),
 C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,
 H79C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C85(H85A,
 H85B,H85C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C89(H89A,H89B,H89C),
 C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C94(H94A,H94B,
 H94C), C95(H95A,H95B,H95C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C99(H99A,
 H99B,H99C), C101(H10M,H10N,H10O), C102(H10P,H10Q,H10R), C103(H10S,H10T,H10U)
;
_shelx_res_checksum              2626
_shelx_hkl_checksum              46485
_olex2_exptl_crystal_mounting_method tip-mounted
_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 1.182
_oxdiff_exptl_absorpt_empirical_full_min 0.835