Flexible macrocycles as versatile supports for catalytically active metal clusters.
Ryan, Jason D.; Gagnon, Kevin J.; Teat, Simon J.; McIntosh, Ruaraidh D.; Chemical communications (Cambridge, England) 52 (2016) 9071–9073; doi:10.1039/c6cc00478d

data_7118744
_publ_section_title
;
 Flexible macrocycles as versatile supports for catalytically active metal
 clusters.
;
_journal_issue                   58
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              9071
_journal_page_last               9073
_journal_paper_doi               10.1039/c6cc00478d
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety
'C186 H218 O30 Ti8, 4(C), 4(C3 H6 O), 2(C3 O), 2(C2 H3 O)'
_chemical_formula_sum            'C200 H254 O24 Ti8'
_chemical_formula_weight         3425.23
_chemical_name_systematic        C212H252O38Ti8
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-11-11
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-01-15 deposited with the CCDC.
2016-02-12 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 95.407(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   42.023(3)
_cell_length_b                   18.0435(14)
_cell_length_c                   30.746(2)
_cell_measurement_reflns_used    9964
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.11
_cell_measurement_theta_min      2.35
_cell_volume                     23209(3)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_unetI/netI     0.2117
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            19092
_diffrn_reflns_theta_full        24.41
_diffrn_reflns_theta_max         24.41
_diffrn_reflns_theta_min         0.97
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.312
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear reddish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    0.980
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             7288
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.858
_refine_diff_density_min         -2.825
_refine_diff_density_rms         0.867
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   3.147
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1026
_refine_ls_number_reflns         19092
_refine_ls_number_restraints     97
_refine_ls_restrained_S_all      3.159
_refine_ls_R_factor_all          0.5505
_refine_ls_R_factor_gt           0.4271
_refine_ls_shift/su_max          35.183
_refine_ls_shift/su_mean         0.534
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.7964
_refine_ls_wR_factor_ref         0.8408
_reflns_number_gt                7058
_reflns_number_total             19092
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6cc00478d2.cif
_cod_data_source_block           titbc8
_cod_depositor_comments
'Adding full bibliography for 7118743--7118745.cif.'
_cod_database_code               7118744
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H) groups
2. Shared sites
{C64, C64A}
{C63A, C63}
3. Restrained distances
 C3AA-C7AA
 1.54 with sigma of 0.02
 C8AA-C7AA
 1.54 with sigma of 0.02
 C9AA-C7AA
 1.54 with sigma of 0.02
 C7AA-C2AA
 1.54 with sigma of 0.02
 C7AA-C8
 1.54 with sigma of 0.02
 C7AA-C1AA
 1.54 with sigma of 0.02
 C21-C22
 1.54 with sigma of 0.02
 C21-C24
 1.54 with sigma of 0.02
 C35-C37
 1.54 with sigma of 0.02
 C35-C38
 1.54 with sigma of 0.02
 C35-C36
 1.54 with sigma of 0.02
 C46-C48
 1.54 with sigma of 0.02
 C46-C47
 1.54 with sigma of 0.02
 C46-C49
 1.54 with sigma of 0.02
 C61-C62
 1.54 with sigma of 0.02
 C61-C63
 1.54 with sigma of 0.02
 C60-C63
 1.54 with sigma of 0.02
 C61-C64
 1.54 with sigma of 0.02
 C60-C64
 1.54 with sigma of 0.02
 C73-C75
 1.54 with sigma of 0.02
 C73-C76
 1.54 with sigma of 0.02
 C73-C74
 1.54 with sigma of 0.02
 C84-C89
 1.54 with sigma of 0.02
 C84-C87
 1.54 with sigma of 0.02
 C84-C85
 1.54 with sigma of 0.02
 C100-C98
 1.54 with sigma of 0.02
 C101-C98
 1.54 with sigma of 0.02
 C21-C23
 1.54 with sigma of 0.02
 C89-C84 = C87-C84 = C85-C84
 1.45 with sigma of 0.02
 C89-C84 = C87-C84 = C85-C84 = C75-C73 = C76-C73 = C74-C73 = C98-C100 = C99-
 C98 = C98-C101 = C36-C35 = C38-C35 = C37-C35 = C23-C21 = C24-C21 = C22-C21 =
 C8AA-C7AA = C8-C7AA = C3AA-C7AA = C7AA-C1AA = C7AA-C9AA = C2AA-C7AA = C64-C61 =
  C62-C61 = C49-C46 = C48-C46 = C47-C46 = C65-C60 = C63-C61
 1.54 with sigma of 0.02
 C87A-C84 = C89A-C84 = C85A-C84
 1.54 with sigma of 0.02
 C24-C21 = C22-C21 = C23-C21
 1.54 with sigma of 0.02
 C209-O208
 1.23 with sigma of 0.02
 O212-C214
 1.23 with sigma of 0.02
 O200-C201
 1.23 with sigma of 0.02
 O204-C206
 1.23 with sigma of 0.02
 O7-H7
 0.87 with sigma of 0.01
 C85A-C89A
 2.54 with sigma of 0.04
 C89A-C87A
 2.54 with sigma of 0.04
 C87A-C85A
 2.54 with sigma of 0.04
 C89-C87
 2.54 with sigma of 0.04
 C87-C85
 2.54 with sigma of 0.04
 C85-C89
 2.54 with sigma of 0.04
 C202-C203
 2.54 with sigma of 0.04
 C202-O200
 2.54 with sigma of 0.04
 O200-C203
 2.54 with sigma of 0.04
 O204-C207
 2.54 with sigma of 0.04
 C207-C205
 2.54 with sigma of 0.04
 C205-O204
 2.54 with sigma of 0.04
 O208-C210
 2.54 with sigma of 0.04
 C211-O208
 2.54 with sigma of 0.04
 C210-C211
 2.54 with sigma of 0.04
 C23-C24
 2.54 with sigma of 0.04
 C85-C87
 2.54 with sigma of 0.04
 C89-C87
 2.54 with sigma of 0.04
 C85-C89
 2.54 with sigma of 0.04
 C89A-C87
 2.54 with sigma of 0.04
 C85-C87A
 2.54 with sigma of 0.04
 C85A-C89
 2.54 with sigma of 0.04
 C83-H7
 1.870047 with sigma of 0.02
 Ti4-H7
 2.160204 with sigma of 0.02
 C89A-C87 \\sim C87A-C85 \\sim C85A-C89
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C2AA) = Uanis(C3AA) = Uanis(C8) = Uanis(C8AA) = Uanis(C1AA) = Uanis(C9AA)
Uanis(C52) = Uanis(C53) = Uanis(C54) = Uanis(C55) = Uanis(C56) = Uanis(C57)
Uanis(C73) = Uanis(C74) = Uanis(C75) = Uanis(C76)
Uanis(C37) = Uanis(C38) = Uanis(C36) = Uanis(C35)
Uanis(C46) = Uanis(C48) = Uanis(C47) = Uanis(C49)
Uanis(C62) = Uanis(C61) = Uanis(C60) = Uanis(C65) = Uanis(C64) = Uanis(C64A) =
Uanis(C63) = Uanis(C63A)
Uanis(C203) = Uanis(C201) = Uanis(C202) = Uanis(O200)
Uanis(C213) = Uanis(C214) = Uanis(C215) = Uanis(O212)
Uanis(O204) = Uanis(C206) = Uanis(C205) = Uanis(C207)
Uanis(C211) = Uanis(C209) = Uanis(O208) = Uanis(C210)
Uanis(C22) = Uanis(C23) = Uanis(C24) = Uanis(C21)
Uanis(C85) = Uanis(C87A) = Uanis(C85A) = Uanis(C84) = Uanis(C87) = Uanis(C89A)
= Uanis(C89)
5. Others
 Fixed Sof: C3AA(0.25) H3AA(0.25) H3AB(0.25) H3AC(0.25) C8AA(0.25) H8AA(0.25)
 H8AB(0.25) H8AC(0.25) C9AA(0.25) H9AA(0.25) H9AB(0.25) H9AC(0.25) C2AA(0.75)
 H2AA(0.75) H2AB(0.75) H2AC(0.75) C8(0.75) H8A(0.75) H8B(0.75) H8C(0.75)
 C1AA(0.75) H1AA(0.75) H1AB(0.75) H1AC(0.75) C52(0.5) H52(0.5) C53(0.5)
 H53(0.5) C54(0.5) C55(0.5) C56(0.5) H56(0.5) C57(0.5) H57(0.5) C61(0.5)
 C60(0.5) C62(0.5) H62A(0.5) H62B(0.5) H62C(0.5) C63(0.5) C64(0.5) C89(0.5)
 C87(0.5) C85(0.5) C65(0.5) H65A(0.5) H65B(0.5) H65C(0.5) C85A(0.5) C87A(0.5)
 C89A(0.5) C64A(0.5) H64D(0.5) H64E(0.5) H64F(0.5) H64A(0.5) H64B(0.5)
 H64C(0.5) C63A(0.5) H63D(0.5) H63E(0.5) H63F(0.5) H63A(0.5) H63B(0.5) H63C(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C28(H28A,H28B), C39(H39A,H39B), C50(H50A,H50B), C66(H66A,
 H66B), C77(H77A,H77B), C91(H91A,H91B), C102(H10G,H10H), C103(H10I,H10J),
 C104(H10K,H10L)
6.b Me refined with riding coordinates:
 C64A(H64D,H64E,H64F), C64A(H64A,H64B,H64C), C63A(H63D,H63E,H63F), C63A(H63A,
 H63B,H63C)
6.c Aromatic/amide H refined with riding coordinates:
 C5AA(H5AA), C12(H12), C16(H16), C18(H18), C30(H30), C32(H32), C41(H41),
 C43(H43), C52(H52), C53(H53), C56(H56), C57(H57), C68(H68), C70(H70), C79(H79),
  C81(H81), C93(H93), C95(H95)
6.d Idealised Me refined as rotating group:
 C3AA(H3AA,H3AB,H3AC), C8AA(H8AA,H8AB,H8AC), C9AA(H9AA,H9AB,H9AC), C2AA(H2AA,
 H2AB,H2AC), C8(H8A,H8B,H8C), C1AA(H1AA,H1AB,H1AC), C22(H22A,H22B,H22C),
 C24(H24A,H24B,H24C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C36(H36A,H36B,
 H36C), C48(H48A,H48B,H48C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C62(H62A,
 H62B,H62C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C74(H74A,H74B,H74C),
 C100(H10A,H10B,H10C), C101(H10D,H10E,H10F), C105(H10M,H10N,H10O), C107(H10P,
 H10Q,H10R), C108(H10S,H10T,H10U), C23(H23A,H23B,H23C), C99(H99A,H99B,H99C),
 C65(H65A,H65B,H65C), C205(H20A,H20B,H20C), C210(H21A,H21B,H21C), C207(H20D,
 H20E,H20F), C203(H20G,H20H,H20I), C202(H20J,H20K,H20L)
;
_olex2_exptl_crystal_mounting_method 'Mounted upon a loop using paratone oil.'
_olex2_submission_original_sample_id TiTBC8
_olex2_submission_special_instructions 'No special instructions were received'