[3+3] Cyclocondensation of Disubstituted Biphenyl Dialdehydes: Access to Inherently Luminescent and Optically Active Hexa-substituted C3-Symmetric and Asymmetric Trianglimine Macrocycles.
Wang, Zhenzhen; Nour, Hany F.; Roch, Loïc M; Guo, Minjie; Li, Wenjiao; Baldridge, Kim K.; Sue, Andrew C. H.; Olson, Mark A.; The Journal of organic chemistry 82 (2017) 2472–2480; doi:10.1021/acs.joc.6b02868

data_4032249
_publ_section_title
;
 [3+3] Cyclocondensation of Disubstituted Biphenyl Dialdehydes: Access to
 Inherently Luminescent and Optically Active Hexa-substituted C3-Symmetric
 and Asymmetric Trianglimine Macrocycles.
;
_journal_issue                   5
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2472
_journal_page_last               2480
_journal_paper_doi               10.1021/acs.joc.6b02868
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C90 H78 N12 O6, 4.5(C2 H6 O S), 0.25(H2O)'
_chemical_formula_sum            'C99 H105.5 N12 O10.75 S4.5'
_chemical_formula_weight         1779.72
_chemical_name_systematic
;
 ? 
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-09-23
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 116.100(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.8628(9)
_cell_length_b                   21.7014(13)
_cell_length_c                   22.9812(10)
_cell_measurement_reflns_used    30553
_cell_measurement_temperature    113
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.0
_cell_volume                     9343.8(8)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.1 b42 (Rigaku, 2015)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.1 b42 (Rigaku, 2015)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.1 b42 (Rigaku, 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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      113
_diffrn_detector                 PILT
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
scan:
    Number of images: 360
               Slice: -105.0000 - 75.0000
         Image width: 0.5000
            Exp time: 10.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 0.0000
                 XTD: 44.9579
              2theta: -15.0805
scan:
    Number of images: 300
               Slice: -105.0000 - 45.0000
         Image width: 0.5000
            Exp time: 10.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 90.0000
                 XTD: 44.9579
              2theta: -15.0805
scan:
    Number of images: 200
               Slice: -105.0000 - -5.0000
         Image width: 0.5000
            Exp time: 10.0000
       Rotation axis: Omega
               Omega: 0.0000
                 Chi: 45.0000
                 Phi: 180.0000
                 XTD: 44.9579
              2theta: -15.0805
;
_diffrn_measurement_device
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'Rigaku Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support Fiber
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.037845
_diffrn_orient_matrix_UB_12      0.003194
_diffrn_orient_matrix_UB_13      0.037502
_diffrn_orient_matrix_UB_21      0.032477
_diffrn_orient_matrix_UB_22      0.004115
_diffrn_orient_matrix_UB_23      0.032430
_diffrn_orient_matrix_UB_31      0.014197
_diffrn_orient_matrix_UB_32      0.041984
_diffrn_orient_matrix_UB_33      -0.019588
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0269
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            82180
_diffrn_reflns_point_group_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        25.020
_diffrn_reflns_theta_max         25.020
_diffrn_reflns_theta_min         3.019
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.179
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.872
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.265
_exptl_crystal_density_method    "'not measured'"
_exptl_crystal_description       Prism
_exptl_crystal_F_000             3766
_exptl_crystal_preparation       Fiber
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.070
_refine_diff_density_min         -0.585
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Flack x determined using 13141 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.026(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2440
_refine_ls_number_reflns         31853
_refine_ls_number_restraints     201
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0424
_refine_ls_R_factor_gt           0.0391
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0591P)^2^+4.0315P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1013
_refine_ls_wR_factor_ref         0.1036
_reflns_Friedel_coverage         0.887
_reflns_Friedel_fraction_full    0.935
_reflns_Friedel_fraction_max     0.935
_reflns_number_gt                30002
_reflns_number_total             31853
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02868_si_002.cif
_cod_data_source_block           m20160709g1
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Multi-scan' changed to
'multi-scan' according to
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 

2025-10-08
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_weight         3559.44
_cod_original_formula_moiety         '2(C90 H78 N12 O6), 9(C2 H6 O S), 0.5(H2O)'
_cod_original_formula_units_Z            2
_cod_original_formula_sum        'C198 H211 N24 O21.50 S9'
_cod_database_code               4032249
_shelx_estimated_absorpt_t_max   0.979
_shelx_estimated_absorpt_t_min   0.965
_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 H(H,H) groups, All C(H,H,H) groups
2. Restrained distances
 S1-O13 = S1'-O13'
 1.48 with sigma of 0.01
 S1-C181 = S1-C182 = S1'-C081 = S1'-C082
 1.78 with sigma of 0.01
 S3-O15 = S3'-O15'
 1.48 with sigma of 0.01
 S6-O18 = S6'-O18'
 1.48 with sigma of 0.02
 S6-C191 = S6-C192 = S6'-C091 = S6'-C092
 1.78 with sigma of 0.01
 S7-O19 = S7'-O19'
 1.48 with sigma of 0.01
 S7-C193 = S7-C194 = S7'-C093 = S7'-C094
 1.78 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(S1) \\sim Ueq, Uanis(S1') \\sim Ueq, Uanis(C181) \\sim Ueq, Uanis(C182)
\\sim Ueq, Uanis(C081) \\sim Ueq, Uanis(C082) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(S7) \\sim Ueq, Uanis(O19) \\sim Ueq, Uanis(C193) \\sim Ueq, Uanis(C194)
\\sim Ueq, Uanis(S7') \\sim Ueq, Uanis(O19') \\sim Ueq, Uanis(C093) \\sim Ueq,
Uanis(C094) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(S3) \\sim Ueq, Uanis(O15) \\sim Ueq, Uanis(C185) \\sim Ueq, Uanis(C186)
\\sim Ueq, Uanis(S3') \\sim Ueq, Uanis(O15') \\sim Ueq, Uanis(C085) \\sim Ueq,
Uanis(C086) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C191) \\sim Ueq, Uanis(C192) \\sim Ueq, Uanis(S6) \\sim Ueq, Uanis(C091)
\\sim Ueq, Uanis(C092) \\sim Ueq, Uanis(S6') \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O18) \\sim Ueq, Uanis(O18') \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C082) = Uanis(C182)
Uanis(C081) = Uanis(C181)
Uanis(O18) = Uanis(O18')
Uanis(C091) = Uanis(C191)
4. Others
 Sof(S1')=Sof(O13')=Sof(C081)=Sof(H08A)=Sof(H08B)=Sof(H08C)=Sof(C082)=
 Sof(H08D)=Sof(H08E)=Sof(H08F)=1-FVAR(1)
 Sof(S1)=Sof(O13)=Sof(C181)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C182)=Sof(H18D)=
 Sof(H18E)=Sof(H18F)=FVAR(1)
 Sof(S3')=Sof(O15')=Sof(C085)=Sof(H08G)=Sof(H08H)=Sof(H08I)=Sof(C086)=
 Sof(H08J)=Sof(H08K)=Sof(H08L)=1-FVAR(2)
 Sof(S3)=Sof(O15)=Sof(C185)=Sof(H18M)=Sof(H18N)=Sof(H18O)=Sof(C186)=Sof(H18P)=
 Sof(H18Q)=Sof(H18R)=FVAR(2)
 Sof(S6')=Sof(O18')=Sof(C091)=Sof(H09A)=Sof(H09B)=Sof(H09C)=Sof(C092)=
 Sof(H09D)=Sof(H09E)=Sof(H09F)=1-FVAR(3)
 Sof(S6)=Sof(O18)=Sof(C191)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C192)=Sof(H19G)=
 Sof(H19H)=Sof(H19I)=FVAR(3)
 Sof(S7')=Sof(O19')=Sof(C093)=Sof(H09G)=Sof(H09H)=Sof(H09I)=Sof(C094)=
 Sof(H09J)=Sof(H09K)=Sof(H09L)=1-FVAR(4)
 Sof(S7)=Sof(O19)=Sof(C193)=Sof(H19J)=Sof(H19K)=Sof(H19L)=Sof(C194)=Sof(H19M)=
 Sof(H19N)=Sof(H19O)=FVAR(4)
 Fixed Sof: O22(0.5)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C6(H6), C31(H31), C36(H36), C61(H61), C66(H66), C91(H91), C96(H96),
 C121(H121), C126(H126), C151(H151), C156(H156)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C32(H32A,H32B), C33(H33A,
 H33B), C34(H34A,H34B), C35(H35A,H35B), C62(H62A,H62B), C63(H63A,H63B),
 C64(H64A,H64B), C65(H65A,H65B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B),
  C95(H95A,H95B), C122(H12A,H12B), C123(H12C,H12D), C124(H12E,H12F), C125(H12G,
 H12H), C152(H15A,H15B), C153(H15C,H15D), C154(H15E,H15F), C155(H15G,H15H)
5.c Aromatic/amide H refined with riding coordinates:
 C46(H46), C7(H7), C9(H9), C10(H10), C12(H12), C15(H15), C16(H16), C17(H17),
 C18(H18), C20(H20), C21(H21), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29),
  C30(H30), C37(H37), C39(H39), C40(H40), C42(H42), C45(H45), C47(H47),
 C48(H48), C50(H50), C51(H51), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59),
  C60(H60), C67(H67), C69(H69), C70(H70), C72(H72), C75(H75), C76(H76),
 C77(H77), C78(H78), C80(H80), C83(H83), C84(H84), C86(H86), C87(H87), C88(H88),
  C89(H89), C90(H90), C97(H97), C99(H99), C100(H100), C102(H102), C105(H105),
 C106(H106), C107(H107), C108(H108), C110(H110), C111(H111), C114(H114),
 C116(H116), C117(H117), C118(H118), C119(H119), C120(H120), C127(H127),
 C129(H129), C130(H130), C132(H132), C135(H135), C136(H136), C137(H137),
 C138(H138), C140(H140), C141(H141), C144(H144), C146(H146), C147(H147),
 C148(H148), C149(H149), C150(H150), C157(H157), C159(H159), C160(H160),
 C162(H162), C165(H165), C166(H166), C167(H167), C168(H168), C170(H170),
 C171(H171), C174(H174), C176(H176), C177(H177), C178(H178), C179(H179),
 C180(H180)
5.d Idealised Me refined as rotating group:
 C181(H18A,H18B,H18C), C182(H18D,H18E,H18F), C081(H08A,H08B,H08C), C082(H08D,
 H08E,H08F), C183(H18G,H18H,H18I), C184(H18J,H18K,H18L), C185(H18M,H18N,H18O),
 C186(H18P,H18Q,H18R), C085(H08G,H08H,H08I), C086(H08J,H08K,H08L), C187(H18S,
 H18T,H18U), C188(H18V,H18W,H18X), C189(H18Y,H,HA), C190(H19A,H19B,H19C),
 C191(H19D,H19E,H19F), C192(H19G,H19H,H19I), C091(H09A,H09B,H09C), C092(H09D,
 H09E,H09F), C193(H19J,H19K,H19L), C194(H19M,H19N,H19O), C093(H09G,H09H,H09I),
 C094(H09J,H09K,H09L), C195(H19P,H19Q,H19R), C196(H19S,H19T,H19U), C197(H19V,
 H19W,H19X), C198(H19Y,HB,HC)
;
_shelx_res_checksum              2101
_shelx_hkl_checksum              69584
_shelx_shelxl_version_number     2014/8
_olex2_submission_special_instructions 'No special instructions were received'