Porphyrin-Hexaphenylbenzene Conjugates via Mixed Cyclotrimerization Reactions.
Martin, Max M.; Dill, Maximilian; Langer, Jens; Jux, Norbert; The Journal of organic chemistry 84 (2019) 1489–1499; doi:10.1021/acs.joc.8b02907

data_4036032
_publ_section_title
;
 Porphyrin-Hexaphenylbenzene Conjugates via Mixed Cyclotrimerization
 Reactions.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1489
_journal_page_last               1499
_journal_paper_doi               10.1021/acs.joc.8b02907
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C240 H263 N12 Ni3, 11.5(C6 H6)'
_chemical_formula_sum            'C309 H332 N12 Ni3'
_chemical_formula_weight         4389.98
_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
_audit_creation_date             2018-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                102.076(3)
_cell_angle_beta                 95.259(3)
_cell_angle_gamma                100.812(3)
_cell_formula_units_Z            2
_cell_length_a                   13.7070(5)
_cell_length_b                   30.1449(13)
_cell_length_c                   33.1513(13)
_cell_measurement_reflns_used    11082
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      50.6750
_cell_measurement_theta_min      4.0630
_cell_volume                     13034.3(9)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.974
_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     46.00 129.00   1.00   57.50    --   60.07  38.00  30.00   83
  2  \w     42.00 132.00   1.00   57.50    --   60.07  38.00 120.00   90
  3  \w     29.00 113.00   1.00   57.50    --   60.07  77.00 150.00   84
  4  \w     17.00  91.00   1.00   57.50    --   60.07 -77.00  30.00   74
  5  \w     10.00 100.00   1.00   57.50    --   60.07 -99.00 -30.00   90
  6  \w     17.00 100.00   1.00   57.50    --   60.07 -99.00-150.00   83
  7  \w    -10.00  60.00   1.00   57.50    --   60.07 -38.00-150.00   70
  8  \w    -67.00  26.00   1.00   12.50    --    0.00 -19.00 150.00   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0178691000
_diffrn_orient_matrix_UB_12      -0.0302142000
_diffrn_orient_matrix_UB_13      -0.0411216000
_diffrn_orient_matrix_UB_21      0.0029021000
_diffrn_orient_matrix_UB_22      0.0414370000
_diffrn_orient_matrix_UB_23      -0.0206287000
_diffrn_orient_matrix_UB_31      0.1140739000
_diffrn_orient_matrix_UB_32      0.0151768000
_diffrn_orient_matrix_UB_33      0.0135859000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0569
_diffrn_reflns_av_unetI/netI     0.0980
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            49548
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        51.248
_diffrn_reflns_theta_max         51.248
_diffrn_reflns_theta_min         3.447
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.681
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70664
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.119
_exptl_crystal_description       block
_exptl_crystal_F_000             4708
_exptl_crystal_size_max          0.142
_exptl_crystal_size_mid          0.086
_exptl_crystal_size_min          0.063
_refine_diff_density_max         1.572
_refine_diff_density_min         -0.743
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.145
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3183
_refine_ls_number_reflns         27529
_refine_ls_number_restraints     3719
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.1655
_refine_ls_R_factor_gt           0.1133
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2996
_refine_ls_wR_factor_ref         0.3540
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16116
_reflns_number_total             27529
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02907_si_002.cif
_cod_data_source_block           compound14_Ni3
_cod_database_code               4036032
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N Ni'
_reflns_odcompleteness_completeness 98.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     50.38
_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. Restrained distances
 C150-C149 \\sim C257-C255 \\sim C152-C149 \\sim C151-C149 \\sim C255-C258
\\sim C256-C255
 with sigma of 0.02
 C67-C63 \\sim C241-C63
 with sigma of 0.02
 C68-C67 \\sim C244-C241 \\sim C69-C67 \\sim C242-C241 \\sim C241-C243 \\sim
C70-C67
 with sigma of 0.02
 C247-C111 \\sim C114-C111 \\sim C246-C111 \\sim C113-C111 \\sim C245-C111
\\sim C112-C111
 with sigma of 0.02
 C248-C117 \\sim C121-C117
 with sigma of 0.02
 C253-C139 \\sim C142-C139 \\sim C254-C139 \\sim C140-C139 \\sim C252-C139
\\sim C141-C139
 with sigma of 0.02
 C122-C121 \\sim C248-C251 \\sim C124-C121 \\sim C248-C249 \\sim C123-C121
\\sim C248-C250
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C149 \\sim C150 \\sim C151 \\sim C152 \\sim C255 \\sim C256 \\sim C257 \\sim
C258: within 3A with sigma of 0.02 and sigma for terminal atoms of 0.04
C241 \\sim C242 \\sim C243 \\sim C244 \\sim C67 \\sim C68 \\sim C69 \\sim C70:
within 3A with sigma of 0.02 and sigma for terminal atoms of 0.04
C111 \\sim C245 \\sim C246 \\sim C247 \\sim C112 \\sim C113 \\sim C114: within
3A with sigma of 0.02 and sigma for terminal atoms of 0.04
C248 \\sim C249 \\sim C250 \\sim C251 \\sim C121 \\sim C122 \\sim C123 \\sim
C124: within 3A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C331) \\sim Ueq, Uanis(C332) \\sim Ueq, Uanis(C333) \\sim Ueq,
Uanis(C334) \\sim Ueq, Uanis(C335) \\sim Ueq, Uanis(C336) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C218)=Sof(H21M)=Sof(H21N)=Sof(H21O)=Sof(C219)=Sof(H21J)=Sof(H21K)=
 Sof(H21L)=Sof(C220)=Sof(H22G)=Sof(H22H)=Sof(H22I)=1-FVAR(1)
 Sof(C259)=Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C260)=Sof(H26D)=Sof(H26E)=
 Sof(H26F)=Sof(C261)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(C252)=Sof(H25M)=Sof(H25N)=Sof(H25O)=Sof(C253)=Sof(H25J)=Sof(H25K)=
 Sof(H25L)=Sof(C254)=Sof(H25P)=Sof(H25Q)=Sof(H25R)=1-FVAR(2)
 Sof(C140)=Sof(H14H)=Sof(H14I)=Sof(H14G)=Sof(C141)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C142)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(2)
 Sof(C255)=Sof(C256)=Sof(H25G)=Sof(H25H)=Sof(H25I)=Sof(C257)=Sof(H25V)=
 Sof(H25W)=Sof(H25X)=Sof(C258)=Sof(H25S)=Sof(H25T)=Sof(H25U)=1-FVAR(3)
 Sof(C149)=Sof(C150)=Sof(H15G)=Sof(H15H)=Sof(H15I)=Sof(C151)=Sof(H15D)=
 Sof(H15E)=Sof(H15F)=Sof(C152)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(3)
 Sof(C241)=Sof(C242)=Sof(H24M)=Sof(H24O)=Sof(H24N)=Sof(C243)=Sof(H24D)=
 Sof(H24E)=Sof(H24F)=Sof(C244)=Sof(H24J)=Sof(H24K)=Sof(H24L)=1-FVAR(4)
 Sof(C67)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69A)=Sof(H69B)=
 Sof(H69C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(4)
 Sof(C112)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C113)=Sof(H11G)=Sof(H11H)=
 Sof(H11I)=Sof(C114)=Sof(H11J)=Sof(H11K)=Sof(H11L)=1-FVAR(5)
 Sof(C245)=Sof(H24V)=Sof(H24W)=Sof(H24X)=Sof(C246)=Sof(H24S)=Sof(H24T)=
 Sof(H24U)=Sof(C247)=Sof(H24G)=Sof(H24H)=Sof(H24I)=FVAR(5)
 Sof(C121)=Sof(C122)=Sof(H12M)=Sof(H12N)=Sof(H12O)=Sof(C123)=Sof(H12P)=
 Sof(H12Q)=Sof(H12R)=Sof(C124)=Sof(H12J)=Sof(H12K)=Sof(H12L)=1-FVAR(6)
 Sof(C248)=Sof(C249)=Sof(H24P)=Sof(H24Q)=Sof(H24R)=Sof(C250)=Sof(H25A)=
 Sof(H25B)=Sof(H25C)=Sof(C251)=Sof(H25Y)=Sof(H)=Sof(HA)=FVAR(6)
 Fixed Sof: C329(0.75) H329(0.75) C328(0.75) H328(0.75) C327(0.75) H327(0.75)
 C326(0.75) H326(0.75) C325(0.75) H325(0.75) C330(0.75) H330(0.75) C332(0.25)
 H332(0.25) C333(0.25) H333(0.25) C334(0.25) H334(0.25) C335(0.25) H335(0.25)
 C336(0.25) H336(0.25) C331(0.25) H331(0.25)
6.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C12(H12), C15(H15), C16(H16), C20(H20), C21(H21),
 C25(H25), C26(H26), C30(H30), C31(H31), C34(H34), C36(H36), C38(H38), C48(H48),
  C50(H50), C52(H52), C64(H64), C66(H66), C76(H76), C77(H77), C79(H79),
 C80(H80), C83(H83), C84(H84), C88(H88), C89(H89), C93(H93), C94(H94), C98(H98),
  C99(H99), C102(H102), C104(H104), C106(H106), C116(H116), C118(H118),
 C120(H120), C130(H130), C132(H132), C134(H134), C144(H144), C145(H145),
 C147(H147), C148(H148), C154(H154), C155(H155), C157(H157), C158(H158),
 C161(H161), C162(H162), C166(H166), C167(H167), C171(H171), C172(H172),
 C176(H176), C177(H177), C180(H180), C182(H182), C184(H184), C194(H194),
 C196(H196), C198(H198), C208(H208), C210(H210), C212(H212), C222(H222),
 C223(H223), C225(H225), C226(H226), C232(H232), C233(H233), C235(H235),
 C236(H236), C265(H265), C264(H264), C263(H263), C262(H262), C267(H267),
 C266(H266), C269(H269), C270(H270), C271(H271), C272(H272), C273(H273),
 C268(H268), C274(H274), C275(H275), C276(H276), C277(H277), C278(H278),
 C279(H279), C280(H280), C281(H281), C282(H282), C283(H283), C284(H284),
 C285(H285), C286(H286), C287(H287), C288(H288), C289(H289), C290(H290),
 C291(H291), C292(H292), C293(H293), C294(H294), C295(H295), C296(H296),
 C297(H297), C298(H298), C299(H299), C300(H300), C301(H301), C302(H302),
 C303(H303), C304(H304), C305(H305), C306(H306), C307(H307), C308(H308),
 C309(H309), C314(H314), C313(H313), C312(H312), C311(H311), C310(H310),
 C315(H315), C316(H316), C317(H317), C318(H318), C319(H319), C320(H320),
 C321(H321), C322(H322), C323(H323), C324(H324), C329(H329), C328(H328),
 C327(H327), C326(H326), C325(H325), C330(H330), C332(H332), C333(H333),
 C334(H334), C335(H335), C336(H336), C331(H331)
6.b Fitted hexagon refined as free rotating group:
 C265(C264,C263,C262,C267,C266), C269(C270,C271,C272,C273,C268), C314(C313,
 C312,C311,C310,C315), C329(C328,C327,C326,C325,C330), C332(C333,C334,C335,C336,
 C331)
6.c Idealised Me refined with riding coordinates:
 C249(H24P,H24Q,H24R), C250(H25A,H25B,H25C), C123(H12P,H12Q,H12R), C253(H25J,
 H25K,H25L)
6.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C54(H54A,H54B,H54C), C55(H55B,
 H55C,H55A), C56(H56A,H56B,H56C), C58(H58B,H58A,H58C), C59(H59A,H59B,H59C),
 C60(H60A,H60B,H60C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,
 H74C), C108(H10A,H10B,H10C), C109(H10D,H10E,H10F), C110(H11A,H11B,H11C),
 C126(H12A,H12B,H12C), C127(H12G,H12H,H12I), C128(H12D,H12E,H12F), C136(H13A,
 H13B,H13C), C137(H13D,H13E,H13F), C138(H13G,H13H,H13I), C186(H18A,H18B,H18C),
 C187(H18D,H18E,H18F), C188(H18G,H18H,H18I), C190(H19D,H19E,H19F), C191(H19G,
 H19H,H19I), C192(H19A,H19B,H19C), C200(H20D,H20E,H20F), C201(H20P,H20Q,H20R),
 C202(H20M,H20N,H20O), C204(H20G,H20H,H20I), C205(H20A,H20B,H20C), C206(H20J,
 H20K,H20L), C214(H21G,H21H,H21I), C215(H21D,H21E,H21F), C216(H21A,H21B,H21C),
 C228(H22D,H22E,H22F), C229(H22A,H22B,H22C), C230(H23A,H23B,H23C), C238(H23D,
 H23E,H23F), C239(H23G,H23H,H23I), C240(H24A,H24B,H24C), C140(H14H,H14I,H14G),
 C141(H14D,H14E,H14F), C142(H14A,H14B,H14C), C150(H15G,H15H,H15I), C151(H15D,
 H15E,H15F), C152(H15A,H15B,H15C), C242(H24M,H24O,H24N), C243(H24D,H24E,H24F),
 C244(H24J,H24K,H24L), C245(H24V,H24W,H24X), C246(H24S,H24T,H24U), C247(H24G,
 H24H,H24I), C251(H25Y,H,HA), C259(H25D,H25E,H25F), C260(H26D,H26E,H26F),
 C261(H26A,H26B,H26C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,
 H70C), C112(H11D,H11E,H11F), C113(H11G,H11H,H11I), C114(H11J,H11K,H11L),
 C122(H12M,H12N,H12O), C124(H12J,H12K,H12L), C218(H21M,H21N,H21O), C219(H21J,
 H21K,H21L), C220(H22G,H22H,H22I), C252(H25M,H25N,H25O), C254(H25P,H25Q,H25R),
 C256(H25G,H25H,H25I), C257(H25V,H25W,H25X), C258(H25S,H25T,H25U)
;
_olex2_date_sample_data_collection 2018-04-15
_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 1.850
_oxdiff_exptl_absorpt_empirical_full_min 0.667