Cyclophane-Sustained Ultrastable Porphyrins.
Liu, Wenqi; Lin, Chenjian; Weber, Jacob Andrew; Stern, Charlotte L.; Young, Ryan M.; Wasielewski, Michael R.; Stoddart, J. Fraser; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c02311

data_4134790
_publ_section_title
;
 Cyclophane-Sustained Ultrastable Porphyrins.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c02311
_journal_year                    2020
_chemical_formula_moiety         'C96 H76 N8, C32 H22 N4, 8(F6 P), 2(C3 H6 O)'
_chemical_formula_sum            'C134 H110 F48 N12 O2 P8'
_chemical_formula_weight         3080.09
_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             2019-08-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                108.9696(10)
_cell_angle_beta                 106.6927(10)
_cell_angle_gamma                102.2968(10)
_cell_formula_units_Z            1
_cell_length_a                   14.66878(16)
_cell_length_b                   17.5021(2)
_cell_length_c                   19.14358(19)
_cell_measurement_reflns_used    21244
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.4730
_cell_measurement_theta_min      2.6410
_cell_volume                     4189.71(10)
_computing_cell_refinement       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.57a (Rigaku OD, 2019)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.971
_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   -109.00 -55.00   0.50    0.71    --  -47.64-152.00 -39.00  108
  2  \w    -87.00 -31.00   0.50    0.71    --  -47.64 121.00-156.00  112
  3  \w   -108.00 -67.00   0.50    0.71    --  -47.64 152.00   2.00   82
  4  \w     56.00  83.00   0.50    0.71    --   47.64-152.00 -39.00   54
  5  \w     22.00  92.00   0.50    0.71    --   47.64-121.00 120.00  140
  6  \w     62.00  91.00   0.50    0.71    --   47.64 152.00   2.00   58
  7  \w   -130.00 -90.00   0.50    2.83    -- -106.00-121.00 120.00   80
  8  \w   -109.00 -66.00   0.50    2.83    -- -106.00 121.00-156.00   86
  9  \w    -82.00 -50.00   0.50    2.83    -- -106.00 152.00   2.00   64
 10  \w   -134.00-109.00   0.50    2.83    -- -106.00-152.00 -39.00   50
 11  \w     58.00  83.00   0.50    2.83    --  107.75-152.00 -39.00   50
 12  \w     85.00 118.00   0.50    2.83    --  107.75 152.00   2.00   66
 13  \w    103.00 128.00   0.50    2.83    --  107.75 121.00-156.00   50
 14  \w     48.00  73.00   0.50    2.83    --  107.75-121.00 120.00   50
 15  \w   -119.00 -75.00   0.50    0.71    --  -47.64-125.00-150.00   88
 16  \w    -29.00  28.00   0.50    0.71    --  -47.64  19.00  30.00  114
 17  \w     -9.00  22.00   0.50    0.71    --  -47.64  19.00-120.00   62
 18  \w     74.00  99.00   0.50    0.71    --   47.64 125.00-180.00   50
 19  \w    -25.00  21.00   0.50    0.71    --   47.64 -19.00-150.00   92
 20  \w     25.00 120.00   0.50    0.71    --   47.64  77.00-180.00  190
 21  \w     78.00 119.00   0.50    0.71    --   47.64 125.00  90.00   82
 22  \w   -164.00-136.00   0.50    2.83    -- -106.00 -94.00  60.00   56
 23  \w    -70.00 -34.00   0.50    2.83    -- -106.00  61.00-120.00   72
 24  \w   -177.00 -93.00   0.50    2.83    -- -106.00 -45.00 -60.00  168
 25  \w   -107.00 -39.00   0.50    2.83    -- -106.00 108.00-147.80  136
 26  \w   -106.00 -61.00   0.50    2.83    -- -106.00 103.00  50.25   90
 27  \w   -112.00 -48.00   0.50    2.83    -- -106.00 125.00 -60.00  128
 28  \w   -177.00-115.00   0.50    2.83    -- -106.00 -30.00-180.00  124
 29  \w   -166.00 -83.00   0.50    2.83    -- -106.00-125.00-180.00  166
 30  \w    -74.00 -33.00   0.50    2.83    -- -106.00  61.00-180.00   82
 31  \w     97.00 167.00   0.50    2.83    --  107.75  30.00  30.00  140
 32  \w     96.00 178.00   0.50    2.83    --  107.75  45.00   0.00  164
 33  \w     56.00 106.00   0.50    2.83    --  107.75 -96.00 100.55  100
 34  \w     76.00 106.00   0.50    2.83    --  107.75 -94.00 150.00   60
 35  \w     41.00  67.00   0.50    2.83    --  107.75 -94.00 150.00   52
 36  \w     37.00  62.00   0.50    2.83    --  107.75 -61.00 -90.00   50
 37  \w     55.00 107.00   0.50    2.83    --  107.75-108.00  32.78  104
 38  \w     37.00  97.00   0.50    2.83    --  107.75 -77.00  60.00  120
 39  \w     50.00 100.00   0.50    2.83    --  107.75 -77.00 150.00  100
 40  \w     36.00  67.00   0.50    2.83    --  107.75 -61.00   0.00   62
 41  \w     36.00  62.00   0.50    2.83    --  107.75 -61.00  30.00   52
 42  \w     36.00  62.00   0.50    2.83    --  107.75 -61.00 120.00   52
 43  \w     36.00 102.00   0.50    2.83    --  107.75 -77.00 -90.00  132
 44  \w     99.00 175.00   0.50    2.83    --  107.75  45.00 120.00  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0737649000
_diffrn_orient_matrix_UB_12      0.0312493000
_diffrn_orient_matrix_UB_13      0.0872016000
_diffrn_orient_matrix_UB_21      0.0878863000
_diffrn_orient_matrix_UB_22      -0.0034655000
_diffrn_orient_matrix_UB_23      -0.0283284000
_diffrn_orient_matrix_UB_31      0.0202245000
_diffrn_orient_matrix_UB_32      0.0937736000
_diffrn_orient_matrix_UB_33      0.0100426000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0648
_diffrn_reflns_av_unetI/netI     0.0562
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            60466
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.109
_diffrn_reflns_theta_min         2.646
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.665
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.370
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
'CrysAlisPro 1.171.40.57a (Rigaku Oxford Diffraction, 2019) Numerical absorption correction based on gaussian integration over 			a multifaceted crystal model Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.221
_exptl_crystal_description       needle
_exptl_crystal_F_000             1566
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.202
_exptl_crystal_size_mid          0.052
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.900
_refine_diff_density_min         -0.989
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1022
_refine_ls_number_reflns         17224
_refine_ls_number_restraints     162
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0672
_refine_ls_R_factor_gt           0.0571
_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^)+(0.0856P)^2^+2.2179P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1601
_refine_ls_wR_factor_ref         0.1671
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14020
_reflns_number_total             17224
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02311_si_002.cif
_cod_data_source_block           cx1598c
_cod_original_cell_volume        4189.71(8)
_cod_database_code               4134790
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C128 H98 F48N12 P8'
_cell_oxdiff_angle_alpha         108.9696(10)
_cell_oxdiff_angle_beta          106.6927(10)
_cell_oxdiff_angle_gamma         102.2968(10)
_cell_oxdiff_length_a            14.66878(16)
_cell_oxdiff_length_b            17.5021(2)
_cell_oxdiff_length_c            19.14358(19)
_cell_oxdiff_measurement_reflns_used 21244
_cell_oxdiff_volume              4189.71(8)
_diffrn_oxdiff_digest_frames
;
01cbf7fed9320db7d673216e211f4d3da504090ec72
;
_diffrn_oxdiff_digest_hkl
;
014defb7c44be2eb47de6e149f8822ce2bed9b
;
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F8A-F12A \\sim F8A-F10A \\sim F8A-F11A \\sim F8A-F9A \\sim F12A-F7A \\sim
F12A-F11A \\sim F12A-F9A ~
 F7A-F10A \\sim F7A-F11A \\sim F7A-F9A \\sim F10A-F11A \\sim F10A-F9A
 with sigma of 0.02
 P2A-F8A \\sim P2A-F12A \\sim P2A-F7A \\sim P2A-F10A \\sim P2A-F11A \\sim
P2A-F9A
 with sigma of 0.01
 F8-F12 \\sim F8-F10 \\sim F8-F11 \\sim F8-F9 \\sim F12-F7 \\sim F12-F11 \\sim
F12-F9 \\sim F7-F10 \\sim F7-
 F11 \\sim F7-F9 \\sim F10-F11 \\sim F10-F9
 with sigma of 0.02
 P2-F8 \\sim P2-F12 \\sim P2-F7 \\sim P2-F10 \\sim P2-F11 \\sim P2-F9
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 F7, F8, F9, F10, F11, F12, F7A, F8A, F9A, F10A, F11A, F12A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1)
 Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(P2A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(2)
 Sof(P2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(2)
 Fixed Sof: H5(0.5) H6A(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C8(H8A,H8B), C25(H25A,H25B), C32(H32A,H32B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C15(H15), C17(H17), C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C27(H27),
  C28(H28), C30(H30), C31(H31), C34(H34), C36(H36), C38(H38), C40(H40),
 C41(H41), C42(H42), C43(H43), C45(H45), C46(H46), C47(H47), C48(H48), N5(H5),
 N6(H6A), C50(H50), C51(H51), C53(H53), C55(H55), C56(H56), C60(H60), C61(H61),
 C62(H62), C63(H63), C64(H64)
5.c Idealised Me refined as rotating group:
 C65(H65A,H65B,H65C), C67(H67A,H67B,H67C)
;
_shelx_res_checksum              94186
_shelx_hkl_checksum              58286
_shelx_fab_checksum              58036
_olex2_date_sample_data_collection 2019-08-12
_olex2_date_sample_submission    2019-07-24
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder with Paratone oil'
_olex2_submission_original_sample_id cx1598c
_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 3.885
_oxdiff_exptl_absorpt_empirical_full_min 0.354