A sequential cyclization/π-extension strategy for modular construction of nanographenes enabled by stannole cycloadditions
Bergman, Harrison; Beattie, D. Dawson; Kiel, Gavin R.; Handford, Rex; Liu, Yi; Tilley, T. Don; Chemical Science  (2022) –; doi:10.1039/D2SC00397J

data_1566730
_publ_section_title
;
 A sequential cyclization/\p-extension strategy for modular construction
 of nanographenes enabled by stannole cycloadditions
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00397J
_journal_year                    2022
_chemical_formula_moiety         'C H Cl3, C60 H44, 0.66[CHCl3]'
_chemical_formula_sum            'C61 H45 Cl3'
_chemical_formula_weight         884.32
_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             2021-11-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2021-11-11 deposited with the CCDC.	2022-03-29 downloaded from the CCDC.
;
_cell_angle_alpha                94.6060(10)
_cell_angle_beta                 111.0410(10)
_cell_angle_gamma                97.9730(10)
_cell_formula_units_Z            2
_cell_length_a                   13.13230(10)
_cell_length_b                   14.2033(2)
_cell_length_c                   14.70790(10)
_cell_measurement_reflns_used    76005
_cell_measurement_temperature    100
_cell_measurement_theta_max      78.7220
_cell_measurement_theta_min      3.1830
_cell_volume                     2510.43(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_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     15.00  70.00   0.50    0.50    --    0.00  48.00 130.00  110
  2  \w     15.00  40.00   0.50    0.50    --   36.00  78.00 163.96   50
  3  \w     38.00  64.00   0.50    0.50    --   56.00  70.00 168.77   52
  4  \w     52.00  78.00   0.50    0.50    --   68.00  70.00 175.15   52
  5  \w     90.00 117.00   0.50    0.50    --   48.00  69.00  88.04   54
  6  \w     93.00 119.00   0.50    0.50    --   60.00  70.00  39.88   52
  7  \w    125.00 164.00   0.50    0.50    --  106.00  48.00 130.00   78
  8  \w     87.00 146.00   0.50    0.50    --  106.00  77.00  30.00  118
  9  \w     87.00 130.00   0.50    0.50    --   60.00  71.00-115.29   86
 10  \w     47.00  73.00   0.50    0.50    --   64.00  71.00 -76.43   52
 11  \w     42.00  73.00   0.50    0.50    --   60.00  71.00-115.29   62
 12  \w     36.00  62.00   0.50    0.50    --   52.00  69.00 -68.53   52
 13  \w     38.00  72.00   0.50    0.50    --   56.00  70.00 -45.01   68
 14  \w     42.00  68.00   0.50    0.50    --   60.00  71.00  -4.24   52
 15  \w     42.00  79.00   0.50    0.50    --   60.00  70.00  39.88   74
 16  \w     54.00  80.00   0.50    0.50    --   72.00  72.00  56.12   52
 17  \w     38.00  74.00   0.50    0.50    --   56.00  72.00  95.35   72
 18  \w     43.00  80.00   0.50    0.50    --   60.00  70.00 132.72   74
 19  \w     38.00  64.00   0.50    0.50    --   56.00  72.00 116.72   52
 20  \w     32.00  58.00   0.50    0.50    --   48.00  69.00  88.04   52
 21  \w     15.00  40.00   0.50    0.50    --   36.00  78.00  62.72   50
 22  \w     33.00  61.00   0.50    0.50    --   48.00  70.00   2.92   56
 23  \w      7.00  32.00   0.50    0.50    --   32.00  86.00  84.28   50
 24  \w     15.00  40.00   0.50    0.50    --   36.00  78.00 -10.48   50
 25  \w      2.00  27.00   0.50    0.50    --   28.00  89.00 -89.29   50
 26  \w     15.00  40.00   0.50    0.50    --   36.00  78.00 -80.21   50
 27  \w     26.00  54.00   0.50    0.50    --   44.00  70.00-113.57   56
 28  \w      7.00  32.00   0.50    0.50    --   32.00  86.00-100.57   50
 29  \w    -71.00   9.00   0.50    0.50    --    0.00 -48.00 -17.00  160
 30  \w    -18.00  68.00   0.50    0.50    --   52.00 -67.00 -80.91  172
 31  \w     58.00 100.00   0.50    0.50    --  106.00 -77.00 -60.00   84
 32  \w     71.00 101.00   0.50    0.50    --  106.00-111.00   0.00   60
 33  \w     51.00 101.00   0.50    0.50    --  106.00-111.00  60.00  100
 34  \w     80.00 106.00   0.50    0.50    --  106.00 -94.00 120.00   52
 35  \w     37.00 101.00   0.50    0.50    --  106.00 -77.00  90.00  128
 36  \w     39.00  67.00   0.50    0.50    --  106.00 -61.00 -30.00   56
 37  \w     37.00  64.00   0.50    0.50    --  106.00 -61.00 -90.00   54
 38  \w     46.00 101.00   0.50    0.50    --  106.00 -77.00-150.00  110
 39  \w     31.00 109.00   0.50    0.50    --  106.00-111.00 -30.00  156
 40  \w     41.00  67.00   0.50    0.50    --  106.00-111.00   0.00   52
 41  \w     36.00  79.00   0.50    0.50    --  106.00 -94.00   0.00   86
 42  \w     31.00 100.00   0.50    0.50    --  106.00 -94.00  60.00  138
 43  \w     38.00  68.00   0.50    0.50    --  106.00 -61.00 120.00   60
 44  \w     31.00  60.00   0.50    0.50    --  106.00 -94.00 120.00   58
 45  \w    -29.00  43.00   0.50    0.50    --   44.00 -48.00 131.78  144
 46  \w    -77.00 -39.00   0.50    0.50    --  -56.00 -71.00 176.21   76
 47  \w    -82.00 -56.00   0.50    0.50    --  -72.00 -66.00  94.36   52
 48  \w    -80.00 -55.00   0.50    0.50    --  -72.00 -69.00  74.17   50
 49  \w    -84.00 -58.00   0.50    0.50    --  -72.00 -67.00 113.71   52
 50  \w    -83.00 -57.00   0.50    0.50    --  -72.00 -66.00  50.36   52
 51  \w    -80.00 -54.00   0.50    0.50    --  -72.00 -70.00  32.03   52
 52  \w    -72.00 -42.00   0.50    0.50    --  -60.00 -70.00 -14.40   60
 53  \w    -82.00 -56.00   0.50    0.50    --  -72.00 -69.00 -48.27   52
 54  \w    -81.00 -55.00   0.50    0.50    --  -72.00 -72.00 -59.67   52
 55  \w    -85.00 -60.00   0.50    0.50    --  -76.00 -67.00-121.10   50
 56  \w    -89.00 -55.00   0.50    0.50    --  -72.00 -68.00-160.91   68
 57  \w    -90.00 -59.00   0.50    0.50    --  -76.00 -69.00-138.15   62
 58  \w    -95.00 -59.00   0.50    0.50    --  -76.00 -68.00 -87.60   72
 59  \w    -84.00 -59.00   0.50    0.50    --  -76.00 -69.00 -26.24   50
 60  \w    -89.00 -59.00   0.50    0.50    --  -76.00 -69.00  -7.44   60
 61  \w    -87.00 -61.00   0.50    0.50    --  -76.00 -65.00   4.12   52
 62  \w    -89.00 -64.00   0.50    0.50    --  -80.00 -66.00  49.76   50
 63  \w   -103.00 -68.00   0.50    0.50    --  -84.00 -66.00  28.56   70
 64  \w    -98.00 -72.00   0.50    0.50    --  -88.00 -66.00 -27.07   52
 65  \w    -93.00 -67.00   0.50    0.50    --  -84.00 -68.00 -53.65   52
 66  \w    -91.00 -66.00   0.50    0.50    --  -84.00 -70.00 -95.63   50
 67  \w   -103.00 -67.00   0.50    0.50    --  -84.00 -68.00-169.64   72
 68  \w    -98.00 -73.00   0.50    0.50    --  -92.00 -73.00-163.28   50
 69  \w   -112.00 -78.00   0.50    0.50    --  -96.00 -71.00-146.23   68
 70  \w   -107.00 -80.00   0.50    0.50    -- -100.00 -76.00-104.51   54
 71  \w   -105.00 -80.00   0.50    0.50    --  -96.00 -67.00 -63.17   50
 72  \w   -108.00 -78.00   0.50    0.50    --  -96.00 -71.00 -12.32   60
 73  \w   -106.00 -80.00   0.50    0.50    -- -100.00 -75.00 -74.81   52
 74  \w   -105.00 -80.00   0.50    0.50    -- -100.00 -77.00-120.00   50
 75  \w   -119.00 -82.00   0.50    0.50    -- -100.00 -72.00-116.29   74
 76  \w   -122.00 -80.00   0.50    0.50    -- -100.00 -77.00 -92.64   84
 77  \w   -128.00-103.00   0.50    0.50    --  -76.00 -67.00-121.10   50
 78  \w   -144.00-118.00   0.50    0.50    --  -76.00 -69.00-138.15   52
 79  \w   -139.00-113.00   0.50    0.50    -- -100.00 -76.00-104.51   52
 80  \w   -154.00-125.00   0.50    0.50    --  -84.00 -70.00 -95.63   58
 81  \w   -128.00 -83.00   0.50    0.50    -- -100.00 -68.00 -37.62   90
 82  \w   -110.00 -80.00   0.50    0.50    --  -96.00 -70.00  -2.64   60
 83  \w   -110.00 -73.00   0.50    0.50    --  -88.00 -64.00  52.60   74
 84  \w    -96.00 -70.00   0.50    0.50    --  -88.00 -70.00  76.31   52
 85  \w    -94.00 -68.00   0.50    0.50    --  -84.00 -68.00 139.57   52
 86  \w    -85.00 -59.00   0.50    0.50    --  -76.00 -68.00 147.24   52
 87  \w    -87.00 -61.00   0.50    0.50    --  -76.00 -63.00 166.76   52
 88  \w    -97.00 -71.00   0.50    0.50    --  -84.00 -64.00 118.98   52
 89  \w   -113.00 -79.00   0.50    0.50    --  -96.00 -69.00 169.26   68
 90  \w   -103.00 -77.00   0.50    0.50    --  -96.00 -73.00 162.79   52
 91  \w   -118.00 -80.00   0.50    0.50    -- -100.00 -75.00  90.52   76
 92  \w   -105.00 -80.00   0.50    0.50    -- -100.00 -77.00  60.00   50
 93  \w   -108.00 -83.00   0.50    0.50    -- -100.00 -69.00  30.80   50
 94  \w   -112.00 -83.00   0.50    0.50    -- -100.00 -70.00   6.49   58
 95  \w   -120.00 -81.00   0.50    0.50    -- -100.00 -74.00  68.82   78
 96  \w   -113.00 -80.00   0.50    0.50    -- -100.00 -76.00 106.78   66
 97  \w   -126.00 -82.00   0.50    0.50    -- -100.00 -79.00  54.02   88
 98  \w   -149.00 -82.00   0.50    0.50    -- -100.00 -71.00 135.77  134
 99  \w   -158.00-127.00   0.50    0.50    -- -100.00 -48.00 -17.00   62
100  \w   -141.00 -81.00   0.50    0.50    -- -100.00 -73.00 -22.07  120
101  \w   -150.00 -85.00   0.50    0.50    -- -100.00 -69.00 -61.89  130
102  \w   -153.00 -82.00   0.50    0.50    -- -100.00 -70.00  19.98  142
103  \w   -145.00-120.00   0.50    0.50    -- -100.00 -75.00 -74.81   50
104  \w   -164.00-138.00   0.50    0.50    --  -96.00 -67.00 -63.17   52
105  \w   -165.00-139.00   0.50    0.50    --  -96.00 -71.00 -12.32   52
106  \w   -168.00-116.00   0.50    0.50    -- -100.00 -69.00  30.80  104
107  \w   -171.00 -82.00   0.50    0.50    -- -100.00 -71.00 -71.47  178
108  \w   -146.00 -83.00   0.50    0.50    -- -100.00 -68.00-156.87  126
109  \w   -150.00 -81.00   0.50    0.50    -- -100.00 -73.00-163.15  138
110  \w   -162.00 -81.00   0.50    0.50    -- -100.00 -73.00 -38.37  162
111  \w   -162.00-129.00   0.50    0.50    -- -100.00 -70.00   6.49   66
112  \w   -168.00 -86.00   0.50    0.50    -- -100.00 -66.00  89.27  164
113  \w    -56.00 -30.00   0.50    0.50    -- -100.00  48.00 130.00   52
114  \w    -53.00 -25.00   0.50    0.50    -- -100.00 111.00 174.33   56
115  \w    -51.00 -25.00   0.50    0.50    -- -100.00 111.00  77.90   52
116  \w    -69.00 -43.00   0.50    0.50    -- -100.00 111.00  30.00   52
117  \w    -99.00 -51.00   0.50    0.50    -- -100.00 111.00  90.00   96
118  \w   -109.00 -63.00   0.50    0.50    -- -100.00 111.00 174.33   92
119  \w   -109.00 -60.00   0.50    0.50    -- -100.00 111.00  77.90   98
120  \w   -109.00 -84.00   0.50    0.50    -- -100.00 111.00  30.00   50
121  \w   -109.00 -52.00   0.50    0.50    -- -100.00 109.00 -25.47  114
122  \w   -107.00 -56.00   0.50    0.50    -- -100.00 111.00-120.00  102
123  \w    -65.00 -24.00   0.50    0.50    -- -100.00 111.00-150.00   82
124  \w   -102.00 -71.00   0.50    0.50    -- -100.00 111.00-150.00   62
125  \w   -163.00-137.00   0.50    0.50    -- -100.00 -74.00  68.82   52
126  \w   -168.00-120.00   0.50    0.50    -- -100.00 -77.00  60.00   96
127  \w   -163.00-137.00   0.50    0.50    --  -96.00 -69.00 169.26   52
128  \w   -170.00 -84.00   0.50    0.50    -- -100.00 -72.00 156.19  172
129  \w   -169.00 -83.00   0.50    0.50    -- -100.00 -69.00 123.06  172
130  \w   -171.00-145.00   0.50    0.50    -- -100.00 -76.00 106.78   52
131  \w   -172.00 -81.00   0.50    0.50    -- -100.00 -77.00 120.00  182
132  \w   -171.00-126.00   0.50    0.50    -- -100.00 -77.00 -92.64   90
133  \w   -166.00 -82.00   0.50    0.50    -- -100.00 -76.00-169.14  168
134  \w   -172.00-163.00   0.50    0.50    -- -100.00 -77.00-120.00   18
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0451
_diffrn_reflns_av_unetI/netI     0.0158
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            100149
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.502
_diffrn_reflns_theta_min         3.173
_exptl_absorpt_coefficient_mu    1.931
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74010
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.170
_exptl_crystal_description       prism
_exptl_crystal_F_000             924
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.065
_refine_diff_density_max         1.048
_refine_diff_density_min         -1.394
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     597
_refine_ls_number_reflns         10239
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0866
_refine_ls_R_factor_gt           0.0846
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1595P)^2^+2.5006P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2557
_refine_ls_wR_factor_ref         0.2578
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9642
_reflns_number_total             10239
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00397j2.cif
_cod_data_source_block           12
_cod_database_code               1566730
_shelx_shelxl_version_number     2018/3
_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. Uiso/Uaniso restraints and constraints
Uanis(C61) = Uanis(C61A)
Uanis(Cl3) = Uanis(Cl3A)
3. Others
 Sof(Cl2A)=Sof(Cl3A)=Sof(C61A)=Sof(H61A)=1-FVAR(1)
 Sof(Cl3)=Sof(Cl2)=Sof(C61)=Sof(H61)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C61(H61), C61A(H61A)
4.b Aromatic/amide H refined with riding coordinates:
 C48(H48), C49(H49), C38(H38), C52(H52), C31(H31), C22(H22), C55(H55),
 C51(H51), C19(H19), C59(H59), C35(H35), C16(H16), C10(H10), C30(H30), C28(H28),
  C34(H34), C56(H56), C13(H13), C29(H29), C45(H45), C37(H37), C23(H23),
 C17(H17), C11(H11), C18(H18), C12(H12), C44(H44), C25(H25), C58(H58), C41(H41),
  C24(H24), C42(H42)
4.c Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C60(H60A,H60B,H60C), C39(H39A,H39B,H39C), C46(H46A,H46B,
 H46C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 76 electrons were 
found in a volume of 192A3 in one void per unit cell. 
This is consistent with the presence of 
0.66[CHCl3] per asymmetric unit 
which account for 77 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.5
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              56639
_shelx_hkl_checksum              56117
_shelx_fab_checksum              31563
_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
;