A shape changing tandem Rh(CNC) catalyst: preparation of bicyclo[4.2.0]octa-1,5,7-trienes from terminal aryl alkynes.
Storey, Caroline M.; Kalpokas, Audrius; Gyton, Matthew R.; Krämer, Tobias; Chaplin, Adrian B.; Chemical science 11 (2020) 2051–2057; doi:10.1039/c9sc06153c

data_1557118
_publ_section_title
;
 A shape changing tandem Rh(CNC) catalyst: preparation of
 bicyclo[4.2.0]octa-1,5,7-trienes from terminal aryl alkynes.
;
_journal_issue                   8
_journal_name_full               'Chemical science'
_journal_page_first              2051
_journal_page_last               2057
_journal_paper_doi               10.1039/c9sc06153c
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C32 H43 N5 Rh, C32 H12 B F24, 0.5(C6 H14)'
_chemical_formula_sum            'C67 H62 B F24 N5 Rh'
_chemical_formula_weight         1506.93
_chemical_melting_point          ?
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-12-04 deposited with the CCDC.	2020-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                84.062(3)
_cell_angle_beta                 73.668(3)
_cell_angle_gamma                70.038(3)
_cell_formula_units_Z            2
_cell_length_a                   11.7452(4)
_cell_length_b                   16.7896(5)
_cell_length_c                   18.5777(7)
_cell_measurement_reflns_used    14260
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      73.0740
_cell_measurement_theta_min      3.7000
_cell_volume                     3304.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.45a (Rigaku OD, 2019)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3046
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -66.00  33.00   1.00   12.50    --  -41.57  37.00 120.00   99
  2  \w    -93.00  -2.00   1.00   12.50    --  -41.57 125.00-180.00   91
  3  \w   -116.00 -17.00   1.00   12.50    --  -41.57 -37.00 -60.00   99
  4  \w      1.00  82.00   1.00   12.50    --   41.57 -99.00-150.00   81
  5  \w      9.00 118.00   1.00   12.50    --   41.57  77.00 -30.00  109
  6  \w     32.00 107.00   1.00   12.50    --   41.57-140.00 140.00   75
  7  \w     34.00 118.00   1.00   50.00    --  107.00-125.00  30.00   84
  8  \w     35.00 136.00   1.00   50.00    --  107.00 -61.00   0.00  101
  9  \w     34.00 118.00   1.00   50.00    --  107.00-125.00 150.00   84
 10  \w     94.00 178.00   1.00   50.00    --  107.00 125.00  90.00   84
 11  \w     24.00 110.00   1.00   50.00    --  107.00 -94.00 150.00   86
 12  \w     34.00 121.00   1.00   50.00    --  107.00-129.00 -46.00   87
 13  \w     31.00 140.00   1.00   50.00    --  107.00 -77.00-120.00  109
 14  \w     94.00 178.00   1.00   50.00    --  107.00 125.00 -60.00   84
 15  \w     94.00 178.00   1.00   50.00    --  107.00 125.00 -30.00   84
 16  \w     81.00 178.00   1.00   50.00    --  107.00  45.00 120.00   97
 17  \w     78.00 178.00   1.00   50.00    --  107.00  61.00  60.00  100
 18  \w     24.00 110.00   1.00   50.00    --  107.00 -94.00  30.00   86
 19  \w     94.00 178.00   1.00   50.00    --  107.00 125.00  60.00   84
 20  \w     34.00 118.00   1.00   50.00    --  107.00-125.00-150.00   84
 21  \w     74.00 178.00   1.00   50.00    --  107.00  77.00 -60.00  104
 22  \w     81.00 178.00   1.00   50.00    --  107.00  45.00  30.00   97
 23  \w   -115.00 -95.00   1.00   12.50    --  -41.57 -57.00  60.00   20
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'Rigaku Oxford Diffraction: 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      -0.0130123000
_diffrn_orient_matrix_UB_12      -0.0057998000
_diffrn_orient_matrix_UB_13      0.0850759000
_diffrn_orient_matrix_UB_21      0.1419046000
_diffrn_orient_matrix_UB_22      -0.0479216000
_diffrn_orient_matrix_UB_23      -0.0147793000
_diffrn_orient_matrix_UB_31      0.0248018000
_diffrn_orient_matrix_UB_32      0.0848563000
_diffrn_orient_matrix_UB_33      -0.0033528000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0564
_diffrn_reflns_av_unetI/netI     0.0604
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            39054
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        70.076
_diffrn_reflns_theta_max         70.076
_diffrn_reflns_theta_min         6.653
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.100
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.309
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.45a (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            'pale yellow'
_exptl_crystal_density_diffrn    1.515
_exptl_crystal_density_meas      ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             1530
_exptl_crystal_recrystallization_method
'Crystals grown from CH2Cl2-hexane at 243 K'
_exptl_crystal_size_max          0.305
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.758
_refine_diff_density_min         -1.957
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1108
_refine_ls_number_reflns         12524
_refine_ls_number_restraints     1045
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0561
_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^)+(0.0808P)^2^+2.3185P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1408
_refine_ls_wR_factor_ref         0.1481
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10611
_reflns_number_total             12524
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc06153c3.cif
_cod_data_source_block           0512abc19s
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value 'not measured' was changed
to '?' -- the value is undefined or not given.

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 1557116--1557122.cif.

 Adding full bibliography for 1557116--1557122.cif.
;
_cod_database_code               1557118
_shelx_shelxl_version_number     2014/7
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C415-F7 \\sim C415-F8 \\sim C415-F9 \\sim C415-F7A \\sim C415-F8A \\sim
C415-F9A
 with sigma of 0.01
 F7-F8 \\sim F8-F9 \\sim F9-F7 \\sim F7A-F8A \\sim F8A-F9A \\sim F9A-F7A
 with sigma of 0.01
 C411-F7 \\sim C411-F8 \\sim C411-F9 \\sim C411-F7A \\sim C411-F8A \\sim
C411-F9A
 with sigma of 0.01
 C431-F19 \\sim C431-F20 \\sim C431-F21 \\sim C431-F19A \\sim C431-F20A \\sim
C431-F21A
 with sigma of 0.01
 F19-F20 \\sim F20-F21 \\sim F21-F19 \\sim F19A-F20A \\sim F20A-F21A \\sim
F21A-F19A
 with sigma of 0.01
 C427-F19 \\sim C427-F20 \\sim C427-F21 \\sim C427-F19A \\sim C427-F20A \\sim
C427-F21A
 with sigma of 0.01
 C432-F22 \\sim C432-F23 \\sim C432-F24 \\sim C432-F22A \\sim C432-F23A \\sim
C432-F24A
 with sigma of 0.01
 F22-F23 \\sim F23-F24 \\sim F24-F22 \\sim F22A-F23A \\sim F23A-F24A \\sim
F24A-F22A
 with sigma of 0.01
 C429-F22 \\sim C429-F23 \\sim C429-F24 \\sim C429-F22A \\sim C429-F23A \\sim
C429-F24A
 with sigma of 0.01
 C91B-C90B \\sim C91A-C90A \\sim C92B-C91B \\sim C92A-C91A \\sim C93A-C92A
\\sim C93B-C92B \\sim C94A-
 C93A \\sim C94B-C93B \\sim C95A-C94A \\sim C95B-C94B
 with sigma of 0.01
 C121-C120 \\sim C221-C120 \\sim C222-C221 \\sim C122-C121 \\sim C223-C222
\\sim C123-C122 \\sim C224-
 C223 \\sim C124-C123 \\sim C125-C124 \\sim C225-C224 \\sim C126-C125 \\sim
C226-C225 \\sim C127-C126 ~
 C226-C127
 with sigma of 0.01
3. Restrained planarity
 C90A, C91A, C92A, C93A, C94A, C95A
 with sigma of 0.01
 C90B, C91B, C92B, C93B, C94B, C95B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C120 \\sim C121 \\sim C221 \\sim C222 \\sim C122 \\sim C123 \\sim C223 \\sim
C124 \\sim C224 \\sim C125 \\sim C225 \\sim C126 \\sim C226 \\sim C127 \\sim F1
\\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F7A \\sim F8 \\sim
F8A \\sim F9 \\sim F9A \\sim F10 \\sim F11 \\sim F12 \\sim F13 \\sim F14 \\sim
F15 \\sim F16 \\sim F17 \\sim F18 \\sim F19 \\sim F19A \\sim F20 \\sim F20A
\\sim F21 \\sim F21A \\sim F22 \\sim F22A \\sim F23 \\sim F23A \\sim F24 \\sim
F24A \\sim C90A \\sim C91A \\sim C92A \\sim C93A \\sim C94A \\sim C95A \\sim
C90B \\sim C91B \\sim C92B \\sim C93B \\sim C94B \\sim C95B: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C120) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C221) \\sim Ueq,
Uanis(C222) \\sim Ueq, Uanis(C122) \\sim Ueq, Uanis(C123) \\sim Ueq,
Uanis(C223) \\sim Ueq, Uanis(C124) \\sim Ueq, Uanis(C224) \\sim Ueq,
Uanis(C125) \\sim Ueq, Uanis(C225) \\sim Ueq, Uanis(C126) \\sim Ueq,
Uanis(C226) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F2)
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F4) \\sim Ueq, Uanis(F5) \\sim Ueq,
Uanis(F6) \\sim Ueq, Uanis(F7) \\sim Ueq, Uanis(F7A) \\sim Ueq, Uanis(F8) \\sim
Ueq, Uanis(F8A) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F9A) \\sim Ueq,
Uanis(F10) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F13)
\\sim Ueq, Uanis(F14) \\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F16) \\sim Ueq,
Uanis(F17) \\sim Ueq, Uanis(F18) \\sim Ueq, Uanis(F19) \\sim Ueq, Uanis(F19A)
\\sim Ueq, Uanis(F20) \\sim Ueq, Uanis(F20A) \\sim Ueq, Uanis(F21) \\sim Ueq,
Uanis(F21A) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F22A) \\sim Ueq, Uanis(F23)
\\sim Ueq, Uanis(F23A) \\sim Ueq, Uanis(F24) \\sim Ueq, Uanis(F24A) \\sim Ueq,
Uanis(C90A) \\sim Ueq, Uanis(C91A) \\sim Ueq, Uanis(C92A) \\sim Ueq,
Uanis(C93A) \\sim Ueq, Uanis(C94A) \\sim Ueq, Uanis(C95A) \\sim Ueq,
Uanis(C90B) \\sim Ueq, Uanis(C91B) \\sim Ueq, Uanis(C92B) \\sim Ueq,
Uanis(C93B) \\sim Ueq, Uanis(C94B) \\sim Ueq, Uanis(C95B) \\sim Ueq: with sigma
of 0.006 and sigma for terminal atoms of 0.012
5. Others
 Sof(H12C)=Sof(H12D)=Sof(H12S)=Sof(H12T)=Sof(C221)=Sof(H22A)=Sof(H22B)=
 Sof(C222)=Sof(H22C)=Sof(H22D)=Sof(C223)=Sof(H22E)=Sof(H22F)=Sof(C224)=
 Sof(H22G)=Sof(H22H)=Sof(C225)=Sof(H22I)=Sof(H22J)=Sof(C226)=Sof(H22K)=
 Sof(H22L)=1-FVAR(1)
 Sof(H12A)=Sof(H12B)=Sof(C121)=Sof(H12E)=Sof(H12F)=Sof(C122)=Sof(H12G)=
 Sof(H12H)=Sof(C123)=Sof(H12I)=Sof(H12J)=Sof(C124)=Sof(H12K)=Sof(H12L)=
 Sof(C125)=Sof(H12M)=Sof(H12N)=Sof(C126)=Sof(H12O)=Sof(H12P)=Sof(H12Q)=
 Sof(H12R)=FVAR(1)
 Sof(C90B)=Sof(H90D)=Sof(H90E)=Sof(H90F)=Sof(C91B)=Sof(H91C)=Sof(H91D)=
 Sof(C92B)=Sof(H92C)=Sof(H92D)=Sof(C93B)=Sof(H93C)=Sof(H93D)=Sof(C94B)=
 Sof(H94C)=Sof(H94D)=Sof(C95B)=Sof(H95D)=Sof(H95E)=Sof(H95F)=0.5*(1-FVAR(3))
 Sof(C90A)=Sof(H90A)=Sof(H90B)=Sof(H90C)=Sof(C91A)=Sof(H91A)=Sof(H91B)=
 Sof(C92A)=Sof(H92A)=Sof(H92B)=Sof(C93A)=Sof(H93A)=Sof(H93B)=Sof(C94A)=
 Sof(H94A)=Sof(H94B)=Sof(C95A)=Sof(H95A)=Sof(H95B)=Sof(H95C)=0.5*FVAR(3)
 Sof(F22A)=Sof(F23A)=Sof(F24A)=1-FVAR(3)
 Sof(F22)=Sof(F23)=Sof(F24)=FVAR(3)
 Sof(F19A)=Sof(F20A)=Sof(F21A)=1-FVAR(4)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(4)
 Sof(F7A)=Sof(F8A)=Sof(F9A)=1-FVAR(5)
 Sof(F7)=Sof(F8)=Sof(F9)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7)
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C107(H10A,H10B), C113(H11A,H11B), C119(H11C,H11D), C120(H12A,
 H12B), C120(H12C,H12D), C121(H12E,H12F), C122(H12G,H12H), C123(H12I,H12J),
 C124(H12K,H12L), C125(H12M,H12N), C126(H12O,H12P), C127(H12Q,H12R), C127(H12S,
 H12T), C128(H12U,H12V), C129(H12W,H12X), C130(H13A,H13B), C221(H22A,H22B),
 C222(H22C,H22D), C223(H22E,H22F), C224(H22G,H22H), C225(H22I,H22J), C226(H22K,
 H22L), C91A(H91A,H91B), C92A(H92A,H92B), C93A(H93A,H93B), C94A(H94A,H94B),
 C91B(H91C,H91D), C92B(H92C,H92D), C93B(H93C,H93D), C94B(H94C,H94D)
6.c Aromatic/amide H refined with riding coordinates:
 C103(H103), C104(H104), C105(H105), C111(H111), C112(H112), C117(H117),
 C118(H118), C402(H402), C404(H404), C406(H406), C410(H410), C412(H412),
 C414(H414), C418(H418), C420(H420), C422(H422), C426(H426), C428(H428),
 C430(H430)
6.d Idealised Me refined as rotating group:
 C90A(H90A,H90B,H90C), C95A(H95A,H95B,H95C), C90B(H90D,H90E,H90F), C95B(H95D,
 H95E,H95F)
;
_shelx_res_checksum              34385
_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 5.660
_oxdiff_exptl_absorpt_empirical_full_min 0.361