Diametric calix[6]arene gold(i) catalysts for intramolecular cyclopropanations of 1,6-dienynes
Giovanardi, Gabriele; Balestri, Davide; Secchi, Andrea; Cera, Gianpiero; Organic & Biomolecular Chemistry  (2022) –; doi:10.1039/D2OB01074G

data_7158800
_publ_section_title
;
 Diametric calix[6]arene gold(i) catalysts for intramolecular
 cyclopropanations of 1,6-dienynes
;
_journal_name_full               'Organic &amp; Biomolecular Chemistry'
_journal_paper_doi               10.1039/D2OB01074G
_journal_year                    2022
_chemical_formula_moiety         'C116 H136 Au2 Cl2 N2 O8 P2, 1.5(C H Cl3)'
_chemical_formula_sum            'C117.5 H137.5 Au2 Cl6.5 N2 O8 P2'
_chemical_formula_weight         2392.08
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-08
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-07-21 deposited with the CCDC.	2022-07-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.541(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.4353(6)
_cell_length_b                   15.4148(2)
_cell_length_c                   25.1048(4)
_cell_measurement_reflns_used    25679
_cell_measurement_temperature    200
_cell_measurement_theta_max      29.9750
_cell_measurement_theta_min      1.7270
_cell_volume                     11777.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      200.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f   -339.92  20.08   0.50   16.00  19.63  -0.86 -59.25    --   720
  2  \w    -63.36   0.14   0.50   16.00    --  -22.06  94.56 145.16  127
  3  \w    -84.56  19.44   0.50   16.00    --   -0.86 -59.25 -51.92  208
  4  \w    -63.36   0.14   0.50   16.00    --  -22.06  94.56   1.16  127
;
_diffrn_measurement_device       'Bruker D8 VENTURE'
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON II'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0631
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            115349
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         1.692
_diffrn_source                   microfocus
_exptl_absorpt_coefficient_mu    2.716
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75038
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_description       needle
_exptl_crystal_F_000             4876
_exptl_crystal_preparation       'Compound from synthesis'
_exptl_crystal_recrystallization_method
'Slow evaporation of chloroform/hexane mixture'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.739
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     794
_refine_ls_number_reflns         11167
_refine_ls_number_restraints     467
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0358
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0527P)^2^+31.6716P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0950
_refine_ls_wR_factor_ref         0.0999
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9507
_reflns_number_total             11167
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ob01074g2.cif
_cod_data_source_block           B_(AuCl)2
_cod_original_formula_sum        'C117.50 H137.50 Au2 Cl6.50 N2 O8 P2'
_cod_database_code               7158800
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.773
_olex2_refinement_description
;
1. Restrained distances
 C62C-C72C = C62C-C92C = C82C-C62C
 1.5 with sigma of 0.02
 C321-C311
 1.5 with sigma of 0.02
 C62-C92 = C62-C72 = C82-C62
 1.5 with sigma of 0.02
 C261-C27A = C271-C261
 1.5 with sigma of 0.02
 C29A-C28A = C27A-C28A
 1.5 with sigma of 0.02
 C311-C301
 1.5 with sigma of 0.02
 C281-C271
 1.5 with sigma of 0.02
 C29A-C30A
 1.5 with sigma of 0.02
 C281-C271 = C271-C261 = C281-C291 = C301-C291
 1.5 with sigma of 0.02
 C31A-C30A = C29A-C30A = C31A-C32A
 1.5 with sigma of 0.02
 C281-C291 = C301-C291
 1.5 with sigma of 0.02
 N11-H11
 0.9 with sigma of 0.02
 Cl4-C25 = Cl6-C25 = Cl5-C25
 1.7 with sigma of 0.02
 C30B-C29B = C30B-C31B = C28B-C29B = C27B-C28B
 1.5 with sigma of 0.02
 C31B-C32B
 1.5 with sigma of 0.02
 C301-C321
 2.5 with sigma of 0.04
 C92-C72
 2.4 with sigma of 0.04
 C72C-C82C
 2.4 with sigma of 0.04
 C92C-C72C
 2.4 with sigma of 0.04
 C72-C82
 2.4 with sigma of 0.04
 C82-C92
 2.4 with sigma of 0.04
 C82C-C92C
 2.4 with sigma of 0.04
 C83-C73
 2.4 with sigma of 0.04
 C93-C83
 2.4 with sigma of 0.04
 C27A-C29A
 2.5 with sigma of 0.04
 C28A-C261
 2.5 with sigma of 0.04
 C251-C27A
 2.5 with sigma of 0.04
 C261-C281
 2.5 with sigma of 0.04
 C30A-C28A
 2.5 with sigma of 0.04
 C32A-C30A
 2.5 with sigma of 0.04
 C251-C271
 2.5 with sigma of 0.04
 C31A-C29A
 2.5 with sigma of 0.04
 C311-C291
 2.5 with sigma of 0.04
 C281-C301
 2.5 with sigma of 0.04
 C291-C271
 2.5 with sigma of 0.04
 C83D-C73D
 2.4 with sigma of 0.04
 C73D-C93D
 2.4 with sigma of 0.04
 C93D-C83D
 2.4 with sigma of 0.04
 C73-C93
 2.4 with sigma of 0.04
 Cl2-Cl1 = Cl6-Cl4
 2.7 with sigma of 0.04
 Cl6-Cl5
 2.7 with sigma of 0.04
 Cl5-Cl4
 2.7 with sigma of 0.04
 C27B-C29B
 2.5 with sigma of 0.04
 C32B-C30B
 2.5 with sigma of 0.04
 C261-C28B
 2.5 with sigma of 0.04
 C28B-C30B
 2.5 with sigma of 0.04
 C31B-C29B
 2.5 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
C301 \\sim C311 \\sim C321: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 1.7A
C82C \\sim C72C \\sim C92C: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 1.7A
C261 \\sim C27A \\sim C28A \\sim C29A \\sim C30A \\sim C31A \\sim C32A: within
1.7A with sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
C281 \\sim C291 \\sim C301: within 1.7A with sigma of 0.004 and sigma for
terminal atoms of 0.008 within 1.7A
C63 \\sim C63D: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 1.7A
C201 \\sim C241 \\sim C231 \\sim C211 \\sim C191 \\sim C221: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
C151 \\sim C171 \\sim C181 \\sim C141 \\sim C161 \\sim C131: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
C62 \\sim C62C: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008 within 1.7A
C27B \\sim C28B \\sim C29B \\sim C30B \\sim C31B \\sim C32B: within 1.7A with
sigma of 0.004 and sigma for terminal atoms of 0.008 within 1.7A
Uanis(C82) \\sim Ueq, Uanis(C82C) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C72C)
\\sim Ueq, Uanis(C92C) \\sim Ueq, Uanis(C92) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C82C) \\sim Ueq, Uanis(C72C) \\sim Ueq, Uanis(C92C) \\sim Ueq: with sigma
of 0.05 and sigma for terminal atoms of 0.1
Uanis(C82) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C72) \\sim Ueq: with sigma of
0.05 and sigma for terminal atoms of 0.1
Uanis(C83) \\sim Ueq, Uanis(C93D) \\sim Ueq, Uanis(C73) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C30A) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C28A) \\sim Ueq,
Uanis(C27A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C271) \\sim Ueq, Uanis(C281) \\sim Ueq, Uanis(C291) \\sim Ueq,
Uanis(C301) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C28A) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C29A) \\sim Ueq,
Uanis(C30A) \\sim Ueq, Uanis(C31A) \\sim Ueq, Uanis(C32A) \\sim Ueq: with sigma
of 0.04 and sigma for terminal atoms of 0.08
Uanis(C261) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C93) \\sim Ueq, Uanis(C83D) \\sim Ueq, Uanis(C73D) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C62C) \\sim Ueq, Uanis(C62) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C63) \\sim Ueq, Uanis(C63D) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C27B) \\sim Ueq, Uanis(C28B) \\sim Ueq, Uanis(C29B) \\sim Ueq,
Uanis(C30B) \\sim Ueq, Uanis(C31B) \\sim Ueq, Uanis(C32B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C25) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl6) \\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(Cl5) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C82C) = Uanis(C72C) = Uanis(C92C)
Uanis(C92) = Uanis(C72) = Uanis(C82)
Uanis(C73) = Uanis(C83) = Uanis(C93)
Uanis(C73D) = Uanis(C83D) = Uanis(C93D)
Uanis(C63) = Uanis(C63D)
Uanis(Cl6) = Uanis(Cl4) = Uanis(Cl5)
3. Others
 Fixed Sof: C63(0.5) C62(0.5) H26E(0.5) H26F(0.5) H26C(0.25) H26D(0.25)
 H26A(0.25) H26B(0.25) C93(0.5) H93A(0.5) H93B(0.5) H93C(0.5) C271(0.5)
 H27A(0.5) H27B(0.5) C83(0.5) H83A(0.5) H83B(0.5) H83C(0.5) C73(0.5) H73A(0.5)
 H73B(0.5) H73C(0.5) C281(0.5) H28A(0.5) H28B(0.5) C72(0.5) H72A(0.5) H72B(0.5)
 H72C(0.5) C82(0.5) H82A(0.5) H82B(0.5) H82C(0.5) C92(0.5) H92A(0.5) H92B(0.5)
 H92C(0.5) Cl1(0.5) Cl2(0.5) Cl3(0.5) C18(0.5) H18(0.5) C83D(0.5) H83D(0.5)
 H83E(0.5) H83F(0.5) C63D(0.5) C93D(0.5) H93D(0.5) H93E(0.5) H93F(0.5)
 C73D(0.5) H73D(0.5) H73E(0.5) H73F(0.5) C62C(0.5) C82C(0.5) H82D(0.5)
 H82E(0.5) H82F(0.5) C72C(0.5) H72D(0.5) H72E(0.5) H72F(0.5) C92C(0.5)
 H92D(0.5) H92E(0.5) H92F(0.5) C291(0.5) H29A(0.5) H29B(0.5) C301(0.5)
 H30A(0.5) H30B(0.5) Cl5(0.25) Cl4(0.25) Cl6(0.25) C25(0.25) H25(0.25)
 C27A(0.25) H27C(0.25) H27D(0.25) C29A(0.25) H29C(0.25) H29D(0.25) C28A(0.25)
 H28C(0.25) H28D(0.25) C30A(0.25) H30C(0.25) H30D(0.25) C31A(0.25) H31A(0.25)
 H31B(0.25) C32A(0.25) H32A(0.25) H32B(0.25) H32C(0.25) C29B(0.25) H29E(0.25)
 H29F(0.25) C31B(0.25) H31C(0.25) H31D(0.25) C27B(0.25) H27E(0.25) H27F(0.25)
 C28B(0.25) H28E(0.25) H28F(0.25) C30B(0.25) H30E(0.25) H30F(0.25) C32B(0.25)
 H32D(0.25) H32E(0.25) H32F(0.25) C311(0.5) H31E(0.5) H31F(0.5) C321(0.5)
 H32G(0.5) H32H(0.5) H32I(0.5)
 Fixed X: H83A(0.6392) H83B(0.6154) H83C(0.6449) H72A(0.9378) H72B(0.91)
 H72C(0.9623) H82A(0.9504) H82B(0.8998) H82C(0.9279) H92A(0.9966) H92B(0.9863)
 H92C(1.0099) H82D(0.9542) H82E(0.9555) H82F(0.9094) H72D(0.9533) H72E(0.9351)
 H72F(0.9025) H92D(0.985) H92E(1.0091) H92F(0.9905) H32G(0.5399) H32H(0.5161)
 H32I(0.5068)
 Fixed Y: H83A(0.5756) H83B(0.4907) H83C(0.5494) H72A(0.3747) H72B(0.4034)
 H72C(0.3952) H82A(0.5458) H82B(0.5365) H82C(0.6176) H92A(0.5881) H92B(0.5529)
 H92C(0.4911) H82D(0.6537) H82E(0.5898) H82F(0.6172) H72D(0.4579) H72E(0.3988)
 H72F(0.4619) H92D(0.4297) H92E(0.516) H92F(0.5105) H32G(0.0886) H32H(0.1806)
 H32I(0.1211)
 Fixed Z: H83A(0.4237) H83B(0.4461) H83C(0.4851) H72A(0.6489) H72B(0.6998)
 H72C(0.7041) H82A(0.7427) H82B(0.7256) H82C(0.7054) H92A(0.6671) H92B(0.6084)
 H92C(0.6511) H82D(0.682) H82E(0.7322) H82F(0.7061) H72D(0.7327) H72E(0.685)
 H72F(0.7163) H92D(0.6469) H92E(0.6673) H92F(0.6075) H32G(0.4766) H32H(0.4706)
 H32I(0.5215)
4.a Ternary CH refined with riding coordinates:
 C18(H18), C25(H25)
4.b Secondary CH2 refined with riding coordinates:
 CM12(HM1A,HM1B), CM13(HM1C,HM1D), CM23(HM2A,HM2B), C251(H25A,H25B), C261(H26E,
 H26F), C261(H26C,H26D), C261(H26A,H26B), C271(H27A,H27B), C281(H28A,H28B),
 C291(H29A,H29B), C301(H30A,H30B), C27A(H27C,H27D), C29A(H29C,H29D), C28A(H28C,
 H28D), C30A(H30C,H30D), C31A(H31A,H31B), C29B(H29E,H29F), C31B(H31C,H31D),
 C27B(H27E,H27F), C28B(H28E,H28F), C30B(H30E,H30F), C311(H31E,H31F)
4.c Aromatic/amide H refined with riding coordinates:
 C121(H121), C41(H41), C22(H22), C23(H23), C81(H81), C21(H21), C43(H43),
 C241(H241), C42(H42), C91(H91), C181(H181), C231(H231), C101(H101), C141(H141),
  C221(H221), C201(H201), C171(H171), C151(H151), C211(H211), C161(H161)
4.d Idealised Me refined as rotating group:
 C103(H10A,H10B,H10C), C102(H10D,H10E,H10F), C93(H93A,H93B,H93C), C73(H73A,
 H73B,H73C), C83D(H83D,H83E,H83F), C93D(H93D,H93E,H93F), C73D(H73D,H73E,H73F),
 C32A(H32A,H32B,H32C), C32B(H32D,H32E,H32F)
;
_shelx_res_checksum              72833
_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
;