Synthesis, structural characterization, and coordination chemistry of imidazole-based alkylidene ketenes.
Feuerstein, Wolfram; Varava, Paul; Fadaei-Tirani, Farzaneh; Scopelliti, Rosario; Severin, Kay; Chemical communications (Cambridge, England) 57 (2021) 11509–11512; doi:10.1039/d1cc05161j

data_7129130
_publ_section_title
;
 Synthesis, structural characterization, and coordination chemistry of
 imidazole-based alkylidene ketenes.
;
_journal_issue                   87
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              11509
_journal_page_last               11512
_journal_paper_doi               10.1039/d1cc05161j
_journal_volume                  57
_journal_year                    2021
_chemical_formula_moiety
'0.471(Br), 0.529(Cl), C H2 Cl2, C58 H73 N4 O2'
_chemical_formula_sum            'C59 H75 Br0.47 Cl2.53 N4 O2'
_chemical_formula_weight         999.53
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-06-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-06 deposited with the CCDC.	2021-10-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.752(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.5239(7)
_cell_length_b                   29.6444(9)
_cell_length_c                   16.5867(5)
_cell_measurement_reflns_used    7195
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      68.2190
_cell_measurement_theta_min      3.5650
_cell_volume                     11997.8(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_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    -74.00   9.00   1.00   10.00    --  -43.13  75.00 125.00   83
  2  \w     25.00  51.00   1.00   10.00    --   43.13 -75.00  -2.00   26
  3  \w    105.00 166.00   1.00   40.00    --  103.80  75.00 125.00   61
  4  \w     35.00 132.00   1.00   40.00    --  103.80 -75.00  -2.00   97
  5  \w     -7.00  30.00   1.00   10.00    --  -43.13  37.00   0.00   37
  6  \w   -117.00 -19.00   1.00   10.00    --  -43.13 -37.00-180.00   98
  7  \w     41.00  69.00   1.00   10.00    --   43.13 -99.00-180.00   28
  8  \w     47.00 108.00   1.00   40.00    --  103.80-111.00-150.00   61
  9  \w     29.00 129.00   1.00   40.00    --  103.80 -30.00   0.00  100
 10  \w    126.00 153.00   1.00   40.00    --  103.80 111.00   0.00   27
 11  \w    106.00 177.00   1.00   40.00    --  103.80 111.00  90.00   71
 12  \w     28.00  96.00   1.00   40.00    --  103.80-111.00 -60.00   68
 13  \w    107.00 163.00   1.00   40.00    --  103.80 111.00 -30.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0241752000
_diffrn_orient_matrix_UB_12      -0.0205058000
_diffrn_orient_matrix_UB_13      -0.0811278000
_diffrn_orient_matrix_UB_21      -0.0268170000
_diffrn_orient_matrix_UB_22      -0.0378414000
_diffrn_orient_matrix_UB_23      0.0461146000
_diffrn_orient_matrix_UB_31      -0.0517649000
_diffrn_orient_matrix_UB_32      0.0291521000
_diffrn_orient_matrix_UB_33      0.0026140000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0860
_diffrn_reflns_av_unetI/netI     0.0971
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            61782
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.610
_diffrn_reflns_theta_min         2.981
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.867
_exptl_absorpt_correction_T_max  0.771
_exptl_absorpt_correction_T_min  0.313
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_density_diffrn    1.107
_exptl_crystal_description       prism
_exptl_crystal_F_000             4260
_exptl_crystal_size_max          0.605
_exptl_crystal_size_mid          0.357
_exptl_crystal_size_min          0.093
_refine_diff_density_max         0.746
_refine_diff_density_min         -0.495
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1356
_refine_ls_number_reflns         23200
_refine_ls_number_restraints     1203
_refine_ls_restrained_S_all      0.991
_refine_ls_R_factor_all          0.1362
_refine_ls_R_factor_gt           0.0727
_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^)+(0.0987P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1748
_refine_ls_wR_factor_ref         0.2142
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12412
_reflns_number_total             23200
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05161j2.cif
_cod_data_source_block           wf446hbr
_cod_depositor_comments
'Adding full bibliography for 7129122--7129133.cif.'
_cod_database_code               7129130
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C61 H79 N4 O2 Cl6 Br1'
_shelx_estimated_absorpt_t_max   0.846
_shelx_estimated_absorpt_t_min   0.398
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C121-C118 \\sim C117-C122
 with sigma of 0.02
 C121-C116 \\sim C117-C116 \\sim C118-C116 \\sim C122-C116
 with sigma of 0.02
 C80-C123 \\sim C82-C80 \\sim C81-C80 \\sim C80-C124
 with sigma of 0.02
 C123-C124 \\sim C82-C81
 with sigma of 0.02
 Cl7-C119 \\sim Cl4-C119 \\sim Cl3-C119 \\sim Cl8-C119
 with sigma of 0.02
 Cl7-Cl8 \\sim Cl4-Cl3
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Br1 \\sim Cl2 \\sim Cl1: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C119 \\sim Cl7 \\sim Cl4 \\sim Cl8 \\sim Cl3: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(Cl1) = Uanis(Br1) = Uanis(Br2) = Uanis(Cl2)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Cl2)=Sof(Cl1)=1-FVAR(1)
 Sof(Br1)=Sof(Br2)=FVAR(1)
 Sof(O5)=Sof(O6)=Sof(H62A)=Sof(C65)=Sof(C66)=1-FVAR(2)
 Sof(O3)=Sof(O4)=Sof(H62)=Sof(C63)=Sof(C64)=FVAR(2)
 Sof(H11G)=Sof(C117)=Sof(H11H)=Sof(H11I)=Sof(H11J)=Sof(C122)=Sof(H12A)=
 Sof(H12B)=Sof(H12C)=1-FVAR(3)
 Sof(H116)=Sof(C118)=Sof(H11K)=Sof(H11L)=Sof(H11M)=Sof(C121)=Sof(H12D)=
 Sof(H12E)=Sof(H12F)=FVAR(3)
 Sof(H80A)=Sof(C124)=Sof(H12G)=Sof(H12H)=Sof(H12I)=Sof(C123)=Sof(H12J)=
 Sof(H12K)=Sof(H12L)=1-FVAR(4)
 Sof(H80)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C82)=Sof(H82A)=Sof(H82B)=
 Sof(H82C)=FVAR(4)
 Sof(H11P)=Sof(H11Q)=Sof(Cl7)=Sof(Cl8)=1-FVAR(5)
 Sof(Cl3)=Sof(Cl4)=Sof(H11N)=Sof(H11O)=FVAR(5)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C17(H17), C20(H20), C29(H29), C32(H32), C41(H41), C44(H44), C53(H53),
 C56(H56), C62(H62), C62(H62A), C77(H77), C80(H80), C80(H80A), C89(H89),
 C92(H92), C101(H101), C104(H104), C113(H113), C116(H11G), C116(H116)
6.b Secondary CH2 refined with riding coordinates:
 C119(H11N,H11O), C119(H11P,H11Q), C120(H12M,H12N)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15), C25(H25),
 C26(H26), C27(H27), C37(H37), C38(H38), C39(H39), C49(H49), C50(H50), C51(H51),
  C60(H60), C61(H61), C69(H69), C70(H70), C73(H73), C74(H74), C75(H75),
 C85(H85), C86(H86), C87(H87), C97(H97), C98(H98), C99(H99), C109(H109),
 C110(H110), C111(H111)
6.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C81(H81A,
 H81B,H81C), C82(H82A,H82B,H82C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C),
 C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C102(H10A,H10B,H10C), C103(H10D,H10E,
 H10F), C105(H10G,H10H,H10I), C106(H10J,H10K,H10L), C114(H11A,H11B,H11C),
 C115(H11D,H11E,H11F), C117(H11H,H11I,H11J), C118(H11K,H11L,H11M), C122(H12A,
 H12B,H12C), C121(H12D,H12E,H12F), C124(H12G,H12H,H12I), C123(H12J,H12K,H12L)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 318 electrons were 
found in a volume of 1540\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
0.95[CH2Cl2] per Asymmetric Unit 
which account for 319 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              10706
_shelx_hkl_checksum              62834
_shelx_fab_checksum              37655
_olex2_date_sample_data_collection 2021-05-27
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.752
_oxdiff_exptl_absorpt_empirical_full_min 0.462