Dehydrogenative coupling of 4-substituted pyridines mediated by a zirconium(ii) synthon: reaction pathways and dead ends.
Merz, Lukas S.; Wadepohl, Hubert; Clot, Eric; Gade, Lutz H.; Chemical science 9 (2018) 5223–5232; doi:10.1039/c8sc01025k

data_1554590
_publ_section_title
;
 Dehydrogenative coupling of 4-substituted pyridines mediated by a
 zirconium(ii) synthon: reaction pathways and dead ends.
;
_journal_issue                   23
_journal_name_full               'Chemical science'
_journal_page_first              5223
_journal_page_last               5232
_journal_paper_doi               10.1039/c8sc01025k
_journal_volume                  9
_journal_year                    2018
_chemical_formula_moiety         'C48 H72 Cl N5 P2 Zr, C4 H10 O'
_chemical_formula_sum            'C52 H82 Cl N5 O P2 Zr'
_chemical_formula_weight         981.83
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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   geom
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_lm19
_audit_creation_date             2017-01-20
_audit_creation_method
;
Olex2 1.2
(compiled Aug 10 2017 17:44:14 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-02-28 deposited with the CCDC.
2018-05-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.4621(19)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   37.6269(7)
_cell_length_b                   12.5284(3)
_cell_length_c                   22.9308(4)
_cell_measurement_reflns_used    11265
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      28.5390
_cell_measurement_theta_min      3.0550
_cell_volume                     10662.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material
'encif (Wadepohl, 2009-17); encifer 1.5.2 (CCDC, 2016)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SUPERFLIP (Palatinus, 2007-2009)'
_diffrn_ambient_environment      'perfluoro polyether oil / N~2~'
_diffrn_ambient_temperature      120(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 7.9621
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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      1.00  92.00   0.50   25.00    --   26.87  77.00-180.00  182
  2  \w      6.00  96.00   0.50   25.00    --   26.87  57.00 -60.00  180
  3  \w    -42.00  48.00   0.50   25.00    --   26.87 -57.00 150.00  180
  4  \w      6.00  96.00   0.50   25.00    --   26.87  57.00 120.00  180
  5  \w    -42.00  42.00   0.50   25.00    --   26.87 -57.00 -30.00  168
  6  \w    -20.00  69.00   0.50   25.00    --   26.87 -99.00 -90.00  178
  7  \w      1.00  94.00   0.50   25.00    --   26.87  77.00   0.00  186
  8  \w    -38.00  49.00   0.50   25.00    --   26.87 -38.00  30.00  174
  9  \w     25.00  69.00   0.50   25.00    --   26.87 -99.00  90.00   88
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Agilent SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'polyimid foil'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0019086000
_diffrn_orient_matrix_UB_12      0.0047957000
_diffrn_orient_matrix_UB_13      -0.0311858000
_diffrn_orient_matrix_UB_21      -0.0035144000
_diffrn_orient_matrix_UB_22      -0.0555110000
_diffrn_orient_matrix_UB_23      -0.0029779000
_diffrn_orient_matrix_UB_31      -0.0186840000
_diffrn_orient_matrix_UB_32      0.0100269000
_diffrn_orient_matrix_UB_33      -0.0015160000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1174
_diffrn_reflns_av_unetI/netI     0.0845
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       52
_diffrn_reflns_limit_h_min       -52
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            90595
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.609
_diffrn_reflns_theta_min         2.552
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.356
_exptl_absorpt_correction_T_max  0.978
_exptl_absorpt_correction_T_min  0.963
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
 a multifaceted crystal model (Busing & Levy, 1957).
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.223
_exptl_crystal_description       irregular
_exptl_crystal_F_000             4192
_exptl_crystal_size_max          0.139
_exptl_crystal_size_mid          0.113
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.842
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     579
_refine_ls_number_reflns         14980
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0940
_refine_ls_R_factor_gt           0.0539
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0320P)^2^+12.5837P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1124
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10345
_reflns_number_total             14980
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01025k3.cif
_cod_data_source_block           ga_lm19
_cod_original_cell_volume        10662.7(4)
_cod_original_sg_symbol_Hall     '-C 2yn'
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               1554590
_audit_block_refno               2805
_audit_block_usercomment         'LM099_2, irregular, orange'
_chemical_oxdiff_formula         'C52 H82 Cl1 N5 O1 P2 Zr1'
_chemical_oxdiff_usercomment     'LM099_2, irregular, orange'
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.965
_reflns_odcompleteness_completeness 92.17
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_shelxl_version_number           2018/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C14(H14), C24(H24), C27(H27), C30(H30), C33(H33)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C51(H51A,H51B), C53(H53A,H53B)
2.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C11(H11), C37(H37), C39(H39), C40(H40), C43(H43),
 C44(H44), C46(H46), C47(H47)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C52(H52A,
 H52B,H52C), C54(H54A,H54B,H54C)
;
_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 1.135
_oxdiff_exptl_absorpt_empirical_full_min 0.900
_shelx_res_checksum              1134
_cell_oxdiff_length_a            37.6320(6)
_cell_oxdiff_length_b            12.5290(2)
_cell_oxdiff_length_c            22.9254(5)
_cell_oxdiff_angle_alpha         90.0303(16)
_cell_oxdiff_angle_beta          99.4420(16)
_cell_oxdiff_angle_gamma         89.9213(14)
_cell_oxdiff_volume              10662.7(3)
_cell_oxdiff_measurement_reflns_used 11265