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_1554588
_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         'C40 H59 Cl N2 P2 Zr'
_chemical_formula_sum            'C40 H59 Cl N2 P2 Zr'
_chemical_formula_weight         756.50
_chemical_properties_physical    'air-sensitive, moisture-sensitive'
_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   mixed
_atom_sites_solution_primary     heavy
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_lm11
_audit_creation_date             2016-08-22
_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                112.686(3)
_cell_angle_beta                 97.711(2)
_cell_angle_gamma                98.630(3)
_cell_formula_units_Z            2
_cell_length_a                   11.9355(4)
_cell_length_b                   12.1743(4)
_cell_length_c                   15.3187(4)
_cell_measurement_reflns_used    3497
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      26.3370
_cell_measurement_theta_min      3.3720
_cell_volume                     1984.93(12)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43c (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43c (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    'DIRDIF (Beurskens et al., 1999-2008)'
_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 0.994
_diffrn_measured_fraction_theta_max 0.994
_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      6.00  97.00   0.50   10.00    --   28.00  57.00 150.00  182
  2  \w    -43.00  60.00   0.50   10.00    --   28.00 -77.00 120.00  206
  3  \w    -20.00  72.00   0.50   10.00    --   28.00 -99.00 -60.00  184
  4  \w    -41.00  50.00   0.50   10.00    --   28.00 -57.00   0.00  182
  5  \w    -41.00  50.00   0.50   10.00    --   28.00 -57.00-180.00  182
  6  \w     -4.00  66.50   0.50   10.00    --   28.00  77.00  60.00  141
;
_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      0.0341998000
_diffrn_orient_matrix_UB_12      -0.0414771000
_diffrn_orient_matrix_UB_13      0.0038237000
_diffrn_orient_matrix_UB_21      -0.0506713000
_diffrn_orient_matrix_UB_22      -0.0418537000
_diffrn_orient_matrix_UB_23      -0.0039428000
_diffrn_orient_matrix_UB_31      -0.0065551000
_diffrn_orient_matrix_UB_32      -0.0268732000
_diffrn_orient_matrix_UB_33      -0.0510393000
_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  0.0754
_diffrn_reflns_av_unetI/netI     0.0790
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            18410
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.170
_diffrn_reflns_theta_max         25.170
_diffrn_reflns_theta_min         2.911
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.454
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7386
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43c (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.266
_exptl_crystal_description       block
_exptl_crystal_F_000             800
_exptl_crystal_size_max          0.100
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.100
_refine_diff_density_max         0.551
_refine_diff_density_min         -0.458
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.924
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         7999
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.924
_refine_ls_R_factor_all          0.0572
_refine_ls_R_factor_gt           0.0360
_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^)+(0.0267P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0653
_refine_ls_wR_factor_ref         0.0684
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6167
_reflns_number_total             7999
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01025k3.cif
_cod_data_source_block           ga_lm11_5
_cod_original_cell_volume        1984.94(11)
_cod_database_code               1554588
_audit_block_refno               2754
_audit_block_usercomment         'LM034 yellow block'
_chemical_oxdiff_formula         'C40 H59 Cl1 N2 P2 Zr1'
_chemical_oxdiff_usercomment     'LM034 yellow block'
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.956
_shelxl_version_number           2018/1
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6635(15)
 0.3365(15)
2. 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
3.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C33(H33)
3.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B)
3.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C11(H11), C37(H37), C38(H38), C39(H39)
3.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)
;
_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 1.171
_oxdiff_exptl_absorpt_empirical_full_min 0.865
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by 5.3347\%
 around [0.86 -0.48 0.18] (reciprocal) or [0.94 -0.32 0.12] (direct)
;
_shelx_res_checksum              11061
_cell_oxdiff_length_a            11.9362(6)
_cell_oxdiff_length_b            12.1721(6)
_cell_oxdiff_length_c            15.3221(7)
_cell_oxdiff_angle_alpha         112.704(5)
_cell_oxdiff_angle_beta          97.724(4)
_cell_oxdiff_angle_gamma         98.615(4)
_cell_oxdiff_volume              1984.85(17)
_cell_oxdiff_measurement_reflns_used 3497