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_1554591
_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_sum            'C57 H80 Cl N3 P2 Zr'
_chemical_formula_weight         995.85
_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     iterative
_atom_sites_solution_secondary   difmap
_audit_block_code                ga_lm10
_audit_creation_date             2016-06-27
_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                100.8658(12)
_cell_angle_beta                 95.4948(13)
_cell_angle_gamma                103.4908(14)
_cell_formula_units_Z            4
_cell_length_a                   12.6621(2)
_cell_length_b                   18.1002(3)
_cell_length_c                   23.9357(3)
_cell_measurement_reflns_used    36948
_cell_measurement_temperature    120(1)
_cell_measurement_theta_max      31.0950
_cell_measurement_theta_min      3.2310
_cell_volume                     5182.35(14)
_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 0.998
_diffrn_measured_fraction_theta_max 0.947
_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    -20.00  72.00   0.50   12.50    --   28.16 -99.00  60.00  184
  2  \w     -3.00  99.00   0.50   12.50    --   28.16  77.00-120.00  204
  3  \w     -3.00  99.00   0.50   12.50    --   28.16  77.00 -30.00  204
  4  \w    -43.00  60.00   0.50   12.50    --   28.16 -77.00 120.00  206
  5  \w    -43.00  62.00   0.50   12.50    --   28.16 -81.00-128.00  210
  6  \w      7.00  97.00   0.50   12.50    --   28.16  57.00  90.00  180
  7  \w    -41.00  50.00   0.50   12.50    --   28.16 -57.00 -60.00  182
  8  \w      7.00  97.00   0.50   12.50    --   28.16  57.00-150.00  180
  9  \w     -3.00  99.00   0.50   12.50    --   28.16  77.00 150.00  204
 10  \w    -41.00  50.00   0.50   12.50    --   28.16 -57.00 120.00  182
 11  \w     -3.00  99.00   0.50   12.50    --   28.16  77.00  60.00  204
 12  \w    -20.00  72.00   0.50   12.50    --   28.16 -99.00 -90.00  184
 13  \w      7.00  97.00   0.50   12.50    --   28.16  57.00 150.00  180
 14  \w      1.00  86.00   0.50   12.50    --   28.16  38.00  30.00  170
 15  \w      1.00 101.00   0.50   12.50    --   28.16  38.00-150.00  200
;
_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      0.0513056000
_diffrn_orient_matrix_UB_12      0.0028635000
_diffrn_orient_matrix_UB_13      -0.0101571000
_diffrn_orient_matrix_UB_21      0.0253188000
_diffrn_orient_matrix_UB_22      0.0304916000
_diffrn_orient_matrix_UB_23      0.0241461000
_diffrn_orient_matrix_UB_31      0.0108574000
_diffrn_orient_matrix_UB_32      -0.0276949000
_diffrn_orient_matrix_UB_33      0.0156278000
_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  0.0705
_diffrn_reflns_av_unetI/netI     0.0612
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            184312
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.338
_diffrn_reflns_theta_min         3.080
_diffrn_source                   'microfocus X-Ray tube'
_diffrn_source_type              'Agilent SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.365
_exptl_absorpt_correction_T_max  0.983
_exptl_absorpt_correction_T_min  0.934
_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    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             2120
_exptl_crystal_size_max          0.283
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.057
_refine_diff_density_max         1.906
_refine_diff_density_min         -0.999
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1197
_refine_ls_number_reflns         35040
_refine_ls_number_restraints     247
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0787
_refine_ls_R_factor_gt           0.0497
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0492P)^2^+2.0752P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1091
_refine_ls_wR_factor_ref         0.1213
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25107
_reflns_number_total             35040
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01025k3.cif
_cod_data_source_block           ga_lm10_sq
_cod_original_cell_volume        5182.33(15)
_cod_database_code               1554591
_audit_block_refno               2727
_audit_block_usercomment         'LM009, block, orange'
_shelx_estimated_absorpt_t_max   0.964
_shelx_estimated_absorpt_t_min   0.964
_reflns_odcompleteness_completeness 99.90
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C76A-C77A \\sim C76A-C78A \\sim C76A-C79A \\sim C76B-C77B \\sim C76B-C78B
\\sim C76B-C79B
 with sigma of 0.02
 C10-C20A \\sim C10-C20B \\sim C65-C76A \\sim C65-C76B
 with sigma of 0.02
 C77A-C78A \\sim C77A-C79A \\sim C78A-C79A \\sim C77B-C78B \\sim C77B-C79B
\\sim C78B-C79B
 with sigma of 0.02
 C93A-C94 \\sim C93B-C94 \\sim C93A-C95A \\sim C93B-C95B
 with sigma of 0.02
 C94-C95A \\sim C94-C95B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10
\\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18
\\sim C19 \\sim C20A \\sim C21A \\sim C22A \\sim C23A \\sim C20B \\sim C21B
\\sim C22B \\sim C23B \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim
C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim
C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim
C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim
C53 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76A
\\sim C77A \\sim C78A \\sim C79A \\sim C76B \\sim C77B \\sim C78B \\sim C79B
\\sim C80 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87
\\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C94 \\sim C93A \\sim
C95A \\sim C93B \\sim C95B \\sim C96 \\sim C97 \\sim C98 \\sim C99 \\sim C100
\\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107
\\sim C108 \\sim C109 \\sim C110 \\sim C111 \\sim C112 \\sim C113: within 1A
with sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C16, C17, C18, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C20A, C21A, C22A, C23A, C20B, C21B, C22B, C23B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C76A, C77A, C78A, C79A, C76B, C77B, C78B, C79B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C80, C81, C82, C83
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C94, C93A, C95A, C93B, C95B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C16, C17, C18, C19} sigma for 1-2: 0.02, 1-3: 0.04
as
{C20A, C21A, C22A, C23A}
{C16, C17, C18, C19} sigma for 1-2: 0.02, 1-3: 0.04
as
{C20B, C21B, C22B, C23B}
{C16, C17, C18, C19} sigma for 1-2: 0.02, 1-3: 0.04
as
{C80, C81, C82, C83}
6. Others
 Sof(C76B)=Sof(C77B)=Sof(H77D)=Sof(H77E)=Sof(H77F)=Sof(C78B)=Sof(H78D)=
 Sof(H78E)=Sof(H78F)=Sof(C79B)=Sof(H79D)=Sof(H79E)=Sof(H79F)=1-FVAR(1)
 Sof(C76A)=Sof(C77A)=Sof(H77A)=Sof(H77B)=Sof(H77C)=Sof(C78A)=Sof(H78A)=
 Sof(H78B)=Sof(H78C)=Sof(C79A)=Sof(H79A)=Sof(H79B)=Sof(H79C)=FVAR(1)
 Sof(H94D)=Sof(H94E)=Sof(H94F)=Sof(C93B)=Sof(H93B)=Sof(C95B)=Sof(H95D)=
 Sof(H95E)=Sof(H95F)=1-FVAR(2)
 Sof(H94A)=Sof(H94B)=Sof(H94C)=Sof(C93A)=Sof(H93A)=Sof(C95A)=Sof(H95A)=
 Sof(H95B)=Sof(H95C)=FVAR(2)
 Sof(C20B)=Sof(C21B)=Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(C22B)=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=Sof(C23B)=Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(3)
 Sof(C20A)=Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22A)=Sof(H22A)=
 Sof(H22B)=Sof(H22C)=Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C24(H24), C27(H27), C30(H30), C33(H33), C84(H84), C87(H87), C90(H90),
 C93A(H93A), C93B(H93B)
7.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C74(H74A,H74B), C75(H75A,H75B)
7.c Me refined with riding coordinates:
 C77A(H77A,H77B,H77C), C78A(H78A,H78B,H78C), C79A(H79A,H79B,H79C), C77B(H77D,
 H77E,H77F), C78B(H78D,H78E,H78F), C79B(H79D,H79E,H79F)
7.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C9(H9), C11(H11), C38(H38), C39(H39), C40(H40), C41(H41),
 C43(H43), C44(H44), C47(H47), C48(H48), C49(H49), C50(H50), C52(H52), C53(H53),
  C64(H64), C66(H66), C69(H69), C71(H71), C98(H98), C99(H99), C100(H100),
 C101(H101), C103(H103), C104(H104), C107(H107), C108(H108), C109(H109),
 C110(H110), C112(H112), C113(H113)
7.e Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21A(H21A,H21B,
 H21C), C22A(H22A,H22B,H22C), C23A(H23A,H23B,H23C), C21B(H21D,H21E,H21F),
 C22B(H22D,H22E,H22F), C23B(H23D,H23E,H23F), 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), C81(H81A,H81B,H81C),
 C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C85(H85A,H85B,H85C), C86(H86A,H86B,
 H86C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C91(H91A,H91B,H91C), C92(H92A,
 H92B,H92C), C94(H94A,H94B,H94C), C94(H94D,H94E,H94F), C95A(H95A,H95B,H95C),
 C95B(H95D,H95E,H95F)
;
_shelx_fab_checksum              93233
_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
;
_shelx_res_checksum              98409
_cell_oxdiff_length_a            12.6621(2)
_cell_oxdiff_length_b            18.1002(3)
_cell_oxdiff_length_c            23.9357(3)
_cell_oxdiff_angle_alpha         100.8658(12)
_cell_oxdiff_angle_beta          95.4948(13)
_cell_oxdiff_angle_gamma         103.4908(14)
_cell_oxdiff_volume              5182.33(14)
_cell_oxdiff_measurement_reflns_used 36948