Exchange coupling and magnetic blocking in dilanthanide complexes bridged by the multi-electron redox-active ligand 2,3,5,6-tetra(2-pyridyl)pyrazine
Demir, Selvan; Nippe, Michael; Gonzalez, Miguel I.; Long, Jeffrey R.; Chem. Sci. 5 (2014) 4701–; doi:10.1039/C4SC02154A

data_1517446
_publ_section_title
;
 Exchange coupling and magnetic blocking in dilanthanide complexes bridged
 by the multi-electron redox-active ligand
 2,3,5,6-tetra(2-pyridyl)pyrazine
;
_journal_issue                   12
_journal_name_full               'Chem. Sci.'
_journal_page_first              4701
_journal_paper_doi               10.1039/C4SC02154A
_journal_volume                  5
_journal_year                    2014
_chemical_formula_sum            'C110 H160 Dy2 K N8 O13'
_chemical_formula_weight         2166.55
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_symmetry_space_group_name_Hall  'C -2yc'
_symmetry_space_group_name_H-M   'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/4
_cell_angle_alpha                90
_cell_angle_beta                 111.311(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.168(3)
_cell_length_b                   25.230(3)
_cell_length_c                   20.706(2)
_cell_measurement_reflns_used    9983
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.357
_cell_measurement_theta_min      2.852
_cell_volume                     10789(2)
_computing_cell_refinement       'Bruker SAINT v8.18c'
_computing_data_collection       'Bruker APEX 2'
_computing_data_reduction        'Bruker SAINT v8.18c'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/4 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT-2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.42
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker PHOTON100 CMOS diffractometer'
_diffrn_measurement_method       '\w/\q scans'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7749
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0614
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            53408
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        27.706
_diffrn_reflns_theta_max         29.497
_diffrn_reflns_theta_min         2.038
_diffrn_source                   'Advanced Light Source Station 11.3.1'
_exptl_absorpt_coefficient_mu    1.844
_exptl_absorpt_correction_T_max  0.955
_exptl_absorpt_correction_T_min  0.754
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2008/1 Bruker AXS Madison WI USA'
_exptl_crystal_colour            'dark purple'
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             4524
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: tetrahydrofuran'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.025
_refine_diff_density_max         2.603
_refine_diff_density_min         -1.296
_refine_diff_density_rms         0.102
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.451(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1492
_refine_ls_number_reflns         22271
_refine_ls_number_restraints     1968
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0753
_refine_ls_R_factor_gt           0.0511
_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^)+(0.0618P)^2^+36.2501P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1190
_refine_ls_wR_factor_ref         0.1351
_reflns_Friedel_coverage         0.999
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                17767
_reflns_number_total             22271
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4sc02154a3.cif
_cod_data_source_block           sd006s
_cod_depositor_comments
;
The following automatic conversions were performed:

'_atom_sites_solution_primary' value 'Direct' changed to 'direct'
according to
/usr/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 2281 2013-09-26 08:29:07Z andrius 

 Adding full bibliography for 1517443--1517446.cif.
;
_cod_database_code               1517446
_shelx_estimated_absorpt_t_min   0.769
_shelx_estimated_absorpt_t_max   0.955
_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
 C109-C110 = C111-C112
 1.45 with sigma of 0.02
 C111-C110
 1.46 with sigma of 0.02
 O13-C109 = O13-C112
 1.43 with sigma of 0.02
 C103-C101
 1.45 with sigma of 0.02
 C103-O11
 1.43 with sigma of 0.02
 C97A-C96A
 1.46 with sigma of 0.02
 C96A-C95A = C98A-C97A
 1.45 with sigma of 0.02
 O10A-C95A = O10A-C98A
 1.43 with sigma of 0.02
 C96B-C97B = C84-C85 = C88-C89 = C101-C100 = C92B-C93B = C106-C105
 1.46 with sigma of 0.02
 C100-C99 = C102-C101 = C90-C89 = C88-C87 = C105-C104 = C106-C107 = C86-C85 =
 C91B-C92B = C93B-C94B = C98B-C97B = C96B-C95B = C84-C83
 1.45 with sigma of 0.02
 O12-C107 = O12-C104 = O8-C90 = O8-C87 = O11-C102 = O11-C99 = O10B-C98B = O10B-
 C95B = O7-C86 = O7-C83 = O9B-C91B = O9B-C94B
 1.43 with sigma of 0.02
 C58B-C59B \\sim C59B-C55B \\sim C59A-C55A \\sim C59A-C58A \\sim C57B-C58B
\\sim C57A-C58A \\sim C56B-
 C57B \\sim C57A-C56A \\sim C56B-C55B \\sim C56A-C55A
 with sigma of 0.02
 C56B-C61B \\sim C56A-C61A \\sim C60B-C55B \\sim C60A-C55A \\sim C59B-C64B
\\sim C59A-C64A \\sim C63A-
 C58A \\sim C62B-C57B \\sim C62A-C57A
 with sigma of 0.02
 C47A-C46A \\sim C48B-C49B \\sim C45A-C46A \\sim C45B-C49B \\sim C49A-C45A
\\sim C45B-C46B \\sim C46B-
 C47B \\sim C48A-C49A \\sim C47A-C48A \\sim C47B-C48B
 with sigma of 0.02
 C63A-C58A \\sim C62B-C57B \\sim C62A-C57A \\sim C56B-C61B \\sim C56A-C61A
\\sim C60B-C55B \\sim C60A-
 C55A \\sim C59B-C64B \\sim C59A-C64A
 with sigma of 0.02
 C63B-C58B \\sim C63A-C58A \\sim C62B-C57B \\sim C62A-C57A \\sim C56B-C61B
\\sim C56A-C61A \\sim C60B-
 C55B \\sim C60A-C55A \\sim C59B-C64B \\sim C59A-C64A
 with sigma of 0.02
 N8-C76 \\sim N8-C70 \\sim N8-C82 \\sim N7-C71 \\sim N7-C77 \\sim N7-C65
 with sigma of 0.02
 C75-C76 \\sim C70-C69 \\sim C81-C82 \\sim C72-C71 \\sim C77-C78 \\sim C66-C65
 with sigma of 0.02
 O1-C66 \\sim O5-C78 \\sim O6-C81 \\sim O2-C69 \\sim O4-C75 \\sim O3-C72
 with sigma of 0.02
 O2-C68 \\sim O1-C67 \\sim O6-C80 \\sim O4-C74 \\sim O3-C73 \\sim O5-C79
 with sigma of 0.02
 C67-C68 \\sim C79-C80 \\sim C74-C73
 with sigma of 0.02
 K1-O2 \\sim K1-O1 \\sim K1-O5 \\sim K1-O4 \\sim K1-O6
 with sigma of 0.02
 K1-N8 \\sim K1-N7
 with sigma of 0.02
 C95B-C98B \\sim C95A-C98A
 with sigma of 0.02
3. Rigid bond restraints
 C49B, C49A, C45A, C59A, C51A, C50A, C45B, C54A, C51B, C50B, C48B, C48A, C60A,
 C52A, C47A, C47B, C46A, C46B, C53B, C52B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C58A, C55B, C60A, C59A, C56A, C64B, C61B, C57A, C62B, C55A, C60B, C59B, C58A,
 C64A, C61A, C58B, C57B, C62A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C58A, C55B, C60A, C59A, C56A, C64B, C61B, C57A, C62B, C55A, C60B, C59B, C56B,
 C64A, C61A, C58B, C57B, C62A, C63A, C63B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C48B, C48A, C49B, C49A, C45A, C53A, C54B, C52A, C51A, C50A, C47A, C47B, C46A,
 C46B, C45B, C53B, C54A, C51B, C50B, C52B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C48B, C48A, C49B, C49A, C45A, C53A, C54B, C52A, C51A, C50A, C47A, C47B, C46A,
 C46B, C45B, C53B, C54A, C51B, C50B, C52B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 K1, O2, O5, N7, O1, O3, C65, H65A, H65B, C68, H68A, H68B, C71, H71A, H71B,
 C69, H69A, H69B, C66, H66A, H66B, C72, H72A, H72B, O4, C78, H78A, H78B, C77,
 H77A, H77B, C75, H75A, H75B, C67, H67A, H67B, C70, C79, H79A, H79B, N8, C73,
 H73A, H73B, C74, H74A, H74B, C80, H80A, H80B, C76, H76A, H76B, O6, C81, C82
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C111, C109, C112, O13, C110
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O13, C110, C109, C111, C112
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C99, C100, C101, C102, O11, C103
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C95B, C96B, C97B, C98B, O10B, C95A, C96A, C97A, C98A, O10A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O8, C89, C87, C90, C88, O12, C104, C105, C107, C106, O11, C99, C100, C101,
 C102, O9B, C93B, C92B, C91B, C94B, O7, C85, C86, C83, C84, O10B, C95B, C97B,
 C96B, C98B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C91B, C92B, C93B, C94B, O9B, O9A, C94A, C93A, C92A, C91A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C58A \\sim C55B \\sim C60A \\sim C59A \\sim C56A \\sim C64B \\sim C61B \\sim
C57A \\sim C62B \\sim C55A \\sim C60B \\sim C59B \\sim C56B \\sim C61A \\sim
C58B \\sim C57B \\sim C62A \\sim C63A \\sim C64A: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04
C58A \\sim C55B \\sim C60A \\sim C59A \\sim C56A \\sim C64B \\sim C61B \\sim
C57A \\sim C55A \\sim C60B \\sim C59B \\sim C56B \\sim C64A \\sim C61A \\sim
C58B \\sim C57B \\sim C62A \\sim C63A \\sim C63B \\sim C62B: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
C48B \\sim C48A \\sim C49B \\sim C49A \\sim C45A \\sim C53A \\sim C54B \\sim
C52A \\sim C51A \\sim C50A \\sim C47A \\sim C47B \\sim C46A \\sim C46B \\sim
C45B \\sim C53B \\sim C54A \\sim C51B \\sim C50B \\sim C52B: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
K1 \\sim O2 \\sim O5 \\sim N7 \\sim O1 \\sim O3 \\sim C65 \\sim H65A \\sim H65B
\\sim C68 \\sim H68A \\sim H68B \\sim C71 \\sim H71A \\sim H71B \\sim C69 \\sim
H69A \\sim H69B \\sim C66 \\sim H66A \\sim H66B \\sim C72 \\sim H72A \\sim H72B
\\sim O4 \\sim C78 \\sim H78A \\sim H78B \\sim C77 \\sim H77A \\sim H77B \\sim
C75 \\sim H75A \\sim H75B \\sim C67 \\sim H67A \\sim C70 \\sim C79 \\sim H79A
\\sim H79B \\sim N8 \\sim C73 \\sim H73A \\sim H73B \\sim C74 \\sim H74A \\sim
H74B \\sim C80 \\sim H80A \\sim H80B \\sim C76 \\sim H76A \\sim H76B \\sim O6
\\sim C81 \\sim C82 \\sim H67B: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C111 \\sim C109 \\sim C112 \\sim O13 \\sim C110: within 1.7A with sigma of 0.04
and sigma for terminal atoms of 0.08
C99 \\sim C100 \\sim C101 \\sim C102 \\sim O11 \\sim C103: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C95B \\sim C96B \\sim C97B \\sim C98B \\sim O10B \\sim C95A \\sim C96A \\sim
C97A \\sim C98A \\sim O10A: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
O12 \\sim C104 \\sim C105 \\sim C107 \\sim C106 \\sim O11 \\sim C99 \\sim C100
\\sim C101 \\sim C102 \\sim O7 \\sim C85 \\sim C86 \\sim C83 \\sim C84 \\sim
O9B \\sim C93B \\sim C92B \\sim C91B \\sim C94B \\sim O10B \\sim C95B \\sim
C97B \\sim C96B \\sim C98B \\sim O8 \\sim C89 \\sim C87 \\sim C90 \\sim C88:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C91B \\sim C92B \\sim C93B \\sim C94B \\sim O9B \\sim O9A \\sim C94A \\sim C93A
\\sim C92A \\sim C91A: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
5. Same fragment restrains
{C91B, C92B, C93B, C94B, O9B}
as
{O9A, C94A, C93A, C92A, C91A}
{C95A, C96A, C97A, C98A, O10A}
as
{C95B, C96B, C97B, C98B, O10B}
6. Others
 Fixed Sof: C45A(0.5) C46A(0.5) C47A(0.5) C48A(0.5) C49A(0.5) C50A(0.5)
 H50A(0.5) H50B(0.5) H50C(0.5) C51A(0.5) H51A(0.5) H51B(0.5) H51C(0.5)
 C52A(0.5) H52A(0.5) H52B(0.5) H52C(0.5) C53A(0.5) H53A(0.5) H53B(0.5)
 H53C(0.5) C54A(0.5) H54A(0.5) H54B(0.5) H54C(0.5) C55A(0.5) C56A(0.5)
 C57A(0.5) C58A(0.5) C59A(0.5) C60A(0.5) H60A(0.5) H60B(0.5) H60C(0.5)
 C61A(0.5) H61A(0.5) H61B(0.5) H61C(0.5) C62A(0.5) H62A(0.5) H62B(0.5)
 H62C(0.5) C63A(0.5) H63A(0.5) H63B(0.5) H63C(0.5) C64A(0.5) H64A(0.5)
 H64B(0.5) H64C(0.5) C45B(0.5) C46B(0.5) C47B(0.5) C48B(0.5) C49B(0.5)
 C50B(0.5) H50D(0.5) H50E(0.5) H50F(0.5) C51B(0.5) H51D(0.5) H51E(0.5)
 H51F(0.5) C52B(0.5) H52D(0.5) H52E(0.5) H52F(0.5) C53B(0.5) H53D(0.5)
 H53E(0.5) H53F(0.5) C54B(0.5) H54D(0.5) H54E(0.5) H54F(0.5) C55B(0.5)
 C56B(0.5) C57B(0.5) C58B(0.5) C59B(0.5) C60B(0.5) H60D(0.5) H60E(0.5)
 H60F(0.5) C61B(0.5) H61D(0.5) H61E(0.5) H61F(0.5) C62B(0.5) H62D(0.5)
 H62E(0.5) H62F(0.5) C63B(0.5) H63D(0.5) H63E(0.5) H63F(0.5) C64B(0.5)
 H64D(0.5) H64E(0.5) H64F(0.5) O9A(0.5) C94A(0.5) H94A(0.5) H94B(0.5) C93A(0.5)
 H93A(0.5) H93B(0.5) C92A(0.5) H92A(0.5) H92B(0.5) C91A(0.5) H91A(0.5)
 H91B(0.5) C91B(0.5) H91C(0.5) H91D(0.5) C92B(0.5) H92C(0.5) H92D(0.5)
 C93B(0.5) H93C(0.5) H93D(0.5) C94B(0.5) H94C(0.5) H94D(0.5) O9B(0.5) H10E(0.5)
 H10F(0.5) H10C(0.5) H10D(0.5) C103(0.5) H10G(0.5) H10H(0.5) C102(0.5)
 H10I(0.5) H10J(0.5) C95B(0.5) H95A(0.5) H95B(0.5) C96B(0.5) H96A(0.5)
 H96B(0.5) C97B(0.5) H97A(0.5) H97B(0.5) C98B(0.5) H98A(0.5) H98B(0.5)
 O10B(0.5) C95A(0.5) H95C(0.5) H95D(0.5) C96A(0.5) H96C(0.5) H96D(0.5)
 C97A(0.5) H97C(0.5) H97D(0.5) C98A(0.5) H98C(0.5) H98D(0.5) O10A(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,
 H69B), C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B),
 C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B),
  C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C87(H87A,
 H87B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B), C94A(H94A,H94B),
 C93A(H93A,H93B), C92A(H92A,H92B), C91A(H91A,H91B), C91B(H91C,H91D), C92B(H92C,
 H92D), C93B(H93C,H93D), C94B(H94C,H94D), C99(H99A,H99B), C100(H10A,H10B),
 C101(H10E,H10F), C101(H10C,H10D), C103(H10G,H10H), C102(H10I,H10J), C104(H10K,
 H10L), C105(H10M,H10N), C106(H10O,H10P), C107(H10Q,H10R), C83(H83A,H83B),
 C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C95B(H95A,H95B), C96B(H96A,
 H96B), C97B(H97A,H97B), C98B(H98A,H98B), C95A(H95C,H95D), C96A(H96C,H96D),
 C97A(H97C,H97D), C98A(H98C,H98D)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23)
7.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C50A(H50A,H50B,H50C),
 C51A(H51A,H51B,H51C), C52A(H52A,H52B,H52C), C53A(H53A,H53B,H53C), C54A(H54A,
 H54B,H54C), C60A(H60A,H60B,H60C), C61A(H61A,H61B,H61C), C62A(H62A,H62B,H62C),
 C63A(H63A,H63B,H63C), C64A(H64A,H64B,H64C), C50B(H50D,H50E,H50F), C51B(H51D,
 H51E,H51F), C52B(H52D,H52E,H52F), C53B(H53D,H53E,H53F), C54B(H54D,H54E,H54F),
 C60B(H60D,H60E,H60F), C61B(H61D,H61E,H61F), C62B(H62D,H62E,H62F), C63B(H63D,
 H63E,H63F), C64B(H64D,H64E,H64F)
;
_shelxl_version_number           2014/4
_shelx_res_checksum              86658