Intermolecular Resonance Correlates Electron Pairs Down a Supermolecular Chain: Antiferromagnetism in K-Doped p-Terphenyl
Gadjieva, Natalia A.; Szirmai, Péter; Sági, Olivér; Alemany, Pere; Bartholomew, Amymarie K.; Stone, Ilana; Conejeros, Sergio; Paley, Daniel W.; Hernández Sánchez, Raúl; Fowler, Brandon; Peurifoy, Samuel R.; Náfrádi, Bálint; Forró, László; Roy, Xavier; Batail, Patrick; Canadell, Enric; Steigerwald, Michael L.; Nuckolls, Colin; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c05606

data_4135377
_publ_section_title
;
 Intermolecular Resonance Correlates Electron Pairs Down a Supermolecular
 Chain: Antiferromagnetism in K-Doped p-Terphenyl
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c05606
_journal_year                    2020
_chemical_formula_moiety         '3(C18 H14), 2(C18 H36 K N2 O6)'
_chemical_formula_sum            'C90 H114 K2 N4 O12'
_chemical_formula_weight         1522.05
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3510 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.9092(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.8962(5)
_cell_length_b                   13.02525(18)
_cell_length_c                   22.6848(4)
_cell_measurement_reflns_used    10474
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      72.3920
_cell_measurement_theta_min      3.7660
_cell_volume                     8093.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0549
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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    -92.00 -35.00   1.00    3.00    --  -19.46-178.00  90.00   57
  2  \w      3.00  92.00   1.00    3.00    --   22.35  37.00 -30.00   89
  3  \w   -103.00 -31.00   1.00    3.00    --  -37.78 -57.00  30.00   72
  4  \w    -11.00  31.00   1.00    3.00    --  -37.78  19.00 -30.00   42
  5  \w      4.00  76.00   1.00    3.00    --   37.78 -99.00-150.00   72
  6  \w     72.00 110.00   1.00    3.00    --   37.78 178.00  30.00   38
  7  \w     58.00 101.00   1.00    3.00    --   37.78 178.00-150.00   43
  8  \w     64.00  99.00   1.00   15.00    --  111.00 -15.00  60.00   35
  9  \w     94.00 132.00   1.00   15.00    --  111.00  15.00 150.00   38
 10  \w     42.00 103.00   1.00   15.00    --  111.00 -94.00 -90.00   61
 11  \w     43.00  89.00   1.00   15.00    --  111.00 -30.00  30.00   46
 12  \w     65.00  97.00   1.00   15.00    --  111.00 -45.00-120.00   32
 13  \w     78.00 151.00   1.00   15.00    --  111.00  15.00   0.00   73
 14  \w    153.00 178.00   1.00   15.00    --  111.00  15.00 150.00   25
 15  \w    148.00 174.00   1.00   15.00    --  111.00   0.00-150.00   26
 16  \w     43.00 105.00   1.00   15.00    --  111.00 -30.00-120.00   62
 17  \w     76.00 102.00   1.00   15.00    --  111.00 -15.00 -90.00   26
 18  \w     89.00 118.00   1.00   15.00    --  111.00 -45.00  60.00   29
 19  \w    150.00 175.00   1.00   15.00    --  111.00  61.00 -90.00   25
 20  \w     94.00 120.00   1.00   15.00    --  111.00  61.00 -90.00   26
 21  \w     47.00 104.00   1.00   15.00    --  111.00 -30.00 -90.00   57
 22  \w    106.00 140.00   1.00   15.00    --  111.00 111.00 -30.00   34
 23  \w    143.00 178.00   1.00   15.00    --  111.00  45.00-150.00   35
 24  \w    118.00 143.00   1.00   15.00    --  111.00 -15.00  60.00   25
 25  \w    100.00 125.00   1.00   15.00    --  111.00 -45.00  30.00   25
 26  \w     47.00  73.00   1.00   15.00    --  111.00 -94.00 -60.00   26
 27  \w     83.00 108.00   1.00   15.00    --  111.00 -94.00 -60.00   25
 28  \w     43.00  68.00   1.00   15.00    --  111.00   0.00-150.00   25
 29  \w     96.00 178.00   1.00   15.00    --  111.00  45.00-180.00   82
 30  \w     41.00  73.00   1.00   15.00    --  111.00-111.00  90.00   32
 31  \w    -95.00 -69.00   1.00    3.00    --  -37.78-178.00 150.00   26
 32  \w    -14.00  20.00   1.00    3.00    --  -37.78  77.00 150.00   34
 33  \w    -71.00 -14.00   1.00    3.00    --  -37.78 -19.00-180.00   57
 34  \w   -109.00 -75.00   1.00    3.00    --  -37.78 -19.00-180.00   34
 35  \w    -63.00 -36.00   1.00    3.00    --  -37.78  77.00 150.00   27
 36  \w     15.00  40.00   1.00    3.00    --   37.78  77.00 -30.00   25
 37  \w     44.00 104.00   1.00    3.00    --   37.78  77.00 -30.00   60
 38  \w     36.00  76.00   1.00    3.00    --   37.78 -99.00  30.00   40
 39  \w     51.00 101.00   1.00   15.00    --  111.00 -77.00  90.00   50
 40  \w     93.00 133.00   1.00   15.00    --  111.00  61.00-120.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0381574000
_diffrn_orient_matrix_UB_12      -0.0517306000
_diffrn_orient_matrix_UB_13      0.0489632000
_diffrn_orient_matrix_UB_21      -0.0260376000
_diffrn_orient_matrix_UB_22      0.0436663000
_diffrn_orient_matrix_UB_23      0.0486811000
_diffrn_orient_matrix_UB_31      -0.0320810000
_diffrn_orient_matrix_UB_32      -0.0969598000
_diffrn_orient_matrix_UB_33      -0.0042234000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            30353
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.929
_diffrn_reflns_theta_min         3.758
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.547
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.796
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.249
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3264
_exptl_crystal_size_max          0.154
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.074
_refine_diff_density_max         0.409
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.037
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.009
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     628
_refine_ls_number_reflns         8022
_refine_ls_number_restraints     660
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0446P)^2^+4.2592P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0904
_refine_ls_wR_factor_ref         0.0967
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6717
_reflns_number_total             8022
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c05606_si_002.cif
_cod_data_source_block           ptp3_k2_222
_cod_database_code               4135377
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C90 H114 K2 N4 O12'
_reflns_odcompleteness_completeness 97.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     73.59
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.01 and sigma
for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 N31, C32, C33, O34, C35, C36, O37, C38, C39, C40, C41, O42, C43, C44, O45,
 C46, C47, C48, C49, O50, C51, C52, O53, C54, C55, N56, K57, N31B, C32B, C33B,
 O34B, C35B, C36B, O37B, C38B, C39B, C40B, C41B, O42B, C43B, C44B, O45B, C46B,
 C47B, C48B, C49B, O50B, C51B, C52B, O53B, C54B, C55B, C51C, C52C, O53C, C54C,
 C55C, N56B, K57B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Same fragment restrains
{N31B, C32B, C33B, O34B, C35B, C36B, O37B, C38B, C39B, C40B, C41B, O42B, C43B,
C44B, O45B, C46B, C47B, C48B, C49B, O50B, C51B, C52B, O53B, C54B, C55B, N56B,
K57B} sigma for 1-2: 0.02, 1-3: 0.04
as
{N31, C32, C33, O34, C35, C36, O37, C38, C39, C40, C41, O42, C43, C44, O45,
C46, C47, C48, C49, O50, C51, C52, O53, C54, C55, N56, K57}
5. Others
 1*[Sof(N31)+Sof(C32)+Sof(H32A)+Sof(H32B)+Sof(C33)+Sof(H33A)+Sof(H33B)+
 Sof(O34)+Sof(C35)+Sof(H35A)+Sof(H35B)+Sof(C36)+Sof(H36A)+Sof(H36B)+Sof(O37)+
 Sof(C38)+Sof(H38A)+Sof(H38B)+Sof(C39)+Sof(H39A)+Sof(H39B)+Sof(C40)+Sof(H40A)+
 Sof(H40B)+Sof(C41)+Sof(H41A)+Sof(H41B)+Sof(O42)+Sof(C43)+Sof(H43A)+Sof(H43B)+
 Sof(C44)+Sof(H44A)+Sof(H44B)+Sof(O45)+Sof(C46)+Sof(H46A)+Sof(H46B)+Sof(C47)+
 Sof(H47A)+Sof(H47B)+Sof(C48)+Sof(H48A)+Sof(H48B)+Sof(C49)+Sof(H49A)+Sof(H49B)+
 Sof(O50)+Sof(C51)+Sof(H51A)+Sof(H51B)+Sof(C52)+Sof(H52A)+Sof(H52B)+Sof(O53)+
 Sof(C54)+Sof(H54A)+Sof(H54B)+Sof(C55)+Sof(H55A)+Sof(H55B)+Sof(N56)+Sof(K57)+
 Sof(N31B)+Sof(C32B)+Sof(H32C)+Sof(H32D)+Sof(C33B)+Sof(H33C)+Sof(H33D)+
 Sof(O34B)+Sof(C35B)+Sof(H35C)+Sof(H35D)+Sof(C36B)+Sof(H36C)+Sof(H36D)+
 Sof(O37B)+Sof(C38B)+Sof(H38C)+Sof(H38D)+Sof(C39B)+Sof(H39C)+Sof(H39D)+
 Sof(C40B)+Sof(H40C)+Sof(H40D)+Sof(C41B)+Sof(H41C)+Sof(H41D)+Sof(O42B)+
 Sof(C43B)+Sof(H43C)+Sof(H43D)+Sof(C44B)+Sof(H44C)+Sof(H44D)+Sof(O45B)+
 Sof(C46B)+Sof(H46C)+Sof(H46D)+Sof(C47B)+Sof(H47C)+Sof(H47D)+Sof(C48B)+
 Sof(H48C)+Sof(H48D)+Sof(C49B)+Sof(H49C)+Sof(H49D)+Sof(O50B)+Sof(N56B)+
 Sof(K57B)]+1*[Sof(C51B)+Sof(H51C)+Sof(H51D)+Sof(C52B)+Sof(H52C)+Sof(H52D)+
 Sof(O53B)+Sof(C54B)+Sof(H54C)+Sof(H54D)+Sof(C55B)+Sof(H55C)+Sof(H55D)]+1*
 [Sof(C51C)+Sof(H51E)+Sof(H51F)+Sof(C52C)+Sof(H52E)+Sof(H52F)+Sof(O53C)+
 Sof(C54C)+Sof(H54E)+Sof(H54F)+Sof(C55C)+Sof(H55E)+Sof(H55F)]=1 with esd of
 0.0001
 Sof(N31B)=Sof(C32B)=Sof(H32C)=Sof(H32D)=Sof(C33B)=Sof(H33C)=Sof(H33D)=
 Sof(O34B)=Sof(C35B)=Sof(H35C)=Sof(H35D)=Sof(C36B)=Sof(H36C)=Sof(H36D)=
 Sof(O37B)=Sof(C38B)=Sof(H38C)=Sof(H38D)=Sof(C39B)=Sof(H39C)=Sof(H39D)=
 Sof(C40B)=Sof(H40C)=Sof(H40D)=Sof(C41B)=Sof(H41C)=Sof(H41D)=Sof(O42B)=
 Sof(C43B)=Sof(H43C)=Sof(H43D)=Sof(C44B)=Sof(H44C)=Sof(H44D)=Sof(O45B)=
 Sof(C46B)=Sof(H46C)=Sof(H46D)=Sof(C47B)=Sof(H47C)=Sof(H47D)=Sof(C48B)=
 Sof(H48C)=Sof(H48D)=Sof(C49B)=Sof(H49C)=Sof(H49D)=Sof(O50B)=Sof(N56B)=
 Sof(K57B)=1-FVAR(1)
 Sof(N31)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(O34)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(O37)=Sof(C38)=
 Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(O42)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=
 Sof(H44A)=Sof(H44B)=Sof(O45)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(C47)=Sof(H47A)=
 Sof(H47B)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(O50)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(O53)=Sof(C54)=
 Sof(H54A)=Sof(H54B)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(N56)=Sof(K57)=FVAR(1)
 Sof(C51B)=Sof(H51C)=Sof(H51D)=Sof(C52B)=Sof(H52C)=Sof(H52D)=Sof(O53B)=
 Sof(C54B)=Sof(H54C)=Sof(H54D)=Sof(C55B)=Sof(H55C)=Sof(H55D)=FVAR(2)
 Sof(C51C)=Sof(H51E)=Sof(H51F)=Sof(C52C)=Sof(H52E)=Sof(H52F)=Sof(O53C)=
 Sof(C54C)=Sof(H54E)=Sof(H54F)=Sof(C55C)=Sof(H55E)=Sof(H55F)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C33(H33A,H33B), C35(H35A,H35B), C36(H36A,H36B), C38(H38A,
 H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C43(H43A,H43B),
 C44(H44A,H44B), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B),
  C51(H51A,H51B), C52(H52A,H52B), C54(H54A,H54B), C55(H55A,H55B), C32B(H32C,
 H32D), C33B(H33C,H33D), C35B(H35C,H35D), C36B(H36C,H36D), C38B(H38C,H38D),
 C39B(H39C,H39D), C40B(H40C,H40D), C41B(H41C,H41D), C43B(H43C,H43D), C44B(H44C,
 H44D), C46B(H46C,H46D), C47B(H47C,H47D), C48B(H48C,H48D), C49B(H49C,H49D),
 C51B(H51C,H51D), C52B(H52C,H52D), C54B(H54C,H54D), C55B(H55C,H55D), C51C(H51E,
 H51F), C52C(H52E,H52F), C54C(H54E,H54F), C55C(H55E,H55F)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C18(H18), C19(H19), C21(H21), C22(H22), C24(H24),
  C25(H25), C26(H26), C27(H27), C28(H28)
;
_shelx_res_checksum              34399
_shelx_hkl_checksum              43884
_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 1.317
_oxdiff_exptl_absorpt_empirical_full_min 0.826