Diverse tetracyanodihydrodipyrazinopyrazine clathrate crystals assembled from weak intermolecular interactions
Watanabe, Kosuke; Sugiyama, Haruki; Segawa, Yasutomo; CrystEngComm 27 (2025) 3552–3559; doi:10.1039/D5CE00289C

data_7250311
_publ_section_title
;
 Diverse tetracyanodihydrodipyrazinopyrazine clathrate crystals assembled
 from weak intermolecular interactions
;
_journal_issue                   21
_journal_name_full               CrystEngComm
_journal_page_first              3552
_journal_page_last               3559
_journal_paper_doi               10.1039/D5CE00289C
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C30 H22 N10, 2(C3 H7 N O)'
_chemical_formula_sum            'C36 H36 N12 O2'
_chemical_formula_weight         668.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-12-23
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-03-10 deposited with the CCDC.	2025-04-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.908(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.0545(2)
_cell_length_b                   12.3215(3)
_cell_length_c                   16.3699(3)
_cell_measurement_reflns_used    3313
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      70.7220
_cell_measurement_theta_min      4.4770
_cell_volume                     1823.96(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      200.15
_diffrn_detector_area_resol_mean 8.1195
_diffrn_detector_type            EosS2
_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     -5.00  20.00   1.00    3.59    --  -34.90  19.00-120.00   25
  2  \w     -5.00  20.00   1.00    3.59    --  -34.90  19.00 120.00   25
  3  \w    -33.00  30.00   1.00    3.59    --   34.90 -37.00  90.00   63
  4  \w     48.00  73.00   1.00    3.59    --   34.90 -99.00 -90.00   25
  5  \w     32.00  94.00   1.00    3.59    --   34.90  57.00-180.00   62
  6  \w     18.00  65.00   1.00    3.59    --   34.90  57.00  30.00   47
  7  \w    -20.00  48.00   1.00    3.59    --   34.90 -57.00  30.00   68
  8  \w     42.00  71.00   1.00    3.59    --   34.90-125.00 -90.00   29
  9  \w     47.00  72.00   1.00    3.59    --   34.90 -99.00  60.00   25
 10  \w     49.00  98.00   1.00   14.35    --  107.04 -94.00-150.00   49
 11  \w     43.00  71.00   1.00   14.35    --  107.04 -45.00  60.00   28
 12  \w     41.00  69.00   1.00   14.35    --  107.04 -45.00  30.00   28
 13  \w     41.00 104.00   1.00   14.35    --  107.04 -94.00 -90.00   63
 14  \w     42.00  67.00   1.00   14.35    --  107.04 -45.00 -30.00   25
 15  \w     43.00  69.00   1.00   14.35    --  107.04 -45.00 120.00   26
 16  \w     54.00  89.00   1.00   14.35    --  107.04 -61.00 -90.00   35
 17  \w     98.00 127.00   1.00   14.35    --  107.04  61.00 150.00   29
 18  \w     39.00  72.00   1.00   14.35    --  107.04 -45.00   0.00   33
 19  \w     39.00  71.00   1.00   14.35    --  107.04 -45.00 -60.00   32
 20  \w     56.00  83.00   1.00   14.35    --  107.04 -61.00  90.00   27
 21  \w     46.00 148.00   1.00   14.35    --  107.04   0.00 -90.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            6480
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.219
_diffrn_reflns_theta_min         4.494
_exptl_absorpt_coefficient_mu    0.652
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75998
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.218
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.168
_refine_diff_density_min         -0.212
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     278
_refine_ls_number_reflns         3330
_refine_ls_number_restraints     77
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0529
_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^)+(0.0891P)^2^+0.3488P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1458
_refine_ls_wR_factor_ref         0.1565
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2803
_reflns_number_total             3330
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00289c2.cif
_cod_data_source_block           TCDP-DMF
_cod_depositor_comments
'Adding full bibliography for 7250300--7250316.cif.'
_cod_database_code               7250311
_shelx_shelxl_version_number     2019/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O22A-C21A = O25-C24
 1.22 with sigma of 0.005
 N19A-C21A = N22-C24
 1.32 with sigma of 0.01
 N19A-C20A = N19A-C18A = N22-C23 = N22-C21
 1.45 with sigma of 0.01
 N19A-C18A \\sim N19A-C20A \\sim N19A-C21A
 with sigma of 0.02
 N22-C23 \\sim N22-C21 \\sim N22-C24
 with sigma of 0.02
 C18A-C21A \\sim C21A-C20A
 with sigma of 0.02
 O22A-C21A \\sim O25-C24
 with sigma of 0.02
 C23-C24 \\sim C24-C21
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O22A) \\sim Ueq, Uanis(O25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(N22)
\\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(N19A) \\sim Ueq, Uanis(C23) \\sim Ueq,
Uanis(C21) \\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C18A) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Fixed Sof: O25(0.5) C21A(0.5) H21D(0.5) C24(0.5) H24(0.5) N19A(0.5) C18A(0.5)
 H18A(0.5) H18B(0.5) H18C(0.5) C20A(0.5) H20A(0.5) H20B(0.5) H20C(0.5) C23(0.5)
 H23A(0.5) H23B(0.5) H23C(0.5) O22A(0.5) C21(0.5) H21A(0.5) H21B(0.5) H21C(0.5)
 N22(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C21A(H21D), C24(H24)
5.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C8(H8A,H8B,H8C), C18A(H18A,H18B,H18C),
 C20A(H20A,H20B,H20C), C23(H23A,H23B,H23C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              72462
_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
;