Use of a Diels–Alder reaction to modify thermal expansion properties in charge-transfer cocrystals
George, Gary C.; Unruh, Daniel K.; Hutchins, Kristin M.; CrystEngComm  (2022) –; doi:10.1039/D2CE01207C

data_7245502
_publ_section_title
;
 Use of a Diels--Alder reaction to modify thermal expansion properties in
 charge-transfer cocrystals
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D2CE01207C
_journal_year                    2022
_chemical_formula_moiety         'C28 H19 Br N2 O4 S2'
_chemical_formula_sum            'C28 H19 Br N2 O4 S2'
_chemical_formula_weight         591.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-12
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-06-17 deposited with the CCDC.	2022-09-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.198(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6744(2)
_cell_length_b                   23.0269(3)
_cell_length_c                   8.48040(10)
_cell_measurement_reflns_used    14850
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.8220
_cell_measurement_theta_min      3.5630
_cell_volume                     2409.65(6)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.968
_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   -123.00 -34.00   0.50    0.55    --  -47.76 -20.00 -86.00  178
  2  \w    -25.00  28.00   0.50    0.55    --  -47.76  20.00  80.00  106
  3  \w    -27.00  29.00   0.50    0.55    --   47.76 -20.00 -86.00  112
  4  \w     35.00 123.00   0.50    0.55    --   47.76  20.00  80.00  176
  5  \w   -166.00 -78.00   0.50    2.19    --  -91.75 -20.00 -86.00  176
  6  \w     94.00 178.00   0.50    2.19    --  107.31  20.00  80.00  168
  7  \w   -120.00 -73.00   0.50    0.55    --  -47.76-125.00  30.00   94
  8  \w    -25.00  28.00   0.50    0.55    --  -47.76  19.00-150.00  106
  9  \w    -25.00  45.00   0.50    0.55    --   47.76 -38.00 150.00  140
 10  \w   -163.00 -86.00   0.50    2.19    --  -91.75 -99.00  30.00  154
 11  \w    -64.00 -19.00   0.50    2.19    --  -91.75  57.00  60.00   90
 12  \w    -85.00 -19.00   0.50    2.19    --  -91.75 125.00 150.00  132
 13  \w    -64.00 -19.00   0.50    2.19    --  -91.75  57.00  30.00   90
 14  \w     35.00  68.00   0.50    2.19    --  107.31 -57.00 -30.00   66
 15  \w     35.00 111.00   0.50    2.19    --  107.31-125.00-180.00  152
 16  \w     35.00  68.00   0.50    2.19    --  107.31 -57.00 -60.00   66
 17  \w     35.00 107.00   0.50    2.19    --  107.31 -77.00 -60.00  144
 18  \w     35.00  68.00   0.50    2.19    --  107.31 -57.00   0.00   66
 19  \w     35.00 106.00   0.50    2.19    --  107.31 -99.00 120.00  142
 20  \w     35.00 106.00   0.50    2.19    --  107.31 -99.00-150.00  142
 21  \w     95.00 178.00   0.50    2.19    --  107.31  19.00 120.00  166
 22  \w     35.00  68.00   0.50    2.19    --  107.31 -57.00-180.00   66
 23  \w     35.00  68.00   0.50    2.19    --  107.31 -57.00-150.00   66
 24  \w     35.00  68.00   0.50    2.19    --  107.31 -57.00  90.00   66
 25  \w   -120.00 -25.00   0.50    0.55    --  -47.76 -77.00 120.00  190
 26  \w   -120.00 -47.00   0.50    0.55    --  -47.76 -57.00 -90.00  146
 27  \w   -120.00 -25.00   0.50    0.55    --  -47.76 -77.00-150.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0002335000
_diffrn_orient_matrix_UB_12      0.0176434000
_diffrn_orient_matrix_UB_13      0.1753273000
_diffrn_orient_matrix_UB_21      -0.1248082000
_diffrn_orient_matrix_UB_22      -0.0008071000
_diffrn_orient_matrix_UB_23      -0.0416651000
_diffrn_orient_matrix_UB_31      0.0016946000
_diffrn_orient_matrix_UB_32      -0.0645343000
_diffrn_orient_matrix_UB_33      0.0485157000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0638
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            26084
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.202
_diffrn_reflns_theta_min         3.582
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.288
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.632
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
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            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.630
_exptl_crystal_description       plate
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.149
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.845
_refine_diff_density_min         -0.957
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     376
_refine_ls_number_reflns         4944
_refine_ls_number_restraints     113
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.0681
_refine_ls_R_factor_gt           0.0624
_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^)+(0.0002P)^2^+8.8259P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1329
_refine_ls_wR_factor_ref         0.1360
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4469
_reflns_number_total             4944
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ce01207c2.cif
_cod_data_source_block           DA2_BrAn_Head_to_Head_CA_Nonsolvated_auto
_cod_database_code               7245502
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N S Br'
_shelx_estimated_absorpt_t_max   0.851
_shelx_estimated_absorpt_t_min   0.394
_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
2. Restrained distances
 C19-C20A = C19-C20B
 1.519 with sigma of 0.02
 C20A-C21A = C20B-C21B
 1.30081 with sigma of 0.02
 C14-Br1 = C7-Br2
 1.81435 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C19 \\sim C20A \\sim C20B \\sim C21B \\sim C21A: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 2A
C17 \\sim C24 \\sim S2 \\sim S3: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 C19, C20A, C20B, C21A, C21B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C17, C24, S2, S3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(H14)=Sof(Br2)=1-FVAR(1)
 Sof(Br1)=Sof(H7)=FVAR(1)
 Sof(H19C)=Sof(H19D)=Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(H21C)=Sof(H21D)=1-FVAR(2)
 Sof(H19A)=Sof(H19B)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(H21B)=FVAR(2)
 Sof(S3)=1-FVAR(6)
 Sof(S2)=FVAR(6)
6.a Ternary CH refined with riding coordinates:
 C14(H14), C7(H7)
6.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C19(H19A,H19B), C19(H19C,H19D)
6.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C10(H10), C2(H2), C9(H9), C5(H5), C3(H3), C27(H27),
 C4(H4), C20A(H20A), C20B(H20B)
6.d X=CH2 refined with riding coordinates:
 C28(H28A,H28B), C21A(H21A,H21B), C21B(H21C,H21D)
;
_shelx_res_checksum              27241
_shelx_hkl_checksum              4137
_olex2_exptl_crystal_mounting_method
'Crystal was mounted on a 75 um MiTeGen cryoloop.'
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 4.134
_oxdiff_exptl_absorpt_empirical_full_min 0.582