Heating enables solid-state motion and improves the yield of a [2 + 2] cycloaddition reaction within an organic cocrystal
George, Gary C.; Owens, Drew; Osbourn, Damon M.; Hutchins, Kristin M.; Groeneman, Ryan; CrystEngComm  (2025) –; doi:10.1039/D5CE00995B

data_7251319
_publ_section_title
;
 Heating enables solid-state motion and improves the yield of a [2 + 2]
 cycloaddition reaction within an organic cocrystal
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D5CE00995B
_journal_year                    2025
_chemical_formula_moiety         '2(C15 H13 N O2), C6 H4 Cl2 O2'
_chemical_formula_sum            'C36 H30 Cl2 N2 O6'
_chemical_formula_weight         657.52
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-07
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-09-08 deposited with the CCDC.	2025-11-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.6060(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.67280(10)
_cell_length_b                   8.59130(10)
_cell_length_c                   23.4511(2)
_cell_measurement_reflns_used    25203
_cell_measurement_temperature    290.0(3)
_cell_measurement_theta_max      79.0530
_cell_measurement_theta_min      3.3110
_cell_volume                     3154.42(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.104a 64-bit (release 22-12-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_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      air
_diffrn_ambient_temperature      290.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.970
_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 -32.00   0.50    0.08    --  -48.01 -11.00  -8.00  182
  2  \w    -26.00  27.00   0.50    0.08    --  -48.01  11.00 164.00  106
  3  \w    -26.00  29.00   0.50    0.08    --   48.01 -11.00  -8.00  110
  4  \w     31.00 123.00   0.50    0.08    --   48.01  11.00 164.00  184
  5  \w   -177.00 -90.00   0.50    0.33    -- -106.00 -11.00  -8.00  174
  6  \w     96.00 178.00   0.50    0.33    --  112.76  11.00 164.00  164
  7  \w    -27.00  28.00   0.50    0.08    --  -48.01  19.00 -60.00  110
  8  \w    -26.00  30.00   0.50    0.08    --   48.01 -19.00-180.00  112
  9  \w     16.00  94.00   0.50    0.08    --   48.01-125.00 -90.00  156
 10  \w    -70.00 -33.00   0.50    0.33    -- -106.00  61.00   0.00   74
 11  \w   -177.00-106.00   0.50    0.33    -- -106.00 -61.00 -60.00  142
 12  \w    -70.00 -33.00   0.50    0.33    -- -106.00  61.00 -30.00   74
 13  \w   -177.00-110.00   0.50    0.33    -- -106.00 -77.00  90.00  134
 14  \w   -101.00 -33.00   0.50    0.33    -- -106.00  77.00 -90.00  136
 15  \w    -70.00 -33.00   0.50    0.33    -- -106.00  61.00 150.00   74
 16  \w   -177.00-110.00   0.50    0.33    -- -106.00 -77.00 -60.00  134
 17  \w   -177.00-110.00   0.50    0.33    -- -106.00 -77.00 -60.00  134
 18  \w   -112.00 -36.00   0.50    0.33    -- -106.00 125.00 150.00  152
 19  \w    -70.00 -33.00   0.50    0.33    -- -106.00  61.00 -90.00   74
 20  \w     40.00  73.00   0.50    0.33    --  112.76 -61.00 -60.00   66
 21  \w     40.00 104.00   0.50    0.33    --  112.76 -77.00-180.00  128
 22  \w     40.00 105.00   0.50    0.33    --  112.76 -95.00 -90.00  130
 23  \w     40.00 105.00   0.50    0.33    --  112.76 -95.00 150.00  130
 24  \w     40.00 105.00   0.50    0.33    --  112.76 -95.00 150.00  130
 25  \w     40.00 105.00   0.50    0.33    --  112.76 -95.00-150.00  130
 26  \w     40.00 105.00   0.50    0.33    --  112.76 -95.00-150.00  130
 27  \w     40.00  73.00   0.50    0.33    --  112.76 -61.00  90.00   66
 28  \w     40.00  73.00   0.50    0.33    --  112.76 -61.00-150.00   66
 29  \w     36.00 121.00   0.50    0.08    --   48.01  38.00-120.00  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0982272000
_diffrn_orient_matrix_UB_12      0.0052899000
_diffrn_orient_matrix_UB_13      0.0064886000
_diffrn_orient_matrix_UB_21      -0.0056429000
_diffrn_orient_matrix_UB_22      0.0249517000
_diffrn_orient_matrix_UB_23      0.0647753000
_diffrn_orient_matrix_UB_31      0.0021151000
_diffrn_orient_matrix_UB_32      -0.1774761000
_diffrn_orient_matrix_UB_33      0.0092674000
_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  0.0306
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.970
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            39106
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.795
_diffrn_reflns_theta_min         3.323
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.271
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.714
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.385
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1368
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.174
_exptl_crystal_size_min          0.154
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.032
_refine_ls_extinction_coef       0.00113(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     582
_refine_ls_number_reflns         6654
_refine_ls_number_restraints     946
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0375
_refine_ls_R_factor_gt           0.0330
_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^)+(0.0511P)^2^+0.4236P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0954
_refine_ls_wR_factor_ref         0.0993
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5784
_reflns_number_total             6654
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00995b2.cif
_cod_data_source_block           4_6_diCl_Res_PEB_290K
_cod_database_code               7251319
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.721
_shelx_estimated_absorpt_t_min   0.559
_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, All O(H) groups
2. Restrained distances
 C8A-C7A = C8A-C7B = C3A-C6A = C3A-C6B
 1.46824 with sigma of 0.02
 C7A-C6A = C7B-C6B
 1.31174 with sigma of 0.02
 C24A-C27A = C24B-C27B = C29-C28B = C29-C28A
 1.46491 with sigma of 0.02
 C27B-C28B = C27A-C28A
 1.30945 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N1 \\sim C11A \\sim C3A \\sim C12A \\sim C8A \\sim C13A \\sim C5A \\sim C10A
\\sim C4A \\sim C6A \\sim C9A \\sim C1A \\sim C2A \\sim C7A \\sim C7B \\sim C6B
\\sim C11B \\sim C12B \\sim C13B \\sim C8B \\sim C9B \\sim C10B \\sim C2B \\sim
C3B \\sim C4B \\sim C5B \\sim C1B: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
N2 \\sim C24A \\sim C23A \\sim C22A \\sim C26A \\sim C25A \\sim C28A \\sim C27A
\\sim C22B \\sim C23B \\sim C24B \\sim C25B \\sim C26B \\sim C27B \\sim C28B:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Rigid body (RIGU) restrains
 N1, C11A, C3A, C12A, C8A, C13A, C5A, C10A, C4A, C6A, C9A, C1A, C2A, C7A, C7B,
 C6B, C11B, C12B, C13B, C8B, C9B, C10B, C2B, C3B, C4B, C5B, C1B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N2, C24A, C23A, C22A, C26A, C25A, C28A, C27A, C22B, C23B, C24B, C25B, C26B,
 C27B, C28B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C7B)=Sof(H6)=Sof(C6B)=Sof(H7)=Sof(C11B)=Sof(C12B)=Sof(H8)=Sof(C13B)=
 Sof(H9)=Sof(C8B)=Sof(C9B)=Sof(H10)=Sof(C10B)=Sof(H11)=Sof(C2B)=Sof(H12)=
 Sof(C3B)=Sof(C4B)=Sof(H13)=Sof(C5B)=Sof(H14)=Sof(C1B)=Sof(H15)=1-FVAR(1)
 Sof(C11A)=Sof(C3A)=Sof(C12A)=Sof(HD)=Sof(C8A)=Sof(C13A)=Sof(HF)=Sof(C5A)=
 Sof(HH)=Sof(C10A)=Sof(HJ)=Sof(C4A)=Sof(HK)=Sof(C6A)=Sof(HS)=Sof(C9A)=Sof(HT)=
 Sof(C1A)=Sof(HU)=Sof(C2A)=Sof(HV)=Sof(C7A)=Sof(HW)=FVAR(1)
 Sof(C22B)=Sof(H)=Sof(C23B)=Sof(HA)=Sof(C24B)=Sof(C25B)=Sof(HB)=Sof(C26B)=
 Sof(HC)=Sof(C27B)=Sof(H17)=Sof(C28B)=Sof(H18)=1-FVAR(4)
 Sof(C24A)=Sof(C23A)=Sof(HE)=Sof(C22A)=Sof(HG)=Sof(C26A)=Sof(HL)=Sof(C25A)=
 Sof(HN)=Sof(C28A)=Sof(HP)=Sof(C27A)=Sof(HR)=FVAR(4)
6.a Aromatic/amide H refined with riding coordinates:
 C22B(H), C23B(HA), C25B(HB), C26B(HC), C16(H16), C19(H19), C12A(HD), C23A(HE),
  C13A(HF), C22A(HG), C5A(HH), C31(HI), C10A(HJ), C4A(HK), C26A(HL), C33(HM),
 C25A(HN), C30(HO), C28A(HP), C34(HQ), C27A(HR), C6A(HS), C9A(HT), C1A(HU),
 C2A(HV), C7A(HW), C7B(H6), C6B(H7), C12B(H8), C13B(H9), C9B(H10), C10B(H11),
 C2B(H12), C4B(H13), C5B(H14), C1B(H15), C27B(H17), C28B(H18)
6.b Fitted hexagon refined as free rotating group:
 N2(C22B,C23B,C24B,C25B,C26B), C11B(C12B,C13B,C8B,C9B,C10B)
6.c Idealised Me refined as rotating group:
 C15(HX,HY,HZ), C36(H1,H2,H5)
6.d Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4)
;
_shelx_res_checksum              98329
_olex2_exptl_crystal_mounting_method
'Crystal was mounted on a 100 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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.104
_oxdiff_exptl_absorpt_empirical_full_min 0.902