Interaction, bond formation or reaction between a dimethylamino group and an adjacent alkene or aldehyde group in aromatic systems controlled by remote molecular constraints
Bristow, Jonathan C.; Cliff, Stacey V. A.; Yang, Songjie; Wallis, John D.; CrystEngComm 23 (2021) 4500–4512; doi:10.1039/D1CE00377A

data_7242930
_publ_section_title
;
 Interaction, bond formation or reaction between a dimethylamino group and
 an adjacent alkene or aldehyde group in aromatic systems controlled by
 remote molecular constraints
;
_journal_issue                   25
_journal_name_full               CrystEngComm
_journal_page_first              4500
_journal_page_last               4512
_journal_paper_doi               10.1039/D1CE00377A
_journal_volume                  23
_journal_year                    2021
_chemical_formula_moiety         'C21 H21 N O4'
_chemical_formula_sum            'C21 H21 N O4'
_chemical_formula_weight         351.39
_chemical_melting_point          472.5(15)
_chemical_name_systematic
1,2,3,4-Tetrahydro-1,2,2-trimethyl-spiro[1,3-dioxane-5,3-acenaphth[5,6-bc]azepine]-4,6-dione
_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   mixed
_audit_creation_date             2019-03-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-03-09 deposited with the CCDC.	2021-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.546(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.4257(3)
_cell_length_b                   8.8243(3)
_cell_length_c                   18.7805(7)
_cell_measurement_reflns_used    2680
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      27.8630
_cell_measurement_theta_min      3.9970
_cell_volume                     1692.83(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9832
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.835
_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    -26.00  54.00   1.00   22.50    --  -13.67  57.00 120.00   80
  2  \w    -11.00  34.00   1.00   22.50    --  -13.67  57.00-120.00   45
  3  \w    -74.00 -30.00   1.00   22.50    --  -13.67 -37.00  30.00   44
  4  \w      7.00  55.00   1.00   22.50    --  -13.67  37.00  30.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0199909000
_diffrn_orient_matrix_UB_12      0.0025392000
_diffrn_orient_matrix_UB_13      0.0383583000
_diffrn_orient_matrix_UB_21      0.0349499000
_diffrn_orient_matrix_UB_22      -0.0688028000
_diffrn_orient_matrix_UB_23      -0.0007465000
_diffrn_orient_matrix_UB_31      0.0565930000
_diffrn_orient_matrix_UB_32      0.0415005000
_diffrn_orient_matrix_UB_33      -0.0036163000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0262
_diffrn_reflns_av_unetI/netI     0.0464
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.835
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            7351
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.835
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.230
_diffrn_reflns_theta_min         3.379
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.096
_exptl_absorpt_correction_T_max  0.986
_exptl_absorpt_correction_T_min  0.978
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             744
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM/hexane'
_exptl_crystal_size_max          0.353
_exptl_crystal_size_mid          0.219
_exptl_crystal_size_min          0.19
_refine_diff_density_max         0.218
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     302
_refine_ls_number_reflns         3489
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0764
_refine_ls_R_factor_gt           0.0552
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0386P)^2^+0.3273P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1024
_refine_ls_wR_factor_ref         0.1132
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2736
_reflns_number_total             3489
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ce00377a2.cif
_cod_data_source_block           jb315abs
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '471-474' was changed to
'472.5(15)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 7242927--7242944.cif.
;
_cod_database_code               7242930
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C21 H21 O4 N1'
_chemical_oxdiff_usercomment     'Orange Block'
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.967
_reflns_odcompleteness_completeness 99.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.07
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O4-C18 \\sim O4A-C18
 with sigma of 0.02
 O4-C19 \\sim O4A-C19A
 with sigma of 0.02
 O3-C17 \\sim O3A-C17
 with sigma of 0.02
 O3-C19 \\sim O3A-C19A
 with sigma of 0.02
 C19-C20 \\sim C19A-C20A
 with sigma of 0.02
 C19-C21 \\sim C19A-C21A
 with sigma of 0.02
 O4-O3 \\sim O4A-O3A
 with sigma of 0.04
 O4-C20 \\sim O4A-C20A
 with sigma of 0.04
 O4-C21 \\sim O4A-C21A
 with sigma of 0.04
 O3-C20 \\sim O3A-C20A
 with sigma of 0.04
 O3-C21 \\sim O3A-C21A
 with sigma of 0.04
 C18-C19 \\sim C18-C19A
 with sigma of 0.04
 C17-C19 \\sim C17-C19A
 with sigma of 0.04
 C20-C21 \\sim C20A-C21A
 with sigma of 0.04
3. Others
 Sof(O3A)=Sof(O4A)=Sof(C19A)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(C21A)=
 Sof(H21D)=Sof(H21E)=Sof(H21F)=1-FVAR(1)
 Sof(O3)=Sof(O4)=Sof(C19)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=
 Sof(H21A)=Sof(H21B)=Sof(H21C)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8)
4.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C21(H21A,H21B,
 H21C), C21A(H21D,H21E,H21F)
;
_shelx_res_checksum              33830
_shelx_hkl_checksum              86275
_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 1.034
_oxdiff_exptl_absorpt_empirical_full_min 0.971