Montmorillonite K-10 catalyzed synthesis of Hantzsch dihydropyridine derivatives from methyl arenes <i>via in situ</i> generated ammonia under microwave irradiation in neat conditions.
Singh, Vishal; Rajput, Khushbu; Singh, Sundaram; Srivastava, Vandana; RSC advances 14 (2024) 27086–27091; doi:10.1039/d4ra04990j

data_7249245
_publ_section_title
;
 Montmorillonite K-10 catalyzed synthesis of Hantzsch dihydropyridine
 derivatives from methyl arenes <i>via in situ</i> generated ammonia under
 microwave irradiation in neat conditions.
;
_journal_issue                   37
_journal_name_full               'RSC advances'
_journal_page_first              27086
_journal_page_last               27091
_journal_paper_doi               10.1039/d4ra04990j
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         'C17 H18 N2 O6'
_chemical_formula_sum            'C17 H18 N2 O6'
_chemical_formula_weight         346.33
_chemical_melting_point          445.15
_chemical_name_common            Nifedipine
_chemical_name_systematic
'dimethyl 2,6-dimethyl-4-(2-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate'
_chemical_properties_physical    Photo-sensitive
_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             2024-06-01
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-06-04 deposited with the CCDC.	2024-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.621(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9599(3)
_cell_length_b                   10.3802(4)
_cell_length_c                   14.7603(4)
_cell_measurement_reflns_used    6918
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.5780
_cell_measurement_theta_min      4.0210
_cell_volume                     1677.46(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (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_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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   -108.00 -62.00   0.50    0.23    --  -40.58-141.00 177.00   92
  2  \w    -89.00 -14.00   0.50    0.23    --  -40.58 129.00  62.00  150
  3  \w     36.00  93.00   0.50    0.23    --   40.58-129.00 -10.00  114
  4  \w   -148.00 -70.00   0.50    0.91    --  -82.50-129.00 -10.00  156
  5  \w   -150.00 -62.00   0.50    0.91    --  -82.50-141.00 177.00  176
  6  \w     42.00 124.00   0.50    0.91    --  104.00-141.00 177.00  164
  7  \w     92.00 170.00   0.50    0.91    --  104.00 129.00  62.00  156
  8  \w     39.00 115.00   0.50    0.91    --  104.00-129.00 -10.00  152
  9  \w    -28.00  31.00   0.50    0.23    --  -40.58  21.00  60.00  118
 10  \w    -28.00  31.00   0.50    0.23    --  -40.58  21.00-180.00  118
 11  \w    -37.00  27.00   0.50    0.23    --  -40.58  32.00 150.00  128
 12  \w    -25.00  48.00   0.50    0.23    --   40.58 -43.00 -60.00  146
 13  \w     41.00 100.00   0.50    0.23    --   40.58-138.00 -60.00  118
 14  \w     42.00 102.00   0.50    0.23    --   40.58-141.00 177.00  120
 15  \w      9.00  42.00   0.50    0.23    --   40.58  91.00 157.96   66
 16  \w    -31.00  28.00   0.50    0.23    --   40.58 -21.00 120.00  118
 17  \w      8.00  42.00   0.50    0.23    --   40.58  92.00 -50.67   68
 18  \w    -47.00 -15.00   0.50    0.91    --  -82.50  42.00 -30.00   64
 19  \w    -47.00 -15.00   0.50    0.91    --  -82.50  42.00 120.00   64
 20  \w   -150.00 -69.00   0.50    0.91    --  -82.50 -33.00  60.00  162
 21  \w   -148.00 -81.00   0.50    0.91    --  -82.50-111.00  90.00  134
 22  \w     36.00  68.00   0.50    0.91    --  104.00 -59.00-120.00   64
 23  \w     82.00 172.00   0.50    0.91    --  104.00  59.00 -90.00  180
 24  \w     89.00 174.00   0.50    0.91    --  104.00  25.00  60.00  170
 25  \w     85.00 171.00   0.50    0.91    --  104.00  50.00-180.00  172
 26  \w     38.00 108.00   0.50    0.91    --  104.00-111.00 -90.00  140
 27  \w     35.00 105.00   0.50    0.91    --  104.00 -77.00   0.00  140
 28  \w     32.00 106.00   0.50    0.91    --  104.00 -93.00 120.00  148
 29  \w     36.00  68.00   0.50    0.91    --  104.00 -59.00   0.00   64
 30  \w     36.00  68.00   0.50    0.91    --  104.00 -59.00-180.00   64
 31  \w     62.00 146.00   0.50    0.91    --  104.00 178.00 150.00  168
 32  \w     38.00 108.00   0.50    0.91    --  104.00-111.00  30.00  140
 33  \w     36.00  83.00   0.50    0.91    --  104.00 -68.00  60.00   94
 34  \w    102.00 170.00   0.50    0.91    --  104.00 111.00 -90.00  136
 35  \w     89.00 174.00   0.50    0.91    --  104.00  25.00  30.00  170
 36  \w     35.00 105.00   0.50    0.91    --  104.00 -77.00  30.00  140
 37  \w     36.00  83.00   0.50    0.91    --  104.00 -68.00-120.00   94
 38  \w     38.00 108.00   0.50    0.91    --  104.00-111.00 -30.00  140
 39  \w     32.00 106.00   0.50    0.91    --  104.00 -93.00 -30.00  148
 40  \w     38.00 108.00   0.50    0.91    --  104.00-111.00  60.00  140
 41  \w     38.00 108.00   0.50    0.91    --  104.00-111.00  90.00  140
 42  \w     40.00 113.00   0.50    0.91    --  104.00-125.00  90.15  146
 43  \w    104.00 177.00   0.50    0.91    --  104.00  93.00 120.00  146
 44  \w     10.00  43.00   0.50    0.23    --   40.58  87.00  91.92   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0631565000
_diffrn_orient_matrix_UB_12      -0.1326459000
_diffrn_orient_matrix_UB_13      -0.0034576000
_diffrn_orient_matrix_UB_21      0.1246616000
_diffrn_orient_matrix_UB_22      -0.0662566000
_diffrn_orient_matrix_UB_23      0.0171512000
_diffrn_orient_matrix_UB_31      -0.0165760000
_diffrn_orient_matrix_UB_32      0.0066273000
_diffrn_orient_matrix_UB_33      0.1029811000
_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  0.0939
_diffrn_reflns_av_unetI/netI     0.0702
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            17221
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.189
_diffrn_reflns_theta_min         4.038
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.885
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50179
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.115a (Rigaku Oxford Diffraction, 2021)
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    1.371
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Ethanol'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.039
_refine_diff_density_min         -0.312
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         3296
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.1041
_refine_ls_R_factor_gt           0.0873
_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^)+(0.1808P)^2^+0.2637P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2781
_refine_ls_wR_factor_ref         0.2991
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2330
_reflns_number_total             3296
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra04990j2.cif
_cod_data_source_block           red1
_cod_database_code               7249245
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N'
_shelx_estimated_absorpt_t_max   0.843
_shelx_estimated_absorpt_t_min   0.777
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C8(H8), C9(H9), C10(H10), C11(H11)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,
 H17C)
;
_shelx_res_checksum              59344
_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 2.654
_oxdiff_exptl_absorpt_empirical_full_min 0.305