A colorimetric and 'OFF-ON' fluorometric chemosensor based on a rhodamine-pyrazole derivative for the detection of Al<sup>3+</sup>, Fe<sup>3+</sup>and Cr<sup>3+</sup>metal ions, and its intracellular application.
Gond, Sarita; Yadav, Pranjalee; Singh, Aayoosh; Garai, Somenath; Shekher, Anusmita; Gupta, Subash Chandra; Singh, Vinod P.; Organic & biomolecular chemistry 21 (2023) 4482–4490; doi:10.1039/d3ob00434a

data_7159348
_publ_section_title
;
 A colorimetric and 'OFF-ON' fluorometric chemosensor based on a
 rhodamine-pyrazole derivative for the detection of Al<sup>3+</sup>,
 Fe<sup>3+</sup>and Cr<sup>3+</sup>metal ions, and its intracellular
 application.
;
_journal_issue                   21
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              4482
_journal_page_last               4490
_journal_paper_doi               10.1039/d3ob00434a
_journal_volume                  21
_journal_year                    2023
_chemical_formula_moiety         'C39 H39 Cl N6 O2'
_chemical_formula_sum            'C39 H39 Cl N6 O2'
_chemical_formula_weight         659.21
_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
_audit_block_doi                 10.5517/ccdc.csd.cc2f5txc
_audit_creation_date             2023-01-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-05 deposited with the CCDC.	2023-05-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.427(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.2907(4)
_cell_length_b                   9.6187(2)
_cell_length_c                   29.8472(7)
_cell_measurement_reflns_used    34649
_cell_measurement_temperature    298
_cell_measurement_theta_max      24.4480
_cell_measurement_theta_min      2.5170
_cell_volume                     3498.95(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.63a (Rigaku OD, 2022)'
_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      298.00
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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    -82.00   4.00   0.50   21.01    --  -11.14 -24.00-139.00  172
  2  \w    -14.00  59.00   0.50   21.01    --  -11.14  24.00  24.00  146
  3  \w    -56.00 -30.00   0.50   21.01    --   11.77 -24.00-139.00   52
  4  \w      1.00  50.00   0.50   21.01    --   11.77  24.00  24.00   98
  5  \w    -41.00 -15.00   0.50   21.01    --  -11.14 -38.00  60.00   52
  6  \w     20.00  51.00   0.50   21.01    --  -11.14  38.00 -30.00   62
  7  \w    -73.00 -48.00   0.50   21.01    --  -11.14 145.00-172.92   50
  8  \w    -44.00 -16.00   0.50   21.01    --  -11.14  93.00  94.43   56
  9  \w    -77.00 -48.00   0.50   21.01    --  -11.14 -38.00  60.00   58
 10  \w    -83.00   5.00   0.50   21.01    --  -11.14 -19.00 120.00  176
 11  \w    -17.00  23.00   0.50   21.01    --  -11.14 -99.00-180.00   80
 12  \w    -31.00  12.00   0.50   21.01    --  -11.14  19.00 -60.00   86
 13  \w    -77.00 -11.00   0.50   21.01    --  -11.14 -38.00  90.00  132
 14  \w    -24.00  22.00   0.50   21.01    --  -11.14 -99.00-120.00   92
 15  \w    -72.00 -39.00   0.50   21.01    --  -11.14 141.00-111.98   66
 16  \w    -78.00 -44.00   0.50   21.01    --  -11.14 150.00-104.01   68
 17  \w    -49.00 -21.00   0.50   21.01    --  -11.14 107.00  92.61   56
 18  \w    -26.00  55.00   0.50   21.01    --  -11.14  38.00-180.00  162
 19  \w    -66.00 -39.00   0.50   21.01    --  -11.14 141.00  64.09   54
 20  \w    -17.00   9.00   0.50   21.01    --  -11.14 -99.00 -30.00   52
 21  \w    -74.00 -49.00   0.50   21.01    --  -11.14 145.00   0.71   50
 22  \w     27.00  61.00   0.50   21.01    --  -11.14  19.00 -60.00   68
 23  \w    -73.00 -45.00   0.50   21.01    --  -11.14 153.00  17.89   56
 24  \w    -77.00  -1.00   0.50   21.01    --  -11.14 -38.00-150.00  152
 25  \w    -24.00  22.00   0.50   21.01    --  -11.14 -99.00 120.00   92
 26  \w    -24.00   6.00   0.50   21.01    --  -11.14  38.00  90.00   60
 27  \w     12.00  55.00   0.50   21.01    --  -11.14  38.00  90.00   86
 28  \w    -58.00  -9.00   0.50   21.01    --  -11.14 -77.00-150.00   98
 29  \w    -66.00 -41.00   0.50   21.01    --  -11.14 136.00-120.27   50
 30  \w    -26.00  12.00   0.50   21.01    --  -11.14  38.00 -30.00   76
 31  \w    -43.00   5.00   0.50   21.01    --   11.77 -19.00 150.00   96
 32  \w     -8.00  76.00   0.50   21.01    --   11.77  77.00-150.00  168
 33  \w     -9.00  79.00   0.50   21.01    --   11.77  57.00-150.00  176
 34  \w     15.00  46.00   0.50   21.01    --   11.77 -99.00-120.00   62
 35  \w    -26.00   2.00   0.50   21.01    --   11.77 -99.00-120.00   56
 36  \w     12.00  47.00   0.50   21.01    --   11.77-125.00-120.00   70
 37  \w    -57.00   0.00   0.50   21.01    --   11.77 -19.00  60.00  114
 38  \w     -3.00  74.00   0.50   21.01    --   11.77  38.00  30.00  154
 39  \w     13.00  60.00   0.50   21.01    --   11.77-125.00  60.00   94
 40  \w      1.00  34.00   0.50   21.01    --   11.77 -77.00-180.00   66
 41  \w    -57.00 -30.00   0.50   21.01    --   11.77 -77.00-180.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            89428
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.525
_exptl_absorpt_coefficient_mu    0.152
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67912
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.63a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.251
_exptl_crystal_description       needle
_exptl_crystal_F_000             1392
_exptl_crystal_recrystallization_method
'The material was recrystallised from Acetonitrile by slow evaporation'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.472
_refine_diff_density_min         -0.205
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     534
_refine_ls_number_reflns         6091
_refine_ls_number_restraints     517
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1082
_refine_ls_R_factor_gt           0.0732
_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^)+(0.1301P)^2^+0.8492P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2133
_refine_ls_wR_factor_ref         0.2474
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3747
_reflns_number_total             6091
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00434a2.cif
_cod_data_source_block           r-1n
_cod_depositor_comments          'Adding full bibliography for 7159348.cif.'
_cod_database_code               7159348
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.949
_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
 C13-C17
 1.54 with sigma of 0.02
3. Rigid body (RIGU) restrains
 N1, Cl1, C38, C41, N6, C5, Cl2, C34, C40, C21, N3, N5, N7, C47, C2, H34, C27,
 C43, C23, C3, C31, C33, N4, C16, H27A, H27B, H27C, H43A, H43B, H43C, C45, H23,
 H3, C49, C7, H33, C15, H31, C10, C1, C8, C22, O2, C30, C11, H45, H49, H7, C29,
 H15, C4, C20, C6, C12, C36, C44, H11, H29, H20, O1, C28, C26, C14, H12, C24,
 H36, C46, H44, C50, H28, C32, H26, H14, C18, N2, H24, H46, H50, N8, C42, C9,
 C19, H9B, H9A, C25, C13, C35, H35B, H35C, H42A, H42B, C48, C37, H19A, H19B,
 C39, H39A, H39B, H37A, H37B, H25A, H25B, H13A, H13B, C17, H17B, H17C, H35A,
 H48A, H48B, H48C, H37C, H39C, H17A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: Cl1(0.7) N6(0.7) N5(0.7) C38(0.7) C40(0.7) C27(0.7) H27A(0.7)
 H27B(0.7) H27C(0.7) C7(0.7) H7(0.7) C29(0.7) H29(0.7) C15(0.7) H15(0.7)
 C31(0.7) H31(0.7) C2(0.7) C33(0.7) H33(0.7) C9(0.5) H9A(0.5) H9B(0.5) C37(0.5)
 H37A(0.5) H37B(0.5) H37C(0.5) C19(0.5) H19A(0.5) H19B(0.5) C39(0.5) H39A(0.5)
 H39B(0.5) H39C(0.5) N3(0.3) C5(0.3) C21(0.3) N7(0.3) C43(0.3) H43A(0.3)
 H43B(0.3) H43C(0.3) Cl2(0.3) C11(0.3) H11(0.3) C45(0.3) H45(0.3) C23(0.3)
 H23(0.3) C47(0.3) C3(0.3) H3(0.3) C49(0.3) H49(0.3)
5.a :
 N3(C5,C41,C21,N7)
5.b Secondary CH2 refined with riding coordinates:
 C42(H42A,H42B), C25(H25A,H25B), C13(H13A,H13B), C9(H9A,H9B), C19(H19A,H19B)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C14(H14), C20(H20), C24(H24), C26(H26), C28(H28), C34(H34),
 C36(H36), C44(H44), C46(H46), C50(H50), C7(H7), C29(H29), C15(H15), C31(H31),
 C33(H33), C11(H11), C45(H45), C23(H23), C3(H3), C49(H49)
5.d Fitted hexagon refined as free rotating group:
 C7(C29,C15,C31,C2,C33), C11(C45,C23,C47,C3,C49)
5.e Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C27(H27A,H27B,H27C), C17(H17A,H17B,H17C), C35(H35A,H35B,
 H35C), C37(H37A,H37B,H37C), C39(H39A,H39B,H39C), C43(H43A,H43B,H43C)
;
_shelx_res_checksum              13263
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_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
;