Intriguing Metal-Ligand Interplays Leading to Diverse Al-H-M (M = Mg, Ca) Heterobimetallic Hydrides on a Picolyl-Based 3N Ligand
Mandal, Chhotan; Kundu, Abhishek; Panda, Sourav; Mukherjee, Debabrata; Chemical Communications  (2025) –; doi:10.1039/D5CC05693D

data_7135259
_publ_section_title
;
 Intriguing Metal-Ligand Interplays Leading to Diverse Al-H-M (M = Mg, Ca)
 Heterobimetallic Hydrides on a Picolyl-Based 3N Ligand
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC05693D
_journal_year                    2025
_chemical_formula_moiety         'C54 H96 Al2 Ca N8 Si4'
_chemical_formula_sum            'C54 H96 Al2 Ca N8 Si4'
_chemical_formula_weight         1063.78
_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   mixed
_audit_creation_date             2025-01-30
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-08-21 deposited with the CCDC.	2025-11-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.3480(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.62070(10)
_cell_length_b                   25.95170(10)
_cell_length_c                   21.11620(10)
_cell_measurement_reflns_used    52062
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      68.1440
_cell_measurement_theta_min      2.6960
_cell_volume                     6264.58(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.119a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.119a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_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   -102.00 -24.00   0.50    2.09    --  -40.58 147.00-109.00  156
  2  \w   -109.00 -57.00   0.50    2.09    --  -40.58-147.00-159.00  104
  3  \w    -87.00 -12.00   0.50    2.09    --  -40.58 125.00  83.00  150
  4  \w     34.00  89.00   0.50    2.09    --   40.58-125.00   6.00  110
  5  \w     45.00 106.00   0.50    2.09    --   40.58-147.00-159.00  122
  6  \w   -147.00 -73.00   0.50   10.35    --  -82.50-125.00   6.00  148
  7  \w   -151.00 -57.00   0.50   10.35    --  -82.50-147.00-159.00  188
  8  \w   -102.00 -24.00   0.50   10.35    --  -82.50 147.00-109.00  156
  9  \w    -87.00 -18.00   0.50   10.35    --  -82.50 125.00  83.00  138
 10  \w     79.00 164.00   0.50   10.35    --   96.67 147.00-109.00  170
 11  \w     45.00 128.00   0.50   10.35    --   96.67-147.00-159.00  166
 12  \w     34.00 112.00   0.50   10.35    --   96.67-125.00   6.00  156
 13  \w    -24.00  35.00   0.50    2.09    --  -40.58  11.00 120.00  118
 14  \w    -24.00  35.00   0.50    2.09    --  -40.58  11.00   0.00  118
 15  \w    -28.00  31.00   0.50    2.09    --  -40.58  21.00-150.00  118
 16  \w    -97.00 -20.00   0.50    2.09    --  -40.58 139.00-180.00  154
 17  \w    -37.00  27.00   0.50    2.09    --  -40.58  32.00 -90.00  128
 18  \w    -31.00  28.00   0.50    2.09    --   40.58 -21.00-120.00  118
 19  \w    -31.00  28.00   0.50    2.09    --   40.58 -21.00-120.00  118
 20  \w    -27.00  37.00   0.50    2.09    --   40.58 -32.00-150.00  128
 21  \w    -47.00 -15.00   0.50   10.35    --  -82.50  42.00 -90.00   64
 22  \w    -68.00 -14.00   0.50   10.35    --  -82.50  59.00 120.00  108
 23  \w   -153.00 -78.00   0.50   10.35    --  -82.50 -87.00 120.00  150
 24  \w     80.00 163.00   0.50   10.35    --   96.67  42.00  90.00  166
 25  \w     82.00 167.00   0.50   10.35    --   96.67  25.00 -90.00  170
 26  \w     80.00 163.00   0.50   10.35    --   96.67  42.00  90.00  166
 27  \w     23.00 106.00   0.50   10.35    --   96.67 -96.00-120.00  166
 28  \w     23.00 106.00   0.50   10.35    --   96.67 -96.00-120.00  166
 29  \w     82.00 167.00   0.50   10.35    --   96.67  25.00 -90.00  170
 30  \w     29.00  83.00   0.50   10.35    --   96.67 -68.00 -30.00  108
 31  \w     30.00  57.00   0.50   10.35    --   96.67 -50.00-150.00   54
 32  \w     30.00  57.00   0.50   10.35    --   96.67 -50.00  60.00   54
 33  \w     29.00  68.00   0.50   10.35    --   96.67 -59.00  30.00   78
 34  \w     33.00 109.00   0.50   10.35    --   96.67-117.00  30.00  152
 35  \w     23.00 106.00   0.50   10.35    --   96.67 -96.00-180.00  166
 36  \w     71.00 170.00   0.50   10.35    --   96.67  17.00-150.00  198
 37  \w     71.00 170.00   0.50   10.35    --   96.67  17.00-150.00  198
 38  \w     99.00 161.00   0.50   10.35    --   96.67 117.00  30.00  124
 39  \w     30.00  57.00   0.50   10.35    --   96.67 -50.00 150.00   54
 40  \w     33.00 109.00   0.50   10.35    --   96.67-117.00-180.00  152
 41  \w     29.00  83.00   0.50   10.35    --   96.67 -68.00-180.00  108
 42  \w     29.00  68.00   0.50   10.35    --   96.67 -59.00 -60.00   78
 43  \w     80.00 163.00   0.50   10.35    --   96.67  42.00   0.00  166
 44  \w     30.00  57.00   0.50   10.35    --   96.67 -50.00   0.00   54
 45  \w   -109.00 -14.00   0.50    2.09    --  -40.58 -77.00 -60.00  190
 46  \w   -107.00 -20.00   0.50    2.09    --  -40.58 -54.00  30.00  174
 47  \w   -109.00 -63.00   0.50    2.09    --  -40.58-139.00  60.00   92
 48  \w   -109.00 -14.00   0.50    2.09    --  -40.58 -77.00 150.00  190
 49  \w   -109.00 -17.00   0.50    2.09    --  -40.58 -66.00 -30.00  184
 50  \w   -109.00 -14.00   0.50    2.09    --  -40.58 -77.00-120.00  190
 51  \w     14.00 109.00   0.50    2.09    --   40.58  77.00  90.00  190
 52  \w     17.00 109.00   0.50    2.09    --   40.58  66.00-150.00  184
 53  \w     14.00 109.00   0.50    2.09    --   40.58  77.00-120.00  190
 54  \w     14.00 109.00   0.50    2.09    --   40.58  77.00  30.00  190
 55  \w    -31.00  28.00   0.50    2.09    --   40.58 -21.00 -30.00  118
 56  \w     17.00 109.00   0.50    2.09    --   40.58  66.00 150.00  184
 57  \w     75.00 164.00   0.50   10.35    --   96.67  59.00 150.00  178
 58  \w     75.00 164.00   0.50   10.35    --   96.67  59.00 -60.00  178
 59  \w     75.00 164.00   0.50   10.35    --   96.67  59.00  30.00  178
 60  \w     75.00 124.00   0.50   10.35    --   96.67  59.00 120.00   98
 61  \w     73.00 165.00   0.50   10.35    --   96.67  68.00-150.00  184
 62  \w     30.00  57.00   0.50   10.35    --   96.67 -50.00-120.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0506
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.999
_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       31
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            98837
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.305
_diffrn_reflns_theta_min         2.725
_exptl_absorpt_coefficient_mu    2.166
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63592
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.119a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear brownish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.128
_exptl_crystal_description       block
_exptl_crystal_F_000             2312
_exptl_crystal_preparation       'solvent diffusion'
_exptl_crystal_size_max          0.0228
_exptl_crystal_size_mid          0.0224
_exptl_crystal_size_min          0.0198
_refine_diff_density_max         0.468
_refine_diff_density_min         -0.344
_refine_diff_density_rms         0.044
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     668
_refine_ls_number_reflns         11421
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0407
_refine_ls_R_factor_gt           0.0373
_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^)+(0.0553P)^2^+2.8026P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1002
_refine_ls_wR_factor_ref         0.1025
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10517
_reflns_number_total             11421
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05693d2.cif
_cod_data_source_block           dm_cm_alca02_auto
_cod_database_code               7135259
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.952
_olex2_refinement_description
;
1.a Ternary CH refined with riding coordinates:
 C15(H15), C48(H48)
1.b Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C16(H16A,H16B), C50(H50A,H50B), C49(H49A,H49B), C20(H20A,
 H20B), C53(H53A,H53B)
1.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C31(H31), C8(H8), C35(H35), C29(H29), C4(H4), C30(H30),
 C37(H37), C10(H10)
1.d Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C26(H26A,H26B,H26C), C25(H25A,H25B,H25C), C45(H45A,H45B,
 H45C), C14(H14A,H14B,H14C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C43(H43A,
 H43B,H43C), C21(H21A,H21B,H21C), C54(H54A,H54B,H54C), C47(H47A,H47B,H47C),
 C27(H27A,H27B,H27C), C22(H22A,H22B,H22C), C39(H39A,H39B,H39C), C12(H12A,H12B,
 H12C), C46(H46A,H46B,H46C), C19(H19A,H19B,H19C), C52(H52A,H52B,H52C), C42(H42A,
 H42B,H42C), C44(H44A,H44B,H44C), C13(H13A,H13B,H13C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              37749
_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
;