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_7135260
_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         'C33 H68 Al Mg N5 Si4'
_chemical_formula_sum            'C33 H68 Al Mg N5 Si4'
_chemical_formula_weight         698.57
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2025-08-20
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7205)
;
_audit_update_record
;
2025-08-21 deposited with the CCDC.	2025-11-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.85853(5)
_cell_length_b                   20.34220(9)
_cell_length_c                   32.09584(12)
_cell_measurement_reflns_used    78385
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      68.2390
_cell_measurement_theta_min      2.4980
_cell_volume                     8395.33(6)
_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 2018/3 (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 0.997
_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    -40.00  26.00   0.50    0.30    --  -40.58  35.00 -45.00  132
  2  \w   -107.00 -26.00   0.50    0.30    --  -40.58 -35.00 156.00  162
  3  \w    -71.00  30.00   0.50    0.30    --  -40.58  87.00 110.00  202
  4  \w    -91.00 -16.00   0.50    0.30    --  -40.58 132.00 177.00  150
  5  \w    -26.00  40.00   0.50    0.30    --   40.58 -35.00 156.00  132
  6  \w    -22.00  71.00   0.50    0.30    --   40.58 -87.00  -6.00  186
  7  \w     38.00  95.00   0.50    0.30    --   40.58-132.00 107.00  114
  8  \w     26.00 108.00   0.50    0.30    --   40.58  35.00 -45.00  164
  9  \w   -153.00 -78.00   0.50    1.00    --  -82.50 -87.00  -6.00  150
 10  \w   -113.00 -12.00   0.50    1.00    --  -82.50  87.00 110.00  202
 11  \w    -96.00 -19.00   0.50    1.00    --  -82.50 138.00  -6.00  154
 12  \w    -91.00 -17.00   0.50    1.00    --  -82.50 132.00 177.00  148
 13  \w   -150.00 -64.00   0.50    1.00    --  -82.50-138.00 -67.00  172
 14  \w   -149.00 -68.00   0.50    1.00    --  -82.50 -35.00 156.00  162
 15  \w     27.00 127.00   0.50    1.00    --   96.67 -87.00  -6.00  200
 16  \w     86.00 164.00   0.50    1.00    --   96.67 138.00  -6.00  156
 17  \w     90.00 162.00   0.50    1.00    --   96.67 132.00 177.00  144
 18  \w     82.00 164.00   0.50    1.00    --   96.67  35.00 -45.00  164
 19  \w    100.00 167.00   0.50    1.00    --   96.67  87.00 110.00  134
 20  \w   -109.00 -63.00   0.50    0.30    --  -40.58-139.00 120.00   92
 21  \w   -109.00 -63.00   0.50    0.30    --  -40.58-139.00-120.00   92
 22  \w    -56.00 -16.00   0.50    1.00    --  -82.50  50.00-120.00   80
 23  \w     29.00  83.00   0.50    1.00    --   96.67 -68.00 -90.00  108
 24  \w     29.00  83.00   0.50    1.00    --   96.67 -68.00   0.00  108
 25  \w     30.00  57.00   0.50    1.00    --   96.67 -50.00 120.00   54
 26  \w     29.00  68.00   0.50    1.00    --   96.67 -59.00-120.00   78
 27  \w     30.00  57.00   0.50    1.00    --   96.67 -50.00 -90.00   54
 28  \w     23.00 106.00   0.50    1.00    --   96.67 -96.00 -90.00  166
 29  \w     29.00  68.00   0.50    1.00    --   96.67 -59.00 120.00   78
 30  \w   -109.00 -63.00   0.50    0.30    --  -40.58-139.00 -30.00   92
 31  \w   -109.00 -14.00   0.50    0.30    --  -40.58 -77.00 120.00  190
 32  \w   -107.00 -20.00   0.50    0.30    --  -40.58 -54.00  30.00  174
 33  \w     21.00 108.00   0.50    0.30    --   40.58  54.00-150.00  174
 34  \w     14.00 109.00   0.50    0.30    --   40.58  77.00  30.00  190
 35  \w     14.00 109.00   0.50    0.30    --   40.58  77.00 120.00  190
 36  \w     14.00 109.00   0.50    0.30    --   40.58  77.00-120.00  190
 37  \w     14.00 109.00   0.50    0.30    --   40.58  77.00 -30.00  190
 38  \w     70.00 165.00   0.50    1.00    --   96.67  77.00-180.00  190
 39  \w     44.00 127.00   0.50    1.00    --   96.67-145.00-120.00  166
 40  \w     78.00 163.00   0.50    1.00    --   96.67  50.00 150.00  170
 41  \w     78.00 163.00   0.50    1.00    --   96.67  50.00   0.00  170
 42  \w     73.00 165.00   0.50    1.00    --   96.67  68.00-120.00  184
 43  \w     75.00 164.00   0.50    1.00    --   96.67  59.00  30.00  178
 44  \w     70.00 165.00   0.50    1.00    --   96.67  77.00-150.00  190
 45  \w     82.00 167.00   0.50    1.00    --   96.67  25.00  90.00  170
 46  \w     75.00 164.00   0.50    1.00    --   96.67  59.00 -90.00  178
 47  \w     73.00 165.00   0.50    1.00    --   96.67  68.00  60.00  184
 48  \w     70.00 165.00   0.50    1.00    --   96.67  77.00  90.00  190
;
_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  0.0494
_diffrn_reflns_av_unetI/netI     0.0165
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            107898
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.360
_diffrn_reflns_theta_min         2.753
_exptl_absorpt_coefficient_mu    1.866
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79248
_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 reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.105
_exptl_crystal_description       block
_exptl_crystal_F_000             3056
_exptl_crystal_preparation       'solvent diffusion'
_exptl_crystal_size_max          0.0128
_exptl_crystal_size_mid          0.0126
_exptl_crystal_size_min          0.0124
_refine_diff_density_max         0.802
_refine_diff_density_min         -0.562
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     435
_refine_ls_number_reflns         7675
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0563P)^2^+9.0380P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1121
_refine_ls_wR_factor_ref         0.1135
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7312
_reflns_number_total             7675
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc05693d2.cif
_cod_data_source_block           dm-cm_mgal14_auto
_cod_database_code               7135260
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.977
_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. Others
 Fixed Sof: C17(0.75) H17A(0.75) H17B(0.75) C18(0.25) H18A(0.25) H18B(0.25)
3.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C21(H21A,H21B), C19(H19A,H19B), C17(H17A,
 H17B), C18(H18A,H18B)
3.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C8(H8), C4(H4), C2(H2)
3.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C27(H27A,H27B,H27C), C14(H14A,H14B,
 H14C), C13(H13A,H13B,H13C), C31(H31A,H31B,H31C), C23(H23A,H23B,H23C), C32(H32A,
 H32B,H32C), C12(H12A,H12B,H12C), C33(H33A,H33B,H33C), C28(H28A,H28B,H28C),
 C25(H25A,H25B,H25C), C34(H34A,H34B,H34C), C22(H22A,H22B,H22C), C24(H24A,H24B,
 H24C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              21304
_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
;