On the existence of low-valent magnesium-calcium complexes.
Mai, Jonathan; Rösch, Bastian; Patel, Neha; Langer, Jens; Harder, Sjoerd; Chemical science 14 (2023) 4724–4734; doi:10.1039/d3sc00909b

data_1568861
_publ_section_title
;
 On the existence of low-valent magnesium-calcium complexes.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              4724
_journal_page_last               4734
_journal_paper_doi               10.1039/d3sc00909b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C90 H134 Ca Mg N4'
_chemical_formula_sum            'C90 H134 Ca Mg N4'
_chemical_formula_weight         1336.39
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-11
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-08 deposited with the CCDC.	2023-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.1984(12)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.38232(18)
_cell_length_b                   28.8484(3)
_cell_length_c                   21.8547(2)
_cell_measurement_reflns_used    15926
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      72.3570
_cell_measurement_theta_min      3.6470
_cell_volume                     7794.56(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2903
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.974
_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   -116.00 -17.00   1.00   10.00    --  -41.48 -38.00-150.00   99
  2  \w     27.00  98.00   1.00   10.00    --   41.48-125.00 150.00   71
  3  \w     27.00  98.00   1.00   10.00    --   41.48-125.00 -90.00   71
  4  \w     31.00 130.00   1.00   40.00    --  104.33 -45.00-120.00   99
  5  \w     75.00 177.00   1.00   40.00    --  104.33  61.00 150.00  102
  6  \w     32.00 133.00   1.00   40.00    --  104.33 -61.00   0.00  101
  7  \w    103.00 178.00   1.00   40.00    --  104.33  77.00-120.00   75
  8  \w     22.00 106.00   1.00   40.00    --  104.33 -94.00-150.00   84
  9  \w   -114.00 -13.00   1.00   10.00    --  -41.48 -57.00 120.00  101
 10  \w   -115.00 -11.00   1.00   10.00    --  -41.48 -69.00  40.00  104
 11  \w     52.00 115.00   1.00   40.00    --  104.33  15.00  30.00   63
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1214051000
_diffrn_orient_matrix_UB_12      0.0121149000
_diffrn_orient_matrix_UB_13      -0.0052695000
_diffrn_orient_matrix_UB_21      -0.0235871000
_diffrn_orient_matrix_UB_22      -0.0401339000
_diffrn_orient_matrix_UB_23      0.0436523000
_diffrn_orient_matrix_UB_31      0.0158818000
_diffrn_orient_matrix_UB_32      0.0330153000
_diffrn_orient_matrix_UB_33      0.0552451000
_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  0.0269
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            44605
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.764
_diffrn_reflns_theta_min         3.064
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.118
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.776
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear orangish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_description       plank
_exptl_crystal_F_000             2936
_exptl_crystal_size_max          0.181
_exptl_crystal_size_mid          0.081
_exptl_crystal_size_min          0.058
_refine_diff_density_max         0.253
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.00013(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     954
_refine_ls_number_reflns         15115
_refine_ls_number_restraints     331
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0362
_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^)+(0.0425P)^2^+2.8654P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0879
_refine_ls_wR_factor_ref         0.0928
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13059
_reflns_number_total             15115
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00909b2.cif
_cod_data_source_block           hasj201117b
_cod_depositor_comments
'Adding full bibliography for 1568860--1568864.cif.'
_cod_original_cell_volume        7794.57(16)
_cod_database_code               1568861
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C90H134CaMgN4
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.823
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C39A-C33 \\sim C39-C33
 with sigma of 0.02
 C42-C39 \\sim C39A-C42A \\sim C39A-C40A \\sim C40-C39
 with sigma of 0.02
 C41-C40 \\sim C40A-C41A \\sim C43A-C42A \\sim C43-C42
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C33 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43 \\sim C39A \\sim C40A
\\sim C41A \\sim C42A \\sim C43A: within 4A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 4A
4. Others
 Sof(C39A)=Sof(H39A)=Sof(C40A)=Sof(H40c)=Sof(H40d)=Sof(C41A)=Sof(H41d)=
 Sof(H41e)=Sof(H41f)=Sof(C42A)=Sof(H42c)=Sof(H42d)=Sof(C43A)=Sof(H43d)=
 Sof(H43e)=Sof(H43f)=1-FVAR(1)
 Sof(C39)=Sof(H39)=Sof(C40)=Sof(H40a)=Sof(H40b)=Sof(C41)=Sof(H41a)=Sof(H41b)=
 Sof(H41c)=Sof(C42)=Sof(H42a)=Sof(H42b)=Sof(C43)=Sof(H43a)=Sof(H43b)=Sof(H43c)=
 FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C18(H18), C23(H23), C34(H34), C65(H65), C70(H70), C81(H81), C86(H86),
 C39(H39), C39A(H39A)
5.b Secondary CH2 refined with riding coordinates:
 C19(H19a,H19b), C21(H21a,H21b), C24(H24a,H24b), C26(H26a,H26b), C35(H35a,
 H35b), C37(H37a,H37b), C66(H66a,H66b), C68(H68a,H68b), C71(H71a,H71b),
 C73(H73a,H73b), C82(H82a,H82b), C84(H84a,H84b), C87(H87a,H87b), C89(H89a,H89b),
  C40(H40a,H40b), C42(H42a,H42b), C40A(H40c,H40d), C42A(H42c,H42d)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C14(H14), C15(H15), C16(H16), C30(H30), C31(H31), C32(H32), C49(H49),
 C50(H50), C51(H51), C52(H52), C56(H56), C61(H61), C62(H62), C63(H63), C77(H77),
  C78(H78), C79(H79)
5.d Idealised Me refined as rotating group:
 C5(H5a,H5b,H5c), C6(H6a,H6b,H6c), C7(H7a,H7b,H7c), C9(H9a,H9b,H9c), C10(H10a,
 H10b,H10c), C11(H11a,H11b,H11c), C20(H20a,H20b,H20c), C22(H22a,H22b,H22c),
 C25(H25a,H25b,H25c), C27(H27a,H27b,H27c), C36(H36a,H36b,H36c), C38(H38a,H38b,
 H38c), C54(H54a,H54b,H54c), C58(H58a,H58b,H58c), C67(H67a,H67b,H67c), C69(H69a,
 H69b,H69c), C72(H72a,H72b,H72c), C74(H74a,H74b,H74c), C83(H83a,H83b,H83c),
 C85(H85a,H85b,H85c), C88(H88a,H88b,H88c), C90(H90a,H90b,H90c), C41(H41a,H41b,
 H41c), C43(H43a,H43b,H43c), C41A(H41d,H41e,H41f), C43A(H43d,H43e,H43f)
;
_shelx_res_checksum              53275
_shelx_hkl_checksum              70839
_olex2_date_sample_data_collection 2020-11-17
_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 1.466
_oxdiff_exptl_absorpt_empirical_full_min 0.835