A low-spin manganese(II) complex with an emissive charge-transfer excited state.
Rhames, Maxwell C.; Burnett, Nora L.; Lee, Annemarie A.; Clark, Colin B.; Tocco, William C.; Ahmed, Ahshabibi; Ruhren, Alexander N.; Besson, Claire; Panetier, Julien A.; Swierk, John R.; Arias-Rotondo, Daniela M; Dalton transactions (Cambridge, England : 2003) 55 (2026) 4097–4101; doi:10.1039/d5dt02990b

data_7720267
_publ_section_title
;
 A low-spin manganese(II) complex with an emissive charge-transfer excited
 state.
;
_journal_issue                   10
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4097
_journal_page_last               4101
_journal_paper_doi               10.1039/d5dt02990b
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C46 H34 Mn N10, 2(F6 P)'
_chemical_formula_sum            'C46 H34 F12 Mn N10 P2'
_chemical_formula_weight         1071.71
_chemical_name_systematic
'di(2,6-bis[3-phenylimidazol-2-35ylidene]pyridine)manganese(II) hexafluorophosphate'
_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   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2m80gd
_audit_creation_date             2025-07-07
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-07 deposited with the CCDC.	2026-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.313(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.3216(12)
_cell_length_b                   13.6024(8)
_cell_length_c                   20.9657(13)
_cell_measurement_reflns_used    3540
_cell_measurement_temperature    296.8(10)
_cell_measurement_theta_max      22.7600
_cell_measurement_theta_min      2.1830
_cell_volume                     4650.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.120a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 44.108a 64-bit (release 25-04-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.43.120a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      296.8(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -74.00 110.00   0.50   40.00    --   20.00  54.00-150.00  368
  2  \w    -74.00  50.00   0.50   40.00    --   20.00  54.00   0.00  248
  3  \w      7.00  74.00   0.50   40.00    --   20.00  54.00   0.00  134
  4  \w     78.00 106.00   0.50   40.00    --   20.00  54.00   0.00   56
  5  \w    -72.00  20.00   0.50   40.00    --   20.00  54.00  90.00  184
  6  \w     70.00 109.00   0.50   40.00    --   20.00  54.00  90.00   78
  7  \w    -73.00  17.00   0.50   40.00    --   20.00  54.00 -60.00  180
  8  \w     80.00 105.00   0.50   40.00    --   20.00  54.00 -60.00   50
  9  \w     41.00  73.00   0.50   40.00    --   20.00  54.00 150.00   64
 10  \w     85.00 110.00   0.50   40.00    --   20.00  54.00 150.00   50
 11  \w    -74.00  64.00   0.50   40.00    --   20.00  54.00 -90.00  276
 12  \w    -72.00  -5.00   0.50   40.00    --   20.00  54.00-150.00  134
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini II'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0037139000
_diffrn_orient_matrix_UB_12      0.0382812000
_diffrn_orient_matrix_UB_13      0.0226591000
_diffrn_orient_matrix_UB_21      -0.0429553000
_diffrn_orient_matrix_UB_22      0.0014366000
_diffrn_orient_matrix_UB_23      -0.0065878000
_diffrn_orient_matrix_UB_31      -0.0057605000
_diffrn_orient_matrix_UB_32      -0.0353825000
_diffrn_orient_matrix_UB_33      0.0242727000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1091
_diffrn_reflns_av_unetI/netI     0.1153
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            57139
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         2.156
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.448
_exptl_absorpt_correction_T_max  0.997
_exptl_absorpt_correction_T_min  0.966
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.120a (Rigaku Oxford Diffraction, 2024)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.531
_exptl_crystal_description       needle
_exptl_crystal_F_000             2172
_exptl_crystal_recrystallization_method
'Slow diffusion of diethyl ether into acetonitrile solution'
_exptl_crystal_size_max          0.39
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.572
_refine_diff_density_min         -0.213
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     768
_refine_ls_number_reflns         8532
_refine_ls_number_restraints     1722
_refine_ls_restrained_S_all      0.959
_refine_ls_R_factor_all          0.1823
_refine_ls_R_factor_gt           0.0710
_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^)+(0.0759P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1395
_refine_ls_wR_factor_ref         0.1778
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3896
_reflns_number_total             8532
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02990b2.cif
_cod_data_source_block           '[Mn(bimPh)2](PF6)2'
_cod_depositor_comments          'Adding full bibliography for 7720267.cif.'
_cod_original_cell_volume        4650.8(5)
_cod_database_code               7720267
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C46H34F12MnN10P2
_cell_oxdiff_angle_alpha         89.985(4)
_cell_oxdiff_angle_beta          129.311(8)
_cell_oxdiff_angle_gamma         89.991(5)
_cell_oxdiff_length_a            16.3186(12)
_cell_oxdiff_length_b            13.6016(7)
_cell_oxdiff_length_c            27.0808(15)
_cell_oxdiff_measurement_reflns_used 3539
_cell_oxdiff_volume              4650.7(5)
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.845
_diffrn_oxdiff_digest_hkl
;
43d72a22b80d6c660cd922515c85086dbfbc63
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 F1A-F3A \\sim F1A-F4A \\sim F1A-F6A \\sim F1A-F5A \\sim F2A-F3A \\sim F2A-F4A
\\sim F2A-F6A \\sim F2A-F5A
 \\sim F3A-F6A \\sim F3A-F5A \\sim F4A-F6A \\sim F4A-F5A \\sim F4C-F6C \\sim
F4C-F5C \\sim F4C-F1C \\sim F4C-
 F2C \\sim F6C-F1C \\sim F6C-F2C \\sim F6C-F3C \\sim F5C-F1C \\sim F5C-F2C
\\sim F5C-F3C \\sim F1C-F3C ~
 F2C-F3C \\sim F1B-F3B \\sim F1B-F4B \\sim F1B-F6B \\sim F1B-F5B \\sim F2B-F3B
\\sim F2B-F4B \\sim F2B-F6B
 \\sim F2B-F5B \\sim F3B-F6B \\sim F3B-F5B \\sim F4B-F6B \\sim F4B-F5B \\sim
F2D-F5D \\sim F2D-F3D \\sim F2D-
 F4D \\sim F2D-F6D \\sim F1D-F5D \\sim F1D-F3D \\sim F1D-F4D \\sim F1D-F6D
\\sim F5D-F3D \\sim F5D-F4D ~
 F3D-F6D \\sim F4D-F6D
 with sigma of 0.04
 P1A-F1A \\sim P1A-F2A \\sim P1A-F3A \\sim P1A-F4A \\sim P1A-F6A \\sim P1A-F5A
\\sim P1C-F4C \\sim P1C-F6C
 \\sim P1C-F5C \\sim P1C-F1C \\sim P1C-F2C \\sim P1C-F3C \\sim P1B-F1B \\sim
P1B-F2B \\sim P1B-F3B \\sim P1B-
 F4B \\sim P1B-F6B \\sim P1B-F5B \\sim P1D-F2D \\sim P1D-F1D \\sim P1D-F5D
\\sim P1D-F3D \\sim P1D-F4D ~
 P1D-F6D
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 0.9A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 0.9A
4. Rigid body (RIGU) restrains
 F1D, F2D, F3D, F4D, F5D, F6D, P1D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1A, F2A, F3A, F4A, F5A, F6A, P1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1B, F2B, F3B, F4B, F5B, F6B, P1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1C, F2C, F3C, F4C, F5C, F6C, P1C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(P1B)=1-FVAR(1)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(P1A)=FVAR(1)
 Sof(F1D)=Sof(F2D)=Sof(F3D)=Sof(F4D)=Sof(F5D)=Sof(F6D)=Sof(P1D)=1-FVAR(2)
 Sof(F1C)=Sof(F2C)=Sof(F3C)=Sof(F4C)=Sof(F5C)=Sof(F6C)=Sof(P1C)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C11(H11), C12(H12),
 C13(H13), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22),
  C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31),
 C34(H34), C35(H35), C36(H36), C39(H39), C40(H40), C41(H41), C42(H42), C43(H43),
  C44(H44), C45(H45)
;
_shelx_res_checksum              17269
_olex2_date_sample_completion    2025-06-11
_olex2_date_sample_data_collection 2025-06-10
_olex2_date_sample_submission    2024-07-29
_olex2_exptl_crystal_mounting_method '150 um Mitegen loop'
_olex2_submission_original_sample_id MCR_05_036
_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 1.038
_oxdiff_exptl_absorpt_empirical_full_min 0.957