Zincafluorene complex with an empty C-Zn π orbital that captures visible light.
Iwamoto, Hidemitsu; Sunada, Yusuke; Wada, Yoshimasa; Chemical science 17 (2026) 3023–3030; doi:10.1039/d5sc09340f

data_1576520
_publ_section_title
;
 Zincafluorene complex with an empty C-Zn &#x3c0; orbital that captures
 visible light.
;
_journal_issue                   6
_journal_name_full               'Chemical science'
_journal_page_first              3023
_journal_page_last               3030
_journal_paper_doi               10.1039/d5sc09340f
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C35 H43 N Zn, 2(C7 H8)'
_chemical_formula_sum            'C49 H59 N Zn'
_chemical_formula_weight         727.34
_chemical_name_systematic        C49H59NZn
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-30
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-09-30 deposited with the CCDC.	2026-01-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.0503(4)
_cell_length_b                   18.7163(5)
_cell_length_c                   26.6927(7)
_cell_measurement_reflns_used    32530
_cell_measurement_temperature    173
_cell_measurement_theta_max      30.5770
_cell_measurement_theta_min      2.6150
_cell_volume                     8018.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (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      173
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.869
_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      2.00  28.00   0.50   41.53    --    3.94  78.00  31.00   52
  2  \w    -73.00   4.00   0.50   41.53    --   -2.84 -38.00 -60.00  154
  3  \w    -66.00 -17.00   0.50   41.53    --    3.94 -38.00-120.00   98
  4  \w    -52.00 -27.00   0.50   41.53    --   -2.69 -78.00 -92.00   50
  5  \w    -11.00  14.00   0.50   41.53    --    3.94 -99.00 150.00   50
  6  \w    -67.00  12.00   0.50   41.53    --    3.94 -38.00  30.00  158
  7  \w    -52.00 -27.00   0.50   41.53    --   -2.69 -78.00 -92.00   50
  8  \w    -56.00 -31.00   0.50   41.53    --   -2.69 -55.00 122.00   50
  9  \w      5.00  30.00   0.50   41.53    --    3.94  78.00  31.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0321280000
_diffrn_orient_matrix_UB_12      0.0090140000
_diffrn_orient_matrix_UB_13      0.0171105000
_diffrn_orient_matrix_UB_21      -0.0190082000
_diffrn_orient_matrix_UB_22      0.0336902000
_diffrn_orient_matrix_UB_23      0.0041889000
_diffrn_orient_matrix_UB_31      -0.0236299000
_diffrn_orient_matrix_UB_32      -0.0148455000
_diffrn_orient_matrix_UB_33      0.0199013000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.869
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            103801
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.869
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.987
_diffrn_reflns_theta_min         2.632
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.646
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27521
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.205
_exptl_crystal_description       needle
_exptl_crystal_F_000             3120
_exptl_crystal_size_max          1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.587
_refine_diff_density_min         -0.622
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.187
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     488
_refine_ls_number_reflns         11104
_refine_ls_number_restraints     352
_refine_ls_restrained_S_all      1.189
_refine_ls_R_factor_all          0.0683
_refine_ls_R_factor_gt           0.0457
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1509
_refine_ls_wR_factor_ref         0.1626
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8322
_reflns_number_total             11104
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09340f2.cif
_cod_data_source_block           C49H59NZn
_cod_database_code               1576520
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'Zn N C44 H50'
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.564
_diffrn_oxdiff_ac3_digest_hkl    41e2730cf24e6fc712178c6b12cfc444685bc0
_diffrn_oxdiff_digest_hkl
;
43ed099d18558a4a43648ce04f1188d4ab232d
;
_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
 C17-C56 \\sim C56-C51 \\sim C51-C53 \\sim C53-C54 \\sim C54-C55 \\sim C55-C17
 with sigma of 0.02
 C17-C54 \\sim C17-C51 \\sim C55-C53 \\sim C56-C55 \\sim C51-C54 \\sim C56-C53
 with sigma of 0.04
 C52-C55 \\sim C52-C56
 with sigma of 0.04
 C52-C17 \\sim C44-C45
 with sigma of 0.02
 C17-C56 \\sim C45-C50
 with sigma of 0.02
 C17-C55 \\sim C45-C46
 with sigma of 0.02
 C56-C51 \\sim C50-C49
 with sigma of 0.02
 C51-C53 \\sim C49-C48
 with sigma of 0.02
 C53-C54 \\sim C48-C47
 with sigma of 0.02
 C54-C55 \\sim C47-C46
 with sigma of 0.02
 C52-C56 \\sim C44-C50
 with sigma of 0.04
 C52-C55 \\sim C44-C46
 with sigma of 0.04
 C17-C51 \\sim C45-C49
 with sigma of 0.04
 C17-C54 \\sim C45-C47
 with sigma of 0.04
 C56-C53 \\sim C50-C48
 with sigma of 0.04
 C56-C55 \\sim C50-C46
 with sigma of 0.04
 C51-C54 \\sim C49-C47
 with sigma of 0.04
 C53-C55 \\sim C48-C46
 with sigma of 0.04
 C38-C39 \\sim C39-C40 \\sim C40-C41 \\sim C41-C42 \\sim C42-C43 \\sim C43-C38
 with sigma of 0.02
 C38-C42 \\sim C38-C40 \\sim C43-C41 \\sim C39-C43 \\sim C40-C42 \\sim C39-C41
 with sigma of 0.04
 C37-C43 \\sim C37-C39
 with sigma of 0.04
3. Restrained planarity
 C52, C17, C56, C51, C53, C54, C55
 with sigma of 0.1
 C37, C38, C39, C40, C41, C42, C43
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C52 \\sim C17 \\sim C56 \\sim C51 \\sim C53 \\sim C54 \\sim C55: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim C43: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C52, C17, C56, C51, C53, C54, C55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37, C38, C39, C40, C41, C42, C43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(C50)=Sof(H50)=Sof(C49)=
 Sof(H49)=Sof(C48)=Sof(H48)=Sof(C47)=Sof(H47)=Sof(C46)=Sof(H46)=1-FVAR(1)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C17)=Sof(C56)=Sof(H56)=Sof(C51)=
 Sof(H51)=Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(H55)=FVAR(1)
7.a Free rotating group:
 C52(C17,C56,C51,C53,C54,C55), C44(C45,C50,C49,C48,C47,C46), C37(C38,C39,C40,
 C41,C42,C43)
7.b Ternary CH refined with riding coordinates:
 C31(H31), C34(H34)
7.c Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C24(H24A,H24B), C20(H20A,H20B), C23(H23A,H23B), C21(H21A,
 H21B), C22(H22A,H22B)
7.d Aromatic/amide H refined with riding coordinates:
 C29(H29), C13(H13), C4(H4), C27(H27), C28(H28), C12(H12), C7(H7), C10(H10),
 C11(H11), C5(H5), C6(H6), C56(H56), C51(H51), C53(H53), C54(H54), C55(H55),
 C50(H50), C49(H49), C48(H48), C47(H47), C46(H46), C39(H39), C40(H40), C41(H41),
  C42(H42), C43(H43)
7.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C35(H35A,H35B,H35C), C33(H33A,H33B,H33C), C19(H19A,H19B,
 H19C), C32(H32A,H32B,H32C), C36(H36A,H36B,H36C), C52(H52A,H52B,H52C), C44(H44A,
 H44B,H44C), C37(H37A,H37B,H37C)
;
_shelx_res_checksum              62848
_olex2_submission_original_sample_id C49H59NZn
_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 1.803
_oxdiff_exptl_absorpt_empirical_full_min 0.413