#------------------------------------------------------------------------------
#$Date: 2025-08-21 00:01:10 +0200 (Thu 21 de Aug de 2025) $
#$Revision: 301838 $
#$URL: svn://www.crystallography.net/cod/cif/4/32/45/4324522.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4324522
loop_
_publ_author_name
'Antonio Otero'
'Juan Fernández-Baeza'
'Juan Tejeda'
'Agustín Lara-Sánchez'
'Sonia Franco'
'Jaime Martínez-Ferrer'
'María P. Carrión'
'I. López-Solera'
'Ana M. Rodríguez'
'Luis F. Sánchez-Barba'
_publ_section_title
;
 Direct Synthesis of NNN-Donor Enantiopure Scorpionate Ligands by an
 Efficient Diastereoselective Nucleophilic Addition to Imines
;
_journal_name_full               'Inorganic Chemistry'
_journal_page_first              1826
_journal_page_last               1839
_journal_paper_doi               10.1021/ic102242x
_journal_volume                  50
_journal_year                    2011
_chemical_absolute_configuration rm
_chemical_formula_sum            'C31 H42 Cl2 Li N5 O'
_chemical_formula_weight         578.54
_space_group_IT_number           78
_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_Hall  'P 4cw'
_symmetry_space_group_name_H-M   'P 43'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.5316(7)
_cell_length_b                   14.5316(7)
_cell_length_c                   15.1786(16)
_cell_measurement_reflns_used    1309
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      18.245
_cell_measurement_theta_min      2.394
_cell_volume                     3205.2(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX'
_computing_data_reduction        'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      180(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'omega and phis scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1152
_diffrn_reflns_av_sigmaI/netI    0.1110
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            23385
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         25.00
_diffrn_reflns_theta_min         1.40
_exptl_absorpt_coefficient_mu    0.234
_exptl_absorpt_correction_T_max  0.9816
_exptl_absorpt_correction_T_min  0.9418
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.199
_exptl_crystal_description       prism
_exptl_crystal_F_000             1232
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.295
_refine_diff_density_min         -0.261
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     367
_refine_ls_number_reflns         5560
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.1178
_refine_ls_R_factor_gt           0.0643
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[σ²(Fo²)+(0.1049P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1596
_refine_ls_wR_factor_ref         0.2066
_reflns_number_gt                3375
_reflns_number_total             5560
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ic102242x_si_002_5.cif
_cod_data_source_block           15
_cod_database_code               4324522
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, z+1/2'
'-y, x, z+3/4'
'y, -x, z+1/4'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
C1 C 0.7486(4) -0.0869(4) 0.1669(4) 0.0415(15) Uani 1 1 d .
C2 C 0.8131(4) -0.0944(4) 0.1013(5) 0.0475(16) Uani 1 1 d .
H7 H 0.8685 -0.1289 0.1038 0.057 Uiso 1 1 calc R
C3 C 0.7822(4) -0.0419(4) 0.0301(4) 0.0437(15) Uani 1 1 d .
C4 C 0.7446(5) -0.1281(5) 0.2560(5) 0.0546(18) Uani 1 1 d .
H10A H 0.7536 -0.0799 0.3003 0.082 Uiso 1 1 calc R
H10B H 0.7931 -0.1745 0.2619 0.082 Uiso 1 1 calc R
H10C H 0.6844 -0.1571 0.2647 0.082 Uiso 1 1 calc R
C5 C 0.8261(5) -0.0247(6) -0.0577(5) 0.069(2) Uani 1 1 d .
H9A H 0.7781 -0.0148 -0.1021 0.103 Uiso 1 1 calc R
H9B H 0.8635 -0.0780 -0.0744 0.103 Uiso 1 1 calc R
H9C H 0.8653 0.0301 -0.0541 0.103 Uiso 1 1 calc R
C6 C 0.6079(4) 0.1499(4) 0.2549(4) 0.0416(15) Uani 1 1 d .
C7 C 0.5947(4) 0.2383(5) 0.2285(5) 0.0502(17) Uani 1 1 d .
H2 H 0.5989 0.2917 0.2643 0.060 Uiso 1 1 calc R
C8 C 0.5739(4) 0.2359(4) 0.1394(5) 0.0458(16) Uani 1 1 d .
C9 C 0.6391(5) 0.1104(5) 0.3410(4) 0.0540(18) Uani 1 1 d .
H5A H 0.5911 0.0700 0.3646 0.081 Uiso 1 1 calc R
H5B H 0.6510 0.1604 0.3828 0.081 Uiso 1 1 calc R
H5C H 0.6957 0.0749 0.3320 0.081 Uiso 1 1 calc R
C10 C 0.5517(5) 0.3140(5) 0.0776(6) 0.064(2) Uani 1 1 d .
H4A H 0.6087 0.3456 0.0608 0.096 Uiso 1 1 calc R
H4B H 0.5104 0.3576 0.1070 0.096 Uiso 1 1 calc R
H4C H 0.5216 0.2897 0.0247 0.096 Uiso 1 1 calc R
C11 C 0.5968(4) -0.0018(4) 0.1738(4) 0.0353(13) Uani 1 1 d .
H11 H 0.5944 -0.0292 0.2342 0.042 Uiso 1 1 calc R
C12 C 0.5131(4) -0.0385(4) 0.1215(4) 0.0308(13) Uani 1 1 d .
H12 H 0.5053 -0.0003 0.0672 0.037 Uiso 1 1 calc R
C13 C 0.5251(4) -0.1381(4) 0.0946(4) 0.0340(13) Uani 1 1 d .
C14 C 0.5273(4) -0.1624(4) 0.0107(4) 0.0393(14) Uani 1 1 d .
H14 H 0.5261 -0.1169 -0.0342 0.047 Uiso 1 1 calc R
C15 C 0.5315(5) -0.2634(4) -0.0133(4) 0.0497(17) Uani 1 1 d .
H15A H 0.5862 -0.2749 -0.0505 0.060 Uiso 1 1 calc R
H15B H 0.4761 -0.2803 -0.0476 0.060 Uiso 1 1 calc R
C16 C 0.5368(4) -0.3229(4) 0.0696(4) 0.0430(15) Uani 1 1 d .
H16 H 0.5431 -0.3905 0.0591 0.052 Uiso 1 1 calc R
C17 C 0.6102(4) -0.2798(4) 0.1317(5) 0.0480(16) Uani 1 1 d .
H17A H 0.6610 -0.2479 0.1008 0.058 Uiso 1 1 calc R
H17B H 0.6336 -0.3221 0.1777 0.058 Uiso 1 1 calc R
C18 C 0.5303(4) -0.2143(4) 0.1635(4) 0.0373(14) Uani 1 1 d .
H24 H 0.5314 -0.1947 0.2267 0.045 Uiso 1 1 calc R
C19 C 0.4615(4) -0.2945(4) 0.1381(5) 0.0415(14) Uani 1 1 d .
C20 C 0.3666(4) -0.2708(5) 0.1070(5) 0.0522(18) Uani 1 1 d .
H20A H 0.3361 -0.3265 0.0851 0.078 Uiso 1 1 calc R
H20B H 0.3705 -0.2253 0.0595 0.078 Uiso 1 1 calc R
H20C H 0.3310 -0.2452 0.1560 0.078 Uiso 1 1 calc R
C21 C 0.4536(5) -0.3656(5) 0.2114(5) 0.063(2) Uani 1 1 d .
H21A H 0.4123 -0.3424 0.2574 0.095 Uiso 1 1 calc R
H21B H 0.5146 -0.3771 0.2367 0.095 Uiso 1 1 calc R
H21C H 0.4288 -0.4231 0.1874 0.095 Uiso 1 1 calc R
C22 C 0.3444(4) -0.0270(4) 0.1469(4) 0.0322(13) Uani 1 1 d .
C23 C 0.3203(4) -0.0080(4) 0.0601(4) 0.0391(14) Uani 1 1 d .
H23 H 0.3669 0.0059 0.0183 0.047 Uiso 1 1 calc R
C24 C 0.2295(4) -0.0090(4) 0.0341(4) 0.0403(15) Uani 1 1 d .
H24A H 0.2134 0.0041 -0.0253 0.048 Uiso 1 1 calc R
C25 C 0.1624(4) -0.0291(4) 0.0951(4) 0.0400(15) Uani 1 1 d .
C26 C 0.1848(4) -0.0484(4) 0.1806(4) 0.0423(15) Uani 1 1 d .
H26 H 0.1379 -0.0624 0.2220 0.051 Uiso 1 1 calc R
C27 C 0.2753(4) -0.0476(4) 0.2065(4) 0.0423(15) Uani 1 1 d .
H27 H 0.2906 -0.0612 0.2659 0.051 Uiso 1 1 calc R
C28 C 0.7911(6) 0.2229(6) 0.0232(6) 0.084(3) Uani 1 1 d .
H28A H 0.8493 0.1880 0.0170 0.100 Uiso 1 1 calc R
H28B H 0.7682 0.2155 0.0842 0.100 Uiso 1 1 calc R
C29 C 0.8059(6) 0.3224(6) 0.0023(8) 0.089(3) Uani 1 1 d .
H29A H 0.7709 0.3622 0.0433 0.107 Uiso 1 1 calc R
H29B H 0.8720 0.3386 0.0058 0.107 Uiso 1 1 calc R
C30 C 0.7718(7) 0.3317(6) -0.0874(8) 0.093(3) Uani 1 1 d .
H30A H 0.7203 0.3763 -0.0891 0.111 Uiso 1 1 calc R
H30B H 0.8214 0.3545 -0.1264 0.111 Uiso 1 1 calc R
C31 C 0.7404(8) 0.2421(6) -0.1174(6) 0.094(3) Uani 1 1 d .
H31A H 0.6831 0.2480 -0.1523 0.112 Uiso 1 1 calc R
H31B H 0.7879 0.2119 -0.1541 0.112 Uiso 1 1 calc R
N1 N 0.7021(3) -0.0013(4) 0.0495(3) 0.0427(13) Uani 1 1 d .
N2 N 0.6833(3) -0.0295(3) 0.1333(3) 0.0352(11) Uani 1 1 d .
N3 N 0.5731(3) 0.1496(3) 0.1100(3) 0.0408(12) Uani 1 1 d .
N4 N 0.5930(3) 0.0975(3) 0.1830(3) 0.0378(12) Uani 1 1 d .
N5 N 0.4345(3) -0.0239(3) 0.1784(3) 0.0370(12) Uani 1 1 d .
H5 H 0.4439 -0.0127 0.2347 0.044 Uiso 1 1 calc R
O1 O 0.7241(3) 0.1907(3) -0.0387(3) 0.0636(14) Uani 1 1 d .
Cl1 Cl 0.52043(12) 0.08555(12) -0.11774(11) 0.0535(5) Uani 1 1 d .
Cl2 Cl 0.04668(10) -0.03320(12) 0.06199(12) 0.0509(4) Uani 1 1 d .
Li1 Li 0.6259(7) 0.1041(7) -0.0103(7) 0.046(3) Uani 1 1 d .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Li Li -0.0003 0.0001 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
N2 C1 C2 104.6(5)
N2 C1 C4 124.2(6)
C2 C1 C4 131.2(6)
C1 C2 C3 107.4(5)
N1 C3 C2 110.5(6)
N1 C3 C5 119.5(6)
C2 C3 C5 130.0(6)
N4 C6 C7 105.8(6)
N4 C6 C9 122.6(6)
C7 C6 C9 131.5(6)
C6 C7 C8 107.1(6)
N3 C8 C7 110.7(6)
N3 C8 C10 119.9(6)
C7 C8 C10 129.4(6)
N4 C11 N2 110.3(4)
N4 C11 C12 111.2(4)
N2 C11 C12 111.5(4)
N5 C12 C13 113.1(4)
N5 C12 C11 105.2(4)
C13 C12 C11 112.1(4)
C14 C13 C12 121.2(5)
C14 C13 C18 117.8(5)
C12 C13 C18 121.0(5)
C13 C14 C15 119.4(6)
C14 C15 C16 110.7(5)
C15 C16 C17 107.8(5)
C15 C16 C19 111.2(5)
C17 C16 C19 88.3(5)
C16 C17 C18 85.6(4)
C13 C18 C17 105.3(5)
C13 C18 C19 109.6(5)
C17 C18 C19 86.9(4)
C20 C19 C21 108.5(5)
C20 C19 C16 119.7(6)
C21 C19 C16 111.1(5)
C20 C19 C18 119.3(5)
C21 C19 C18 111.6(6)
C16 C19 C18 85.1(4)
C27 C22 C23 118.6(5)
C27 C22 N5 117.7(5)
C23 C22 N5 123.7(5)
C24 C23 C22 120.7(6)
C25 C24 C23 119.2(6)
C26 C25 C24 120.9(5)
C26 C25 Cl2 119.5(5)
C24 C25 Cl2 119.6(5)
C25 C26 C27 119.9(6)
C26 C27 C22 120.7(6)
O1 C28 C29 105.9(7)
C30 C29 C28 103.8(7)
C31 C30 C29 108.5(8)
O1 C31 C30 105.0(8)
C3 N1 N2 104.3(5)
C3 N1 Li1 133.3(5)
N2 N1 Li1 121.2(5)
C1 N2 N1 113.2(5)
C1 N2 C11 127.7(5)
N1 N2 C11 118.9(4)
C8 N3 N4 104.3(5)
C8 N3 Li1 126.0(5)
N4 N3 Li1 117.0(5)
C6 N4 N3 112.0(5)
C6 N4 C11 129.3(5)
N3 N4 C11 118.7(5)
C22 N5 C12 122.1(5)
C31 O1 C28 105.5(6)
C31 O1 Li1 130.0(6)
C28 O1 Li1 124.3(5)
O1 Li1 N3 104.9(5)
O1 Li1 N1 100.4(5)
N3 Li1 N1 92.7(5)
O1 Li1 Cl1 114.5(5)
N3 Li1 Cl1 114.9(5)
N1 Li1 Cl1 125.8(5)
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
C1 N2 1.363(7)
C1 C2 1.372(9)
C1 C4 1.480(9)
C2 C3 1.397(9)
C3 N1 1.338(7)
C3 C5 1.499(10)
C6 N4 1.349(7)
C6 C7 1.360(9)
C6 C9 1.498(9)
C7 C8 1.385(9)
C8 N3 1.331(7)
C8 C10 1.508(10)
C11 N4 1.450(7)
C11 N2 1.456(7)
C11 C12 1.547(8)
C12 N5 1.448(7)
C12 C13 1.514(8)
C13 C14 1.322(9)
C13 C18 1.525(8)
C14 C15 1.513(8)
C15 C16 1.529(9)
C16 C17 1.555(9)
C16 C19 1.565(8)
C17 C18 1.577(8)
C18 C19 1.584(8)
C19 C20 1.497(9)
C19 C21 1.524(9)
C22 C27 1.384(8)
C22 C23 1.391(8)
C22 N5 1.395(7)
C23 C24 1.377(8)
C24 C25 1.376(8)
C25 C26 1.368(9)
C25 Cl2 1.756(6)
C26 C27 1.372(8)
C28 O1 1.431(9)
C28 C29 1.496(12)
C29 C30 1.456(14)
C30 C31 1.452(12)
C31 O1 1.428(9)
N1 N2 1.364(7)
N1 Li1 2.096(12)
N3 N4 1.372(7)
N3 Li1 2.088(12)
O1 Li1 1.952(11)
Cl1 Li1 2.254(11)
loop_
_cod_related_entry_id
_cod_related_entry_database
_cod_related_entry_code
1 PubChem 139135467
