# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_agr2977
_database_code_depnum_ccdc_archive 'CCDC 2095751'
loop_
_audit_author_name
_audit_author_address
'Raul Garcia-Rodriguez'
;University of Valladolid
Spain
;
_audit_update_record             
;
2021-07-11 deposited with the CCDC.	2021-08-16 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT241_agr2977             
;
PROBLEM: High   'MainMol' Ueq as Compared to Neighbors of        C3S Check
RESPONSE: The alert is related to an incipient disorder affecting the molecule of THF and leading to some atoms with a prolate ellipsoid.
;
_vrf_PLAT242_agr2977             
;
PROBLEM: Low    'MainMol' Ueq as Compared to Neighbors of        O1S Check
RESPONSE: The alert is related to an incipient disorder affecting the molecule of THF and leading to some atoms with a prolate ellipsoid.
;
_vrf_PLAT242_agr2977_2           
;
PROBLEM: Low    'MainMol' Ueq as Compared to Neighbors of         C1 Check
RESPONSE: This is triggered by the fact that C1 is bonded to atoms C2 and C3, which are two components of the terminal methyl group in a disordered ethyl chain and have significantly stretched (prolate) displacement ellipsoids; it is C2 and C3 that warrant the warning. This anisotropic refinement was preferred over the alternative of two isotropic atoms for the disordered methyl group.
;
_audit_creation_method           
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_formula_moiety         'C21 H25 Al Li N3 O'
_chemical_formula_sum            'C21 H25 Al Li N3 O'
_chemical_formula_weight         369.36
_exptl_crystal_recrystallization_method THF/toluene
_chemical_melting_point          ?
_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_diffrn_ambient_temperature      220.0(4)
_chemical_oxdiff_formula         'C21 H25 Al Li N3 O'
_chemical_oxdiff_usercomment     'white block'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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'
Al Al 0.2130 0.2455 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Li Li 0.0008 0.0003 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
_chemical_absolute_configuration ?
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   10.0339(8)
_cell_length_b                   10.0431(6)
_cell_length_c                   15.9941(12)
_cell_angle_alpha                81.015(6)
_cell_angle_beta                 76.374(7)
_cell_angle_gamma                60.358(7)
_cell_volume                     1359.90(19)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    2865
_cell_measurement_temperature    220.0(4)
_cell_measurement_theta_max      74.1030
_cell_measurement_theta_min      5.0490
_shelx_estimated_absorpt_T_max   0.904
_shelx_estimated_absorpt_T_min   0.728
_exptl_absorpt_coefficient_mu    0.728
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.387
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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_absorpt_special_details   ?
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.902
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             392
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-6 0 -3 0.1364
6 0 3 0.1364
-2 -5 5 0.1836
2 5 -5 0.1836
0 -1 -10 0.0704
0 1 10 0.0704
-2 4 -3 0.1687
1 -5 4 0.1431
-2 -2 -10 0.0633
4 3 10 0.1115

_exptl_crystal_size_max          0.466
_exptl_crystal_size_mid          0.273
_exptl_crystal_size_min          0.141
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-6.0030 0.0001 -2.9971 -0.9839 0.3631 0.1853
6.0030 -0.0001 2.9971 0.9839 -0.3631 -0.1853
-2.0043 -5.0037 4.9895 0.3038 -0.0559 0.9296
2.0043 5.0037 -4.9895 -0.3038 0.0559 -0.9296
-0.0036 -1.0038 -10.0006 -0.3865 -0.8174 -0.4261
0.0036 1.0038 10.0006 0.3865 0.8174 0.4261
-1.9977 4.0038 -2.9903 -0.7052 0.4581 -0.4826
0.9966 -5.0045 3.9884 0.6813 -0.4120 0.7031
-2.0053 -2.0046 -10.0019 -0.5972 -0.7458 -0.2015
4.0070 3.0054 10.0032 0.8080 0.6741 -0.0231

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0224
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            8565
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.596
_diffrn_reflns_theta_max         66.596
_diffrn_reflns_theta_min         5.073
_diffrn_ambient_environment      N~2~
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4757
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -64.00  33.00   1.00    5.24    --  -41.06  37.00-150.00   97
  2  ω   -107.00 -17.00   1.00    5.24    --  -41.06 -37.00  30.00   90
  3  ω    -64.00  -8.00   1.00    5.24    --  -41.06  77.00 -60.00   56
  4  ω      1.00  29.00   1.00    5.24    --  -41.06  77.00 -60.00   28
  5  ω     97.00 130.00   1.00    5.24    --   41.06 178.00-180.00   33
  6  ω     56.00  85.00   1.00    5.24    --   41.06-178.00  60.00   29
  7  ω     91.00 121.00   1.00    5.24    --   41.06 178.00 -90.00   30
  8  ω     97.00 175.00   1.00   20.97    --  110.01  30.00 -30.00   78
  9  ω    129.00 166.00   1.00   20.97    --  110.01  30.00   0.00   37
 10  ω     49.00 138.00   1.00   20.97    --  110.01 -30.00 150.00   89
 11  ω     85.00 110.00   1.00   20.97    --  110.01 -94.00  30.00   25
 12  ω     41.00 137.00   1.00   20.97    --  110.01 -61.00-120.00   96
 13  ω     30.00  55.00   1.00   20.97    --  110.01 -94.00  30.00   25
 14  ω     85.00 152.00   1.00   20.97    --  110.01  77.00  30.00   67
 15  ω     84.00 116.00   1.00   20.97    --  110.01-125.00 -30.00   32
 16  ω     50.00 138.00   1.00   20.97    --  110.01 -30.00   0.00   88
 17  ω     47.00  99.00   1.00   20.97    --  110.01 -94.00 120.00   52
 18  ω     27.00  89.00   1.00   20.97    --  110.01 -94.00-150.00   62
 19  ω    125.00 152.00   1.00   20.97    --  110.01 125.00 -90.00   27
 20  ω     90.00 118.00   1.00   20.97    --  110.01-125.00-180.00   28
 21  ω     85.00 135.00   1.00   20.97    --  110.01 -77.00 -60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1410485000
_diffrn_orient_matrix_UB_12      -0.0715721000
_diffrn_orient_matrix_UB_13      0.0457784000
_diffrn_orient_matrix_UB_21      -0.0953472000
_diffrn_orient_matrix_UB_22      0.1189903000
_diffrn_orient_matrix_UB_23      0.0698300000
_diffrn_orient_matrix_UB_31      -0.0576200000
_diffrn_orient_matrix_UB_32      -0.1092577000
_diffrn_orient_matrix_UB_33      0.0535968000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3543
_reflns_number_total             4778
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_refine_diff_density_max         0.457
_refine_diff_density_min         -0.303
_refine_diff_density_rms         0.051
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         4778
_refine_ls_number_restraints     44
_refine_ls_R_factor_all          0.0847
_refine_ls_R_factor_gt           0.0709
_refine_ls_restrained_S_all      1.071
_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/[σ²(Fo²)+(0.1679P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2208
_refine_ls_wR_factor_ref         0.2392
_refine_special_details          SQUEEZE
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 C1, C2, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08 within 2A
O1S \\sim C3S \\sim C2S \\sim C5S \\sim C4S: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
4. Others
 Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=1-FVAR(1)
 Sof(H1BC)=Sof(H1BD)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1(H1BC,H1BD), C5S(H5SA,H5SB), C4S(H4SA,H4SB), C2S(H2SA,H2SB),
 C3S(H3SA,H3SB)
5.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C22(H22), C23(H23), C24(H24),
 C25(H25), C32(H32), C33(H33), C34(H34), C35(H35)
5.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Al1 Al 0.52136(8) 0.66893(7) 0.21302(5) 0.0662(3) Uani 1 1 d . . . . .
O1S O 0.8250(3) -0.0055(3) 0.33009(17) 0.1067(8) Uani 1 1 d . U . . .
N1 N 0.8661(3) 0.8179(2) 0.16525(18) 0.0749(6) Uani 1 1 d . . . . .
N2 N 0.0709(2) 0.9968(2) 0.15969(17) 0.0743(6) Uani 1 1 d . . . . .
N3 N 0.6872(3) 0.2000(2) 0.16470(17) 0.0760(6) Uani 1 1 d . . . . .
C1 C 0.4707(5) 0.6718(5) 0.3404(2) 0.1088(11) Uani 1 1 d . U . . .
H1A H 0.568294 0.603933 0.361452 0.131 Uiso 0.298(11) 1 calc R U P A -2
H1B H 0.437997 0.775857 0.355483 0.131 Uiso 0.298(11) 1 calc R U P A -2
H1BC H 0.437949 0.775575 0.355997 0.131 Uiso 0.702(11) 1 calc R U P A -1
H1BD H 0.379904 0.654607 0.359495 0.131 Uiso 0.702(11) 1 calc R U P A -1
C11 C 0.7224(3) 0.6781(3) 0.16965(18) 0.0665(6) Uani 1 1 d . . . . .
C12 C 0.7382(3) 0.7990(3) 0.18798(19) 0.0700(7) Uani 1 1 d . . . . .
H12 H 0.649841 0.876829 0.219896 0.084 Uiso 1 1 calc R U . . .
C5S C 0.6879(10) 0.0085(15) 0.3842(5) 0.240(4) Uani 1 1 d . U . . .
H5SA H 0.599276 0.080039 0.356337 0.288 Uiso 1 1 calc R U . . .
H5SB H 0.690822 -0.091541 0.391368 0.288 Uiso 1 1 calc R U . . .
C13 C 0.9900(3) 0.7084(3) 0.1192(2) 0.0830(8) Uani 1 1 d . . . . .
H13 H 1.081065 0.718170 0.101161 0.100 Uiso 1 1 calc R U . . .
C4S C 0.6640(12) 0.0580(19) 0.4624(6) 0.307(6) Uani 1 1 d . U . . .
H4SA H 0.639138 -0.008067 0.507924 0.368 Uiso 1 1 calc R U . . .
H4SB H 0.578702 0.163503 0.468282 0.368 Uiso 1 1 calc R U . . .
C14 C 0.9905(3) 0.5827(4) 0.0970(3) 0.0956(10) Uani 1 1 d . . . . .
H14 H 1.081120 0.506518 0.065416 0.115 Uiso 1 1 calc R U . . .
C15 C 0.8572(3) 0.5679(3) 0.1211(2) 0.0843(8) Uani 1 1 d . . . . .
H15 H 0.857005 0.482188 0.104705 0.101 Uiso 1 1 calc R U . . .
C2S C 0.8975(10) 0.0166(15) 0.3857(5) 0.234(4) Uani 1 1 d . U . . .
H2SA H 0.996970 -0.076301 0.389605 0.281 Uiso 1 1 calc R U . . .
H2SB H 0.920299 0.100846 0.362396 0.281 Uiso 1 1 calc R U . . .
C3S C 0.8094(13) 0.050(2) 0.4661(6) 0.326(7) Uani 1 1 d . U . . .
H3SA H 0.792087 0.147731 0.482635 0.391 Uiso 1 1 calc R U . . .
H3SB H 0.861709 -0.030715 0.508283 0.391 Uiso 1 1 calc R U . . .
C21 C 0.3499(3) 0.8517(3) 0.16229(18) 0.0652(6) Uani 1 1 d . . . . .
C22 C 0.1966(3) 0.8813(3) 0.1884(2) 0.0714(7) Uani 1 1 d . . . . .
H22 H 0.178306 0.813152 0.230815 0.086 Uiso 1 1 calc R U . . .
C23 C 0.0967(3) 1.0944(3) 0.1000(2) 0.0766(7) Uani 1 1 d . . . . .
H23 H 0.011397 1.176421 0.078415 0.092 Uiso 1 1 calc R U . . .
C24 C 0.2429(3) 1.0799(3) 0.0690(2) 0.0808(8) Uani 1 1 d . . . . .
H24 H 0.257212 1.150990 0.027250 0.097 Uiso 1 1 calc R U . . .
C25 C 0.3679(3) 0.9593(3) 0.1001(2) 0.0755(7) Uani 1 1 d . . . . .
H25 H 0.468207 0.948765 0.078971 0.091 Uiso 1 1 calc R U . . .
C31 C 0.5459(3) 0.4797(3) 0.16921(18) 0.0665(6) Uani 1 1 d . . . . .
C32 C 0.6585(3) 0.3331(3) 0.1912(2) 0.0710(7) Uani 1 1 d . . . . .
H32 H 0.720949 0.327366 0.228633 0.085 Uiso 1 1 calc R U . . .
C33 C 0.5986(4) 0.2083(3) 0.1113(2) 0.0874(9) Uani 1 1 d . . . . .
H33 H 0.616880 0.116862 0.090850 0.105 Uiso 1 1 calc R U . . .
C34 C 0.4834(5) 0.3432(4) 0.0853(3) 0.0987(11) Uani 1 1 d . . . . .
H34 H 0.422134 0.344748 0.048471 0.118 Uiso 1 1 calc R U . . .
C35 C 0.4579(4) 0.4782(3) 0.1141(2) 0.0852(8) Uani 1 1 d . . . . .
H35 H 0.378903 0.571876 0.095890 0.102 Uiso 1 1 calc R U . . .
Li1 Li 0.8616(5) 0.0032(4) 0.2052(3) 0.0706(10) Uani 1 1 d . . . . .
C2 C 0.350(3) 0.628(4) 0.3919(12) 0.200(12) Uani 0.298(11) 1 d . U P A -2
H2A H 0.400757 0.520360 0.409926 0.300 Uiso 0.298(11) 1 calc R U P A -2
H2B H 0.275454 0.646554 0.356495 0.300 Uiso 0.298(11) 1 calc R U P A -2
H2C H 0.295678 0.689467 0.442222 0.300 Uiso 0.298(11) 1 calc R U P A -2
C3 C 0.5848(15) 0.5686(15) 0.3886(6) 0.218(7) Uani 0.702(11) 1 d . U P A -1
H3A H 0.597105 0.466605 0.388211 0.328 Uiso 0.702(11) 1 calc R U P A -1
H3B H 0.552877 0.600428 0.447403 0.328 Uiso 0.702(11) 1 calc R U P A -1
H3C H 0.683215 0.567478 0.363366 0.328 Uiso 0.702(11) 1 calc R U P A -1


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Al1 C1 1.982(4) . ?
Al1 C11 2.015(3) . ?
Al1 C21 2.014(3) . ?
Al1 C31 2.009(3) . ?
O1S C5S 1.395(7) . ?
O1S C2S 1.377(8) . ?
O1S Li1 1.941(6) . ?
N1 C12 1.347(4) . ?
N1 C13 1.329(4) . ?
N1 Li1 2.036(5) 1_565 ?
N2 C22 1.344(4) . ?
N2 C23 1.334(4) . ?
N2 Li1 2.026(5) 1_465 ?
N3 C32 1.338(3) . ?
N3 C33 1.337(4) . ?
N3 Li1 2.026(5) . ?
C1 H1A 0.9800 . ?
C1 H1B 0.9800 . ?
C1 H1BC 0.9800 . ?
C1 H1BD 0.9800 . ?
C1 C2 1.51(2) . ?
C1 C3 1.404(11) . ?
C11 C12 1.382(3) . ?
C11 C15 1.396(4) . ?
C12 H12 0.9400 . ?
C5S H5SA 0.9800 . ?
C5S H5SB 0.9800 . ?
C5S C4S 1.343(11) . ?
C13 H13 0.9400 . ?
C13 C14 1.361(4) . ?
C4S H4SA 0.9800 . ?
C4S H4SB 0.9800 . ?
C4S C3S 1.435(13) . ?
C14 H14 0.9400 . ?
C14 C15 1.376(4) . ?
C15 H15 0.9400 . ?
C2S H2SA 0.9800 . ?
C2S H2SB 0.9800 . ?
C2S C3S 1.360(11) . ?
C3S H3SA 0.9800 . ?
C3S H3SB 0.9800 . ?
C21 C22 1.383(4) . ?
C21 C25 1.401(4) . ?
C22 H22 0.9400 . ?
C23 H23 0.9400 . ?
C23 C24 1.374(4) . ?
C24 H24 0.9400 . ?
C24 C25 1.375(4) . ?
C25 H25 0.9400 . ?
C31 C32 1.395(3) . ?
C31 C35 1.393(4) . ?
C32 H32 0.9400 . ?
C33 H33 0.9400 . ?
C33 C34 1.359(5) . ?
C34 H34 0.9400 . ?
C34 C35 1.383(4) . ?
C35 H35 0.9400 . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?
C2 H2C 0.9700 . ?
C3 H3A 0.9700 . ?
C3 H3B 0.9700 . ?
C3 H3C 0.9700 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 Al1 C11 109.81(17) . . ?
C1 Al1 C21 109.93(15) . . ?
C1 Al1 C31 112.63(16) . . ?
C21 Al1 C11 108.67(10) . . ?
C31 Al1 C11 108.05(10) . . ?
C31 Al1 C21 107.64(11) . . ?
C5S O1S Li1 125.4(4) . . ?
C2S O1S C5S 101.7(5) . . ?
C2S O1S Li1 130.7(4) . . ?
C12 N1 Li1 119.5(2) . 1_565 ?
C13 N1 C12 116.0(2) . . ?
C13 N1 Li1 124.5(2) . 1_565 ?
C22 N2 Li1 118.1(2) . 1_465 ?
C23 N2 C22 116.4(2) . . ?
C23 N2 Li1 125.4(2) . 1_465 ?
C32 N3 Li1 118.6(2) . . ?
C33 N3 C32 116.5(2) . . ?
C33 N3 Li1 124.8(2) . . ?
Al1 C1 H1A 107.0 . . ?
Al1 C1 H1B 107.0 . . ?
Al1 C1 H1BC 107.5 . . ?
Al1 C1 H1BD 107.5 . . ?
H1A C1 H1B 106.7 . . ?
H1BC C1 H1BD 107.0 . . ?
C2 C1 Al1 121.3(10) . . ?
C2 C1 H1A 107.0 . . ?
C2 C1 H1B 107.0 . . ?
C3 C1 Al1 119.4(5) . . ?
C3 C1 H1BC 107.5 . . ?
C3 C1 H1BD 107.5 . . ?
C12 C11 Al1 120.99(19) . . ?
C12 C11 C15 113.3(2) . . ?
C15 C11 Al1 125.71(19) . . ?
N1 C12 C11 127.3(2) . . ?
N1 C12 H12 116.3 . . ?
C11 C12 H12 116.3 . . ?
O1S C5S H5SA 108.7 . . ?
O1S C5S H5SB 108.7 . . ?
H5SA C5S H5SB 107.6 . . ?
C4S C5S O1S 114.2(7) . . ?
C4S C5S H5SA 108.7 . . ?
C4S C5S H5SB 108.7 . . ?
N1 C13 H13 118.6 . . ?
N1 C13 C14 122.7(3) . . ?
C14 C13 H13 118.6 . . ?
C5S C4S H4SA 111.0 . . ?
C5S C4S H4SB 111.0 . . ?
C5S C4S C3S 104.0(8) . . ?
H4SA C4S H4SB 109.0 . . ?
C3S C4S H4SA 111.0 . . ?
C3S C4S H4SB 111.0 . . ?
C13 C14 H14 120.2 . . ?
C13 C14 C15 119.5(3) . . ?
C15 C14 H14 120.2 . . ?
C11 C15 H15 119.4 . . ?
C14 C15 C11 121.2(3) . . ?
C14 C15 H15 119.4 . . ?
O1S C2S H2SA 109.1 . . ?
O1S C2S H2SB 109.1 . . ?
H2SA C2S H2SB 107.8 . . ?
C3S C2S O1S 112.7(8) . . ?
C3S C2S H2SA 109.1 . . ?
C3S C2S H2SB 109.1 . . ?
C4S C3S H3SA 110.5 . . ?
C4S C3S H3SB 110.5 . . ?
C2S C3S C4S 106.3(8) . . ?
C2S C3S H3SA 110.5 . . ?
C2S C3S H3SB 110.5 . . ?
H3SA C3S H3SB 108.7 . . ?
C22 C21 Al1 120.44(19) . . ?
C22 C21 C25 113.2(2) . . ?
C25 C21 Al1 126.34(19) . . ?
N2 C22 C21 127.2(2) . . ?
N2 C22 H22 116.4 . . ?
C21 C22 H22 116.4 . . ?
N2 C23 H23 118.7 . . ?
N2 C23 C24 122.6(3) . . ?
C24 C23 H23 118.7 . . ?
C23 C24 H24 120.6 . . ?
C23 C24 C25 118.7(3) . . ?
C25 C24 H24 120.6 . . ?
C21 C25 H25 119.1 . . ?
C24 C25 C21 121.8(2) . . ?
C24 C25 H25 119.1 . . ?
C32 C31 Al1 121.8(2) . . ?
C35 C31 Al1 125.22(19) . . ?
C35 C31 C32 113.0(2) . . ?
N3 C32 C31 126.9(3) . . ?
N3 C32 H32 116.5 . . ?
C31 C32 H32 116.5 . . ?
N3 C33 H33 118.6 . . ?
N3 C33 C34 122.9(3) . . ?
C34 C33 H33 118.6 . . ?
C33 C34 H34 120.6 . . ?
C33 C34 C35 118.7(3) . . ?
C35 C34 H34 120.6 . . ?
C31 C35 H35 119.0 . . ?
C34 C35 C31 122.0(3) . . ?
C34 C35 H35 119.0 . . ?
O1S Li1 N1 109.0(2) . 1_545 ?
O1S Li1 N2 108.7(2) . 1_645 ?
O1S Li1 N3 108.5(2) . . ?
N2 Li1 N1 109.3(2) 1_645 1_545 ?
N2 Li1 N3 110.9(2) 1_645 . ?
N3 Li1 N1 110.5(2) . 1_545 ?
C1 C2 H2A 109.5 . . ?
C1 C2 H2B 109.5 . . ?
C1 C2 H2C 109.5 . . ?
H2A C2 H2B 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
C1 C3 H3A 109.5 . . ?
C1 C3 H3B 109.5 . . ?
C1 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Al1 C11 C12 N1 178.1(2) . . . . ?
Al1 C11 C15 C14 -177.9(3) . . . . ?
Al1 C21 C22 N2 -179.1(2) . . . . ?
Al1 C21 C25 C24 179.5(2) . . . . ?
Al1 C31 C32 N3 -178.7(2) . . . . ?
Al1 C31 C35 C34 178.8(3) . . . . ?
O1S C5S C4S C3S -10.9(19) . . . . ?
O1S C2S C3S C4S -3.1(19) . . . . ?
N1 C13 C14 C15 1.4(6) . . . . ?
N2 C23 C24 C25 0.5(5) . . . . ?
N3 C33 C34 C35 1.1(6) . . . . ?
C12 N1 C13 C14 -1.1(5) . . . . ?
C12 C11 C15 C14 1.1(5) . . . . ?
C5S O1S C2S C3S -3.1(14) . . . . ?
C5S C4S C3S C2S 8(2) . . . . ?
C13 N1 C12 C11 0.9(5) . . . . ?
C13 C14 C15 C11 -1.4(6) . . . . ?
C15 C11 C12 N1 -0.8(5) . . . . ?
C2S O1S C5S C4S 9.0(14) . . . . ?
C22 N2 C23 C24 -0.2(5) . . . . ?
C22 C21 C25 C24 -0.6(4) . . . . ?
C23 N2 C22 C21 -0.6(5) . . . . ?
C23 C24 C25 C21 -0.1(5) . . . . ?
C25 C21 C22 N2 1.0(4) . . . . ?
C32 N3 C33 C34 -0.9(5) . . . . ?
C32 C31 C35 C34 -0.2(5) . . . . ?
C33 N3 C32 C31 0.2(5) . . . . ?
C33 C34 C35 C31 -0.5(6) . . . . ?
C35 C31 C32 N3 0.4(4) . . . . ?
Li1 O1S C5S C4S -155.3(10) . . . . ?
Li1 O1S C2S C3S 160.1(10) . . . . ?
Li1 N1 C12 C11 -177.3(3) 1_565 . . . ?
Li1 N1 C13 C14 177.0(3) 1_565 . . . ?
Li1 N2 C22 C21 176.4(3) 1_465 . . . ?
Li1 N2 C23 C24 -177.0(3) 1_465 . . . ?
Li1 N3 C32 C31 178.8(3) . . . . ?
Li1 N3 C33 C34 -179.5(3) . . . . ?

_smtbx_masks_special_details     
;
A solvent mask was calculated and 86 electrons were found in a volume of 376 cubic angstroms in 1 void per unit cell. 
The crystallization solvent was THF/toluene and this is consistent with the presence of 2THF per Unit Cell which account for 80 electrons per unit cell and is also consistent with the NMR data.
;
loop_
_smtbx_masks_void_nr
_smtbx_masks_void_average_x
_smtbx_masks_void_average_y
_smtbx_masks_void_average_z
_smtbx_masks_void_volume
_smtbx_masks_void_count_electrons
_smtbx_masks_void_content
1 0.000 0.500 0.500 375.7 86.2 '2 THF'

_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 1.669
_oxdiff_exptl_absorpt_empirical_full_min 0.729
