# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 2020

####################################################################### 
# 
# 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_lw-2-105-sq
_database_code_depnum_ccdc_archive 'CCDC 1847461'
loop_
_audit_author_name
_audit_author_address
'Retailleau Pascal' 'Institut de Chimie des Substances Naturelles-CNRS-UPR2301'
_audit_update_record             
;
2018-06-05 deposited with the CCDC.	2020-02-11 downloaded from the CCDC.
;

_vrf_CHEMW03_ALERT_2_A           
;
PROBLEM: The ratio of given/expected molecular weight as calculated from the _atom_site* data lies outside...
RESPONSE: SQUEEZE used to remove disordered solvent molecule, but the reported formula includes the solvent. See _refine_special_details.
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2018/1
_shelx_SHELXL_version_number     2018/1
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C11 H15 N O3, 0.36 [C6 H14]'
_chemical_formula_sum            'C13.16 H20.04 N O3'
_chemical_formula_weight         240.26

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'
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'

_space_group_crystal_system      hexagonal
_space_group_IT_number           169
_space_group_name_H-M_alt        'P 61'
_space_group_name_Hall           'P 61'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'x-y, x, z+1/6'
'-y, x-y, z+1/3'
'-x, -y, z+1/2'
'-x+y, -x, z+2/3'
'y, -x+y, z+5/6'

_cell_length_a                   14.9300(18)
_cell_length_b                   14.9300(18)
_cell_length_c                   9.2555(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1786.7(5)
_cell_formula_units_Z            6
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    818
_cell_measurement_theta_min      6.8
_cell_measurement_theta_max      69.0

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.340
_exptl_crystal_F_000             780
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.14
_exptl_absorpt_coefficient_mu    0.766
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.688
_exptl_absorpt_process_details   'Reqab (Higashi-Rigaku, 1998)'
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     1.54187
_diffrn_radiation_type           CuK\a
_diffrn_source                   'Rigaku mm007HF rotating Anode'
_diffrn_radiation_monochromator  'OSMIC CMF Confocal'
_diffrn_measurement_specimen_support Fiber
_diffrn_detector                 'Rigaku Rapid2 IP'
_diffrn_measurement_device       
;
Crystal Goniometer chi partial
;
_diffrn_measurement_device_type  
;
Rigaku Spider Rapid 2
;
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measurement_method       'profile data from ω-scans'
_diffrn_reflns_number            13001
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_av_R_equivalents  0.0375
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         7.624
_diffrn_reflns_theta_max         71.931
_diffrn_reflns_theta_full        67.687
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measured_fraction_theta_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_point_group_measured_fraction_full 0.979
_reflns_number_total             2266
_reflns_number_gt                1477
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.839
_reflns_Friedel_fraction_max     0.944
_reflns_Friedel_fraction_full    0.968

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
# SQUEEZE RESULTS
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material
loop_
  _platon_squeeze_void_nr
  _platon_squeeze_void_average_x
  _platon_squeeze_void_average_y
  _platon_squeeze_void_average_z
  _platon_squeeze_void_volume
  _platon_squeeze_void_count_electrons
  _platon_squeeze_void_content
   1  0.000 -0.000 -0.018       207        18 ' '
_platon_squeeze_void_probe_radius                  1.20
_platon_squeeze_details
)
TITL shelx in P61 #169
CELL   14.9300   14.9300    9.2555     90.00     90.00    120.00
SPGR P61
# Solvent Accessible Volume =     210.6
# Electrons Found in S.A.V. =      17.9
# Note: Atoms in Void as Cxxx and Qxxx all others
C101 0.992 1.000 0.723 !       1.07 eA-3
)

 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.
;

_computing_data_collection       
;
CrystalClear-SM Expert 2.0 r16 (Rigaku, 2014)
;
_computing_cell_refinement       
;
CrystalClear-SM Expert 2.0 r16 (Rigaku, 2014)
;
_computing_data_reduction        
;
CrystalClear-SM Expert 2.0 r16 (Rigaku, 2014)
;

_computing_structure_solution    'SHELXT Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2018/1 (Sheldrick, 2015)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          SQUEEZE
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0671P)²+0.0050P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 534 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.13(7)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         2266
_refine_ls_number_parameters     139
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0717
_refine_ls_R_factor_gt           0.0438
_refine_ls_wR_factor_ref         0.1380
_refine_ls_wR_factor_gt          0.1011
_refine_ls_goodness_of_fit_ref   1.122
_refine_ls_restrained_S_all      1.122
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

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
C11 C 0.7205(4) 0.6999(5) -0.0164(6) 0.0878(15) Uani 1 1 d . . . . .
H11A H 0.673320 0.650822 -0.085149 0.132 Uiso 1 1 calc R U . . .
H11B H 0.761830 0.673775 0.025394 0.132 Uiso 1 1 calc R U . . .
H11C H 0.764700 0.764289 -0.064189 0.132 Uiso 1 1 calc R U . . .
C10 C 0.6918(3) 0.7335(3) 0.2407(4) 0.0550(9) Uani 1 1 d . . . . .
C9 C 0.5744(3) 0.7213(3) 0.0716(5) 0.0632(11) Uani 1 1 d . . . . .
C8 C 0.5348(3) 0.7357(3) 0.2105(4) 0.0598(10) Uani 1 1 d . . . . .
H8A H 0.472313 0.672834 0.238338 0.072 Uiso 1 1 calc R U . . .
H8AB H 0.519421 0.791438 0.203822 0.072 Uiso 1 1 calc R U . . .
C7 C 0.6210(3) 0.7620(3) 0.3200(4) 0.0513(9) Uani 1 1 d . . . . .
H7 H 0.658868 0.837424 0.330259 0.062 Uiso 1 1 calc R U . . .
C6 C 0.6833(3) 0.7689(4) 0.5759(5) 0.0736(13) Uani 1 1 d . . . . .
H6A H 0.661343 0.742581 0.671902 0.110 Uiso 1 1 calc R U . . .
H6B H 0.710607 0.842335 0.575631 0.110 Uiso 1 1 calc R U . . .
H6C H 0.735849 0.754034 0.544924 0.110 Uiso 1 1 calc R U . . .
C5 C 0.4333(4) 0.6492(4) 0.6248(5) 0.0802(14) Uani 1 1 d . . . . .
H5A H 0.364697 0.619295 0.582808 0.096 Uiso 1 1 calc R U . . .
H5AB H 0.430681 0.669550 0.723487 0.096 Uiso 1 1 calc R U . . .
C4 C 0.4722(5) 0.5726(4) 0.6198(6) 0.0914(17) Uani 1 1 d . . . . .
H4A H 0.414750 0.502188 0.615587 0.110 Uiso 1 1 calc R U . . .
H4AB H 0.513597 0.579901 0.704436 0.110 Uiso 1 1 calc R U . . .
C3 C 0.5374(4) 0.5993(3) 0.4830(6) 0.0767(13) Uani 1 1 d . . . . .
H3A H 0.494270 0.566785 0.399147 0.092 Uiso 1 1 calc R U . . .
H3AB H 0.588149 0.577039 0.490706 0.092 Uiso 1 1 calc R U . . .
O3 O 0.7644(2) 0.7277(3) 0.2868(3) 0.0841(10) Uani 1 1 d . . . . .
C2 C 0.5904(3) 0.7171(3) 0.4723(4) 0.0546(10) Uani 1 1 d . . . . .
O2 O 0.5387(3) 0.7139(3) -0.0492(4) 0.0938(11) Uani 1 1 d . . . . .
C1 C 0.5094(3) 0.7393(3) 0.5384(5) 0.0614(11) Uani 1 1 d . . . . .
N1 N 0.6618(3) 0.7162(3) 0.0982(4) 0.0597(9) Uani 1 1 d . . . . .
O1 O 0.5103(3) 0.8207(3) 0.5225(4) 0.0913(11) Uani 1 1 d . . . . .


_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
C11 N1 1.472(6) . ?
C10 O3 1.207(5) . ?
C10 N1 1.375(5) . ?
C10 C7 1.512(5) . ?
C9 O2 1.219(5) . ?
C9 N1 1.368(5) . ?
C9 C8 1.475(6) . ?
C8 C7 1.527(5) . ?
C7 C2 1.530(5) . ?
C6 C2 1.539(5) . ?
C5 C1 1.487(6) . ?
C5 C4 1.520(8) . ?
C4 C3 1.524(7) . ?
C3 C2 1.529(5) . ?
C2 C1 1.531(6) . ?
C1 O1 1.217(5) . ?

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
O3 C10 N1 123.0(4) . . ?
O3 C10 C7 128.9(4) . . ?
N1 C10 C7 108.1(3) . . ?
O2 C9 N1 123.1(4) . . ?
O2 C9 C8 128.6(4) . . ?
N1 C9 C8 108.3(3) . . ?
C9 C8 C7 105.6(3) . . ?
C10 C7 C8 102.9(3) . . ?
C10 C7 C2 115.0(3) . . ?
C8 C7 C2 118.0(3) . . ?
C1 C5 C4 104.9(4) . . ?
C5 C4 C3 105.3(4) . . ?
C4 C3 C2 104.5(4) . . ?
C3 C2 C7 115.6(3) . . ?
C3 C2 C1 102.3(3) . . ?
C7 C2 C1 111.7(3) . . ?
C3 C2 C6 110.8(3) . . ?
C7 C2 C6 110.9(3) . . ?
C1 C2 C6 104.7(3) . . ?
O1 C1 C5 126.1(4) . . ?
O1 C1 C2 123.5(4) . . ?
C5 C1 C2 110.4(4) . . ?
C9 N1 C10 113.1(3) . . ?
C9 N1 C11 122.9(4) . . ?
C10 N1 C11 123.9(4) . . ?

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
O2 C9 C8 C7 -168.6(4) . . . . ?
N1 C9 C8 C7 12.0(5) . . . . ?
O3 C10 C7 C8 -169.9(4) . . . . ?
N1 C10 C7 C8 11.7(4) . . . . ?
O3 C10 C7 C2 -40.2(6) . . . . ?
N1 C10 C7 C2 141.4(3) . . . . ?
C9 C8 C7 C10 -14.0(4) . . . . ?
C9 C8 C7 C2 -141.8(3) . . . . ?
C1 C5 C4 C3 -24.2(5) . . . . ?
C5 C4 C3 C2 35.9(5) . . . . ?
C4 C3 C2 C7 -154.0(4) . . . . ?
C4 C3 C2 C1 -32.4(5) . . . . ?
C4 C3 C2 C6 78.7(4) . . . . ?
C10 C7 C2 C3 -57.2(5) . . . . ?
C8 C7 C2 C3 64.6(5) . . . . ?
C10 C7 C2 C1 -173.6(3) . . . . ?
C8 C7 C2 C1 -51.8(5) . . . . ?
C10 C7 C2 C6 70.1(4) . . . . ?
C8 C7 C2 C6 -168.1(3) . . . . ?
C4 C5 C1 O1 -175.2(5) . . . . ?
C4 C5 C1 C2 3.7(5) . . . . ?
C3 C2 C1 O1 -163.1(5) . . . . ?
C7 C2 C1 O1 -38.9(6) . . . . ?
C6 C2 C1 O1 81.2(5) . . . . ?
C3 C2 C1 C5 18.0(5) . . . . ?
C7 C2 C1 C5 142.3(4) . . . . ?
C6 C2 C1 C5 -97.7(4) . . . . ?
O2 C9 N1 C10 175.8(4) . . . . ?
C8 C9 N1 C10 -4.7(5) . . . . ?
O2 C9 N1 C11 -0.8(7) . . . . ?
C8 C9 N1 C11 178.6(4) . . . . ?
O3 C10 N1 C9 176.6(4) . . . . ?
C7 C10 N1 C9 -4.8(5) . . . . ?
O3 C10 N1 C11 -6.7(7) . . . . ?
C7 C10 N1 C11 171.8(4) . . . . ?

_refine_diff_density_max         0.138
_refine_diff_density_min         -0.168
_refine_diff_density_rms         0.041







_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: hexane / ethyl acetate'
