# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_TMK135_a
_database_code_depnum_ccdc_archive 'CCDC 1814265'
_audit_update_record             
;
2018-01-02 deposited with the CCDC.
2018-12-18 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          315
_chemical_formula_moiety         'C15 H19 N O3'
_chemical_formula_sum            'C15 H19 N O3'
_chemical_formula_weight         261.31

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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_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+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   10.3681(6)
_cell_length_b                   11.3036(6)
_cell_length_c                   13.4537(8)
_cell_angle_alpha                90
_cell_angle_beta                 111.487(4)
_cell_angle_gamma                90
_cell_volume                     1467.15(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    2593
_cell_measurement_theta_min      3.44
_cell_measurement_theta_max      28.71

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.183
_exptl_crystal_F_000             560
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.320
_exptl_crystal_size_mid          0.290
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    0.667
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.105
_exptl_absorpt_correction_T_max  0.325
_exptl_absorpt_process_details   'multi-scan absorbtion correction'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            8912
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_av_R_equivalents  0.0412
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         4.583
_diffrn_reflns_theta_max         66.642
_diffrn_reflns_theta_full        66.642
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measured_fraction_theta_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_point_group_measured_fraction_full 0.992
_reflns_number_total             2593
_reflns_number_gt                1866
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1000P)²+0.3787P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2573
_refine_ls_number_parameters     175
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0841
_refine_ls_R_factor_gt           0.0622
_refine_ls_wR_factor_ref         0.1845
_refine_ls_wR_factor_gt          0.1690
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_restrained_S_all      1.045
_refine_ls_shift/su_max          0.005
_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
O001 O 0.59733(16) 0.41168(17) 0.38886(12) 0.0555(5) Uani 1 1 d . . . . .
O002 O 0.3781(2) 0.37314(19) -0.05808(15) 0.0705(6) Uani 1 1 d . . . . .
N003 N 0.4470(2) 0.4532(2) 0.10843(16) 0.0569(6) Uani 1 1 d . . . . .
H003 H 0.4870 0.5143 0.0946 0.068 Uiso 1 1 calc R U . . .
C004 C 0.1980(2) 0.3739(2) 0.19777(18) 0.0462(6) Uani 1 1 d . . . . .
O005 O 0.6704(2) 0.3448(3) 0.26235(18) 0.1095(11) Uani 1 1 d . . . . .
C006 C 0.4445(2) 0.4305(2) 0.21297(19) 0.0523(6) Uani 1 1 d . . . . .
H006 H 0.4147 0.5016 0.2404 0.063 Uiso 1 1 calc R U . . .
C007 C 0.1335(3) 0.4746(2) 0.1442(2) 0.0592(7) Uani 1 1 d . . . . .
H007 H 0.1749 0.5179 0.1051 0.071 Uiso 1 1 calc R U . . .
C008 C 0.3828(2) 0.3727(2) 0.0346(2) 0.0546(6) Uani 1 1 d . . . . .
C009 C 0.3345(2) 0.3306(2) 0.1937(2) 0.0516(6) Uani 1 1 d . . . . .
H009 H 0.3720 0.2687 0.2475 0.062 Uiso 1 1 calc R U . . .
C00A C 0.7159(2) 0.3686(2) 0.48231(19) 0.0537(6) Uani 1 1 d . . . . .
C00B C 0.1327(3) 0.3114(3) 0.2539(2) 0.0610(7) Uani 1 1 d . . . . .
H00B H 0.1735 0.2432 0.2908 0.073 Uiso 1 1 calc R U . . .
C00C C 0.5853(2) 0.3907(3) 0.2901(2) 0.0582(7) Uani 1 1 d . . . . .
C00D C 0.0083(3) 0.5121(3) 0.1478(2) 0.0664(8) Uani 1 1 d . . . . .
H00D H -0.0329 0.5807 0.1120 0.080 Uiso 1 1 calc R U . . .
C00E C -0.0552(3) 0.4493(3) 0.2033(3) 0.0708(8) Uani 1 1 d . . . . .
H00E H -0.1396 0.4745 0.2053 0.085 Uiso 1 1 calc R U . . .
C00F C 0.3192(3) 0.2816(2) 0.0840(2) 0.0600(7) Uani 1 1 d . . . . .
H00A H 0.3673 0.2065 0.0913 0.072 Uiso 1 1 calc R U . . .
H00C H 0.2222 0.2698 0.0404 0.072 Uiso 1 1 calc R U . . .
C00G C 0.0062(3) 0.3495(3) 0.2556(3) 0.0753(9) Uani 1 1 d . . . . .
H00G H -0.0371 0.3061 0.2932 0.090 Uiso 1 1 calc R U . . .
C00H C 0.8437(3) 0.4341(4) 0.4869(3) 0.1032(13) Uani 1 1 d . . . . .
H00F H 0.8675 0.4121 0.4269 0.155 Uiso 1 1 calc R U . . .
H00H H 0.9188 0.4143 0.5519 0.155 Uiso 1 1 calc R U . . .
H00I H 0.8266 0.5177 0.4850 0.155 Uiso 1 1 calc R U . . .
C00I C 0.6769(4) 0.4024(4) 0.5751(3) 0.1155(16) Uani 1 1 d . . . . .
H00J H 0.6702 0.4870 0.5779 0.173 Uiso 1 1 calc R U . . .
H00K H 0.7465 0.3745 0.6401 0.173 Uiso 1 1 calc R U . . .
H00L H 0.5892 0.3675 0.5669 0.173 Uiso 1 1 calc R U . . .
C00J C 0.7275(5) 0.2384(3) 0.4746(4) 0.1286(18) Uani 1 1 d . . . . .
H00M H 0.6425 0.2018 0.4716 0.193 Uiso 1 1 calc R U . . .
H00N H 0.8025 0.2099 0.5360 0.193 Uiso 1 1 calc R U . . .
H00O H 0.7448 0.2191 0.4111 0.193 Uiso 1 1 calc R U . . .


_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
O001 C00C 1.309(3) . ?
O001 C00A 1.482(3) . ?
O002 C008 1.230(3) . ?
N003 C008 1.332(3) . ?
N003 C006 1.439(3) . ?
N003 H003 0.8600 . ?
C004 C00B 1.380(3) . ?
C004 C007 1.382(3) . ?
C004 C009 1.517(3) . ?
O005 C00C 1.195(3) . ?
C006 C00C 1.517(3) . ?
C006 C009 1.558(4) . ?
C006 H006 0.9800 . ?
C007 C00D 1.383(4) . ?
C007 H007 0.9300 . ?
C008 C00F 1.503(4) . ?
C009 C00F 1.529(4) . ?
C009 H009 0.9800 . ?
C00A C00J 1.483(5) . ?
C00A C00I 1.496(4) . ?
C00A C00H 1.499(4) . ?
C00B C00G 1.388(4) . ?
C00B H00B 0.9300 . ?
C00D C00E 1.361(4) . ?
C00D H00D 0.9300 . ?
C00E C00G 1.359(5) . ?
C00E H00E 0.9300 . ?
C00F H00A 0.9700 . ?
C00F H00C 0.9700 . ?
C00G H00G 0.9300 . ?
C00H H00F 0.9600 . ?
C00H H00H 0.9600 . ?
C00H H00I 0.9600 . ?
C00I H00J 0.9600 . ?
C00I H00K 0.9600 . ?
C00I H00L 0.9600 . ?
C00J H00M 0.9600 . ?
C00J H00N 0.9600 . ?
C00J H00O 0.9600 . ?

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
C00C O001 C00A 122.82(19) . . ?
C008 N003 C006 115.1(2) . . ?
C008 N003 H003 122.5 . . ?
C006 N003 H003 122.5 . . ?
C00B C004 C007 117.8(2) . . ?
C00B C004 C009 120.4(2) . . ?
C007 C004 C009 121.8(2) . . ?
N003 C006 C00C 111.41(19) . . ?
N003 C006 C009 103.91(19) . . ?
C00C C006 C009 111.2(2) . . ?
N003 C006 H006 110.1 . . ?
C00C C006 H006 110.1 . . ?
C009 C006 H006 110.1 . . ?
C004 C007 C00D 121.0(3) . . ?
C004 C007 H007 119.5 . . ?
C00D C007 H007 119.5 . . ?
O002 C008 N003 125.2(3) . . ?
O002 C008 C00F 126.2(2) . . ?
N003 C008 C00F 108.6(2) . . ?
C004 C009 C00F 112.6(2) . . ?
C004 C009 C006 113.3(2) . . ?
C00F C009 C006 103.6(2) . . ?
C004 C009 H009 109.1 . . ?
C00F C009 H009 109.1 . . ?
C006 C009 H009 109.1 . . ?
O001 C00A C00J 109.3(2) . . ?
O001 C00A C00I 103.3(2) . . ?
C00J C00A C00I 111.5(3) . . ?
O001 C00A C00H 108.6(2) . . ?
C00J C00A C00H 113.6(3) . . ?
C00I C00A C00H 110.1(3) . . ?
C004 C00B C00G 120.4(3) . . ?
C004 C00B H00B 119.8 . . ?
C00G C00B H00B 119.8 . . ?
O005 C00C O001 126.1(2) . . ?
O005 C00C C006 123.4(2) . . ?
O001 C00C C006 110.5(2) . . ?
C00E C00D C007 120.6(3) . . ?
C00E C00D H00D 119.7 . . ?
C007 C00D H00D 119.7 . . ?
C00G C00E C00D 119.2(3) . . ?
C00G C00E H00E 120.4 . . ?
C00D C00E H00E 120.4 . . ?
C008 C00F C009 105.7(2) . . ?
C008 C00F H00A 110.6 . . ?
C009 C00F H00A 110.6 . . ?
C008 C00F H00C 110.6 . . ?
C009 C00F H00C 110.6 . . ?
H00A C00F H00C 108.7 . . ?
C00E C00G C00B 121.0(3) . . ?
C00E C00G H00G 119.5 . . ?
C00B C00G H00G 119.5 . . ?
C00A C00H H00F 109.5 . . ?
C00A C00H H00H 109.5 . . ?
H00F C00H H00H 109.5 . . ?
C00A C00H H00I 109.5 . . ?
H00F C00H H00I 109.5 . . ?
H00H C00H H00I 109.5 . . ?
C00A C00I H00J 109.5 . . ?
C00A C00I H00K 109.5 . . ?
H00J C00I H00K 109.5 . . ?
C00A C00I H00L 109.5 . . ?
H00J C00I H00L 109.5 . . ?
H00K C00I H00L 109.5 . . ?
C00A C00J H00M 109.5 . . ?
C00A C00J H00N 109.5 . . ?
H00M C00J H00N 109.5 . . ?
C00A C00J H00O 109.5 . . ?
H00M C00J H00O 109.5 . . ?
H00N C00J H00O 109.5 . . ?

_refine_diff_density_max         0.379
_refine_diff_density_min         -0.245
_refine_diff_density_rms         0.044


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: n-Hexane/Dichloromethane'
