# Electronic Supplementary Material (ESI) for Catalysis Science & Technology.
# 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_les150_sq
_database_code_depnum_ccdc_archive 'CCDC 2044161'
loop_
_audit_author_name
_audit_author_address
'Martin Nieger'
;University of Helsinki
Finland
;
_audit_update_record             
;
2020-11-13 deposited with the CCDC.	2021-09-02 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
'N-(amino(dimethylamino)methylene)-N-methylmethanaminiumhydrogen carbonate'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C5 H14 N3, C H O3'
_chemical_formula_sum            'C6 H15 N3 O3'
_chemical_formula_weight         177.21

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/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   7.4094(2)
_cell_length_b                   9.2008(2)
_cell_length_c                   14.0802(3)
_cell_angle_alpha                90
_cell_angle_beta                 94.270(1)
_cell_angle_gamma                90
_cell_volume                     957.22(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    123(2)
_cell_measurement_reflns_used    6846
_cell_measurement_theta_min      5.7
_cell_measurement_theta_max      72.1

_exptl_crystal_description       blocks
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_F_000             384
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.140
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    0.827
_shelx_estimated_absorpt_T_min   0.893
_shelx_estimated_absorpt_T_max   0.968
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8550
_exptl_absorpt_correction_T_max  0.9705
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2014)'
_exptl_absorpt_special_details   ?

_exptl_special_details           
;
 dx = 40 mm, 1 deg., 8+1 runs, 1650 frames, 15/30/60 sec./frame
;

_diffrn_ambient_temperature      123(2)
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_type           CuK\a
_diffrn_source                   'INCOATEC microfocus sealed tube'
_diffrn_measurement_device_type  'Bruker D8 VENTURE with PhotonII CPAD detector'
_diffrn_measurement_method       'rotation in φ and ω, 1°, shutterless'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            9917
_diffrn_reflns_av_unetI/netI     0.0211
_diffrn_reflns_av_R_equivalents  0.0266
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         5.749
_diffrn_reflns_theta_max         72.112
_diffrn_reflns_theta_full        67.679
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             1889
_reflns_number_gt                1746
_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.
 
 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       'APEX3 (Bruker AXS Inc., 2016)'
_computing_cell_refinement       'APEX3 (Bruker AXS Inc., 2016)'
_computing_data_reduction        'SAINT (Bruker AXS Inc., 2016)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  'publCIF (Westrip, 2010)'

_refine_special_details          
;Refinement with the listed atoms show residual electron density due to
traces of solvent acetonitrile which could not be refined. 
In 2 voids are approx. 3 electron per void.  Therefore the option "SQUEEZE" 
of the program package PLATON (Spek, A.L. (2009). Acta Cryst. D65, 148-155. 
Spek, A.L. (2015). Acta Cryst. C71, 9-18.) was used to create a hkl
file taking into account the residual electron density in the void areas.

The small fraction of the solvent acetonitrile was not included in the unit card.,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)+(0.0356P)²+0.2911P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1889
_refine_ls_number_parameters     122
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0332
_refine_ls_R_factor_gt           0.0308
_refine_ls_wR_factor_ref         0.0799
_refine_ls_wR_factor_gt          0.0783
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_restrained_S_all      1.037
_refine_ls_shift/su_max          0.000
_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
N1 N 0.51576(13) 0.49892(11) 0.36056(6) 0.0262(2) Uani 1 1 d D . . . .
H1A H 0.5747(19) 0.4321(16) 0.3975(10) 0.039 Uiso 1 1 d D U . . .
H1B H 0.4537(19) 0.5662(16) 0.3891(10) 0.039 Uiso 1 1 d D U . . .
C1 C 0.50908(14) 0.48658(11) 0.26668(7) 0.0227(2) Uani 1 1 d . . . . .
N2 N 0.63246(12) 0.40495(11) 0.22579(6) 0.0255(2) Uani 1 1 d . . . . .
C21 C 0.58865(17) 0.31954(14) 0.13937(8) 0.0331(3) Uani 1 1 d . . . . .
H21A H 0.4617 0.3353 0.1172 0.050 Uiso 1 1 calc R U . . .
H21B H 0.6084 0.2162 0.1534 0.050 Uiso 1 1 calc R U . . .
H21C H 0.6666 0.3500 0.0897 0.050 Uiso 1 1 calc R U . . .
C22 C 0.79576(15) 0.35714(14) 0.28160(8) 0.0312(3) Uani 1 1 d . . . . .
H22A H 0.8377 0.4345 0.3257 0.047 Uiso 1 1 calc R U . . .
H22B H 0.8904 0.3350 0.2387 0.047 Uiso 1 1 calc R U . . .
H22C H 0.7687 0.2698 0.3178 0.047 Uiso 1 1 calc R U . . .
N3 N 0.38027(12) 0.55621(11) 0.21197(6) 0.0259(2) Uani 1 1 d . . . . .
C31 C 0.22500(15) 0.61967(14) 0.25480(8) 0.0320(3) Uani 1 1 d . . . . .
H31A H 0.1891 0.5565 0.3062 0.048 Uiso 1 1 calc R U . . .
H31B H 0.1239 0.6294 0.2062 0.048 Uiso 1 1 calc R U . . .
H31C H 0.2578 0.7157 0.2808 0.048 Uiso 1 1 calc R U . . .
C32 C 0.40779(16) 0.60733(14) 0.11570(8) 0.0310(3) Uani 1 1 d . . . . .
H32A H 0.5336 0.5898 0.1017 0.047 Uiso 1 1 calc R U . . .
H32B H 0.3818 0.7117 0.1113 0.047 Uiso 1 1 calc R U . . .
H32C H 0.3264 0.5547 0.0696 0.047 Uiso 1 1 calc R U . . .
C11 C 0.60496(13) 0.19520(12) 0.50651(7) 0.0214(2) Uani 1 1 d . . . . .
O11 O 0.53856(12) 0.14009(9) 0.58379(5) 0.0302(2) Uani 1 1 d D . . . .
H11 H 0.492(2) 0.0547(16) 0.5735(11) 0.045 Uiso 1 1 d D U . . .
O12 O 0.60838(11) 0.11510(9) 0.43264(5) 0.0307(2) Uani 1 1 d . . . . .
O13 O 0.66236(10) 0.32331(8) 0.51102(5) 0.02660(19) 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
N1 C1 1.3240(14) . ?
N1 H1A 0.898(13) . ?
N1 H1B 0.885(13) . ?
C1 N3 1.3436(14) . ?
C1 N2 1.3453(14) . ?
N2 C22 1.4606(15) . ?
N2 C21 1.4644(15) . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
N3 C31 1.4600(14) . ?
N3 C32 1.4633(14) . ?
C31 H31A 0.9800 . ?
C31 H31B 0.9800 . ?
C31 H31C 0.9800 . ?
C32 H32A 0.9800 . ?
C32 H32B 0.9800 . ?
C32 H32C 0.9800 . ?
C11 O13 1.2531(13) . ?
C11 O12 1.2765(13) . ?
C11 O11 1.3277(13) . ?
O11 H11 0.865(14) . ?

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 N1 H1A 120.0(10) . . ?
C1 N1 H1B 122.1(10) . . ?
H1A N1 H1B 117.5(14) . . ?
N1 C1 N3 120.25(10) . . ?
N1 C1 N2 119.94(10) . . ?
N3 C1 N2 119.81(9) . . ?
C1 N2 C22 120.00(9) . . ?
C1 N2 C21 122.65(9) . . ?
C22 N2 C21 114.14(9) . . ?
N2 C21 H21A 109.5 . . ?
N2 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
N2 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
N2 C22 H22A 109.5 . . ?
N2 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
N2 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C1 N3 C31 120.12(9) . . ?
C1 N3 C32 122.84(9) . . ?
C31 N3 C32 115.00(9) . . ?
N3 C31 H31A 109.5 . . ?
N3 C31 H31B 109.5 . . ?
H31A C31 H31B 109.5 . . ?
N3 C31 H31C 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 109.5 . . ?
N3 C32 H32A 109.5 . . ?
N3 C32 H32B 109.5 . . ?
H32A C32 H32B 109.5 . . ?
N3 C32 H32C 109.5 . . ?
H32A C32 H32C 109.5 . . ?
H32B C32 H32C 109.5 . . ?
O13 C11 O12 123.86(9) . . ?
O13 C11 O11 117.56(9) . . ?
O12 C11 O11 118.57(10) . . ?
C11 O11 H11 112.1(11) . . ?

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
N1 C1 N2 C22 -13.81(16) . . . . ?
N3 C1 N2 C22 165.69(10) . . . . ?
N1 C1 N2 C21 144.74(11) . . . . ?
N3 C1 N2 C21 -35.75(15) . . . . ?
N1 C1 N3 C31 -13.21(16) . . . . ?
N2 C1 N3 C31 167.29(10) . . . . ?
N1 C1 N3 C32 149.70(11) . . . . ?
N2 C1 N3 C32 -29.80(16) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1A O13 0.898(13) 1.955(13) 2.8171(12) 160.4(13) .
N1 H1B O13 0.885(13) 1.982(13) 2.8358(12) 161.5(14) 3_666
C22 H22B O11 0.98 2.52 3.4265(14) 152.9 4_665
C22 H22C O12 0.98 2.52 3.4423(14) 157.2 .
C31 H31B O12 0.98 2.51 3.4783(14) 169.3 2
O11 H11 O12 0.865(14) 1.731(14) 2.5912(12) 172.9(16) 3_656

_refine_diff_density_max         0.187
_refine_diff_density_min         -0.167
_refine_diff_density_rms         0.034



# SQUEEZE RESULTS (Version =  30118)
# 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 0.500 0.500 28 3 'traces of CH3CN'
2 0.500 1.000 0.000 28 3 'traces of CH3CN'
_platon_squeeze_void_probe_radius 1.20
_platon_squeeze_details          ?
