# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_exp_2511
_database_code_depnum_ccdc_archive 'CCDC 1935576'
loop_
_audit_author_name
_audit_author_address
DHP
;Tsinghua University
China
;
_audit_update_record             
;
2019-06-21 deposited with the CCDC.	2019-11-25 downloaded from the CCDC.
;
_audit_creation_date             2018-06-05
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C6 H5 D N2'
_chemical_formula_sum            'C6 H5 D N2'
_chemical_formula_weight         107.13
_chemical_melting_point          ?
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'
D D 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'

_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      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z-1/2'
'-x-1/2, y-1/2, z'

_cell_length_a                   6.0431(2)
_cell_length_b                   13.3857(4)
_cell_length_c                   14.3592(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1161.53(6)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    1163
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.5170
_cell_measurement_theta_min      6.1600
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.613
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61230
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.225
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             448
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0169
_diffrn_reflns_av_unetI/netI     0.0209
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            2497
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.697
_diffrn_reflns_theta_min         6.164
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2137
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -40.00 -10.00   1.00    1.00    --  -40.81 -77.00  90.00   30
  2  ω   -116.00 -91.00   1.00    1.00    --  -40.81 -77.00  90.00   25
  3  ω     17.00  54.00   1.00    1.00    --   40.81 -38.00-120.00   37
  4  ω    -30.00  67.00   1.00    1.00    --   40.81 -57.00 150.00   97
  5  ω     38.00 117.00   1.00    2.00    --  111.58-125.00 -60.00   79
  6  ω    114.00 144.00   1.00    2.00    --  111.58  45.00-150.00   30
  7  ω     97.00 178.00   1.00    2.00    --  111.58  45.00 -30.00   81
  8  ω     52.00  98.00   1.00    2.00    --  111.58 -61.00  60.00   46
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0145307000
_diffrn_orient_matrix_UB_12      0.0800564000
_diffrn_orient_matrix_UB_13      0.0767866000
_diffrn_orient_matrix_UB_21      0.0047642000
_diffrn_orient_matrix_UB_22      0.0826628000
_diffrn_orient_matrix_UB_23      -0.0746946000
_diffrn_orient_matrix_UB_31      -0.2544434000
_diffrn_orient_matrix_UB_32      -0.0029920000
_diffrn_orient_matrix_UB_33      -0.0057283000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\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                976
_reflns_number_total             1181
_reflns_odcompleteness_completeness 99.45
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.365
_refine_diff_density_min         -0.559
_refine_diff_density_rms         0.213
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     81
_refine_ls_number_reflns         1181
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0746
_refine_ls_R_factor_gt           0.0667
_refine_ls_restrained_S_all      1.099
_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)+(0.0923P)²+0.0614P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1497
_refine_ls_wR_factor_ref         0.1598
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C4(H4), C5(H5)
;
_atom_sites_solution_hydrogens   mixed
_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
N1 N 0.4451(3) 0.18645(10) 0.34871(11) 0.0644(4) Uani 1 1 d . . . . .
H1 H 0.4943 0.1290 0.3316 0.077 Uiso 1 1 calc R . . . .
C2 C 0.4974(2) 0.36050(11) 0.36046(9) 0.0472(4) Uani 1 1 d . . . . .
C1 C 0.5688(2) 0.26920(12) 0.33650(10) 0.0503(4) Uani 1 1 d . . . . .
H1A H 0.7090 0.2627 0.3105 0.060 Uiso 1 1 calc R . . . .
C3 C 0.2740(3) 0.37816(14) 0.40479(14) 0.0626(5) Uani 1 1 d . . . . .
C4 C 0.1558(3) 0.28076(15) 0.41545(11) 0.0628(5) Uani 1 1 d . . . . .
H4 H 0.0159 0.2812 0.4424 0.075 Uiso 1 1 calc R . . . .
C6 C 0.6372(3) 0.44337(13) 0.34485(12) 0.0611(5) Uani 1 1 d . . . . .
N2 N 0.7472(3) 0.51219(14) 0.33310(17) 0.0922(7) Uani 1 1 d . . . . .
C5 C 0.2381(3) 0.19490(14) 0.38903(13) 0.0649(5) Uani 1 1 d . . . . .
H5 H 0.1542 0.1374 0.3977 0.078 Uiso 1 1 calc R . . . .
D3A D 0.290(4) 0.415(2) 0.4658(19) 0.092(7) Uiso 1 1 d . . . . .
H3B H 0.181(4) 0.4237(18) 0.3680(16) 0.081(6) Uiso 1 1 d . . . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
N1 0.0700(9) 0.0454(8) 0.0779(10) -0.0047(7) -0.0001(7) 0.0047(7)
C2 0.0414(7) 0.0506(8) 0.0497(7) -0.0033(6) -0.0010(5) 0.0004(6)
C1 0.0435(7) 0.0563(9) 0.0512(8) -0.0042(6) 0.0007(5) 0.0064(6)
C3 0.0507(9) 0.0661(10) 0.0710(11) -0.0077(9) 0.0100(7) 0.0094(7)
C4 0.0441(7) 0.0876(13) 0.0566(9) 0.0058(8) 0.0053(6) -0.0033(8)
C6 0.0530(9) 0.0578(9) 0.0726(10) -0.0086(7) 0.0009(7) -0.0038(8)
N2 0.0772(11) 0.0673(10) 0.1320(17) -0.0120(11) 0.0103(10) -0.0193(9)
C5 0.0630(9) 0.0674(11) 0.0644(10) 0.0103(8) -0.0030(7) -0.0149(8)

_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 H1 0.8600 . ?
N1 C1 1.348(2) . ?
N1 C5 1.383(2) . ?
C2 C1 1.341(2) . ?
C2 C3 1.511(2) . ?
C2 C6 1.412(2) . ?
C1 H1A 0.9300 . ?
C3 C4 1.494(2) . ?
C3 D3A 1.01(3) . ?
C3 H3B 0.98(2) . ?
C4 H4 0.9300 . ?
C4 C5 1.308(3) . ?
C6 N2 1.149(2) . ?
C5 H5 0.9300 . ?

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 H1 120.4 . . ?
C1 N1 C5 119.26(14) . . ?
C5 N1 H1 120.4 . . ?
C1 C2 C3 122.56(14) . . ?
C1 C2 C6 118.85(13) . . ?
C6 C2 C3 118.59(13) . . ?
N1 C1 H1A 118.8 . . ?
C2 C1 N1 122.49(13) . . ?
C2 C1 H1A 118.8 . . ?
C2 C3 D3A 110.8(14) . . ?
C2 C3 H3B 112.3(13) . . ?
C4 C3 C2 109.49(13) . . ?
C4 C3 D3A 112.3(14) . . ?
C4 C3 H3B 108.9(14) . . ?
D3A C3 H3B 103(2) . . ?
C3 C4 H4 118.1 . . ?
C5 C4 C3 123.70(15) . . ?
C5 C4 H4 118.1 . . ?
N2 C6 C2 178.38(19) . . ?
N1 C5 H5 118.8 . . ?
C4 C5 N1 122.48(16) . . ?
C4 C5 H5 118.8 . . ?

_iucr_refine_instructions_details 
;

    exp_2511.res created by SHELXL-2014/7

TITL exp_2511_a.res in Pbca
REM Old TITL exp_2511 in Pbca
REM SHELXT solution in Pbca
REM R1 0.181, Rweak 0.351, Alpha 0.021, Orientation as input
REM Formula found by SHELXT: C6 N2
CELL 1.54184 6.0431 13.3857 14.3592 90 90 90
ZERR 8 0.0002 0.0004 0.0004 0 0 0
LATT 1
SYMM 0.5-X,-Y,0.5+Z
SYMM -X,0.5+Y,0.5-Z
SYMM 0.5+X,0.5-Y,-Z
SFAC C H D N
UNIT 48 40 8 16
 
L.S. 40
PLAN  20
BOND $H
list 4
fmap 2 53
ACTA
REM <olex2.extras>
REM <HklSrc "%.\\exp_2511.hkl">
REM </olex2.extras>
 
WGHT    0.092300    0.061400
FVAR       0.82093
N1    4    0.445097    0.186449    0.348710    11.00000    0.06997    0.04540 =
         0.07788   -0.00466   -0.00010    0.00471
AFIX  43
H1    2    0.494342    0.129026    0.331620    11.00000   -1.20000
AFIX   0
C2    1    0.497369    0.360498    0.360462    11.00000    0.04143    0.05060 =
         0.04966   -0.00326   -0.00098    0.00039
C1    1    0.568784    0.269200    0.336502    11.00000    0.04352    0.05630 =
         0.05121   -0.00421    0.00075    0.00639
AFIX  43
H1A   2    0.708976    0.262738    0.310474    11.00000   -1.20000
AFIX   0
C3    1    0.274018    0.378155    0.404793    11.00000    0.05070    0.06614 =
         0.07104   -0.00772    0.00998    0.00937
C4    1    0.155812    0.280762    0.415447    11.00000    0.04407    0.08761 =
         0.05660    0.00579    0.00528   -0.00335
AFIX  43
H4    2    0.015856    0.281202    0.442378    11.00000   -1.20000
AFIX   0
C6    1    0.637214    0.443369    0.344853    11.00000    0.05302    0.05777 =
         0.07257   -0.00860    0.00086   -0.00383
N2    4    0.747242    0.512193    0.333100    11.00000    0.07724    0.06732 =
         0.13203   -0.01201    0.01035   -0.01926
C5    1    0.238096    0.194903    0.389027    11.00000    0.06302    0.06736 =
         0.06443    0.01027   -0.00295   -0.01490
AFIX  43
H5    2    0.154226    0.137395    0.397685    11.00000   -1.20000
AFIX   0
D3A   3    0.290325    0.414591    0.465817    11.00000    0.09225
H3B   2    0.181335    0.423699    0.367988    11.00000    0.08109
HKLF 4
 
REM  exp_2511_a.res in Pbca
REM R1 =  0.0667 for     976 Fo > 4sig(Fo)  and  0.0746 for all    1181 data
REM     81 parameters refined using      0 restraints
 
END  
     
WGHT      0.0923      0.0614 

REM Highest difference peak  0.365,  deepest hole -0.559,  1-sigma level  0.213
Q1    1   0.4542  0.4763  0.5016  11.00000  0.05    0.37
Q2    1   0.8634  0.4435  0.2395  11.00000  0.05    0.36
Q3    1   0.3485  0.3793  0.5057  11.00000  0.05    0.36
Q4    1   0.9208  0.5267  0.2426  11.00000  0.05    0.36
Q5    1   0.2803  0.2818  0.5166  11.00000  0.05    0.35
Q6    1   0.0950  0.4636  0.5022  11.00000  0.05    0.35
Q7    1   0.9331  0.4810  0.2529  11.00000  0.05    0.35
Q8    1   0.4728  0.3768  0.2439  11.00000  0.05    0.34
Q9    1  -0.0672  0.4331  0.4963  11.00000  0.05    0.34
Q10   1   0.6169  0.1097  0.2386  11.00000  0.05    0.34
Q11   1   0.4653  0.0353  0.2555  11.00000  0.05    0.34
Q12   1   0.7148  0.5830  0.2408  11.00000  0.05    0.33
Q13   1  -0.1971  0.3519  0.4940  11.00000  0.05    0.33
Q14   1   0.5084  0.1348  0.2440  11.00000  0.05    0.33
Q15   1   0.3755  0.1745  0.2401  11.00000  0.05    0.33
Q16   1   0.2444  0.1760  0.5129  11.00000  0.05    0.32
Q17   1   0.1600  0.4201  0.2666  11.00000  0.05    0.32
Q18   1   0.8420  0.2720  0.2559  11.00000  0.05    0.32
Q19   1   0.7677  0.4907  0.2277  11.00000  0.05    0.31
Q20   1   0.1259  0.0815  0.5022  11.00000  0.05    0.31

  REM The information below was added by Olex2.
  REM
  REM R1 = 0.0667 for 976 Fo > 4sig(Fo) and 0.0746 for all 2843 data
  REM n/a parameters refined using n/a restraints
  REM Highest difference peak 0.37, deepest hole -0.56
  REM Mean Shift 0, Max Shift 0.000.

  REM +++ Tabular Listing of Refinement Information +++
  REM R1_all = 0.0746
  REM R1_gt = 0.0667
  REM wR_ref = 0.1598
  REM GOOF = 1.099
  REM Shift_max = 0.000
  REM Shift_mean = 0
  REM Reflections_all = 2843
  REM Reflections_gt = 976
  REM Parameters = n/a
  REM Hole = -0.56
  REM Peak = 0.37
  REM Flack = n/a

  
;
_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 1.394
_oxdiff_exptl_absorpt_empirical_full_min 0.627
