# 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 t~exp~ \w \q \k \f Frames #-------------------------------------------------------------------------- 1 \w -40.00 -10.00 1.00 1.00 -- -40.81 -77.00 90.00 30 2 \w -116.00 -91.00 1.00 1.00 -- -40.81 -77.00 90.00 25 3 \w 17.00 54.00 1.00 1.00 -- 40.81 -38.00-120.00 37 4 \w -30.00 67.00 1.00 1.00 -- 40.81 -57.00 150.00 97 5 \w 38.00 117.00 1.00 2.00 -- 111.58-125.00 -60.00 79 6 \w 114.00 144.00 1.00 2.00 -- 111.58 45.00-150.00 30 7 \w 97.00 178.00 1.00 2.00 -- 111.58 45.00 -30.00 81 8 \w 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 '\w 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 > 2\s(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/[\s^2^(Fo^2^)+(0.0923P)^2^+0.0614P] where P=(Fo^2^+2Fc^2^)/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 REM REM 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