# Electronic Supplementary Material (ESI) for Green Chemistry # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_CRYSTALS_cif _audit_creation_date 07-01-26 _audit_creation_method CRYSTALS_ver_12.84 _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 15.0238(16) _cell_length_b 11.6122(10) _cell_length_c 20.9195(19) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 3649.6(6) _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'P b c a ' _symmetry_space_group_name_Hall '-P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x+1/2,y+1/2,z x+1/2,-y+1/2,-z x,-y+1/2,z+1/2 -x,y+1/2,-z+1/2 -x+1/2,-y,z+1/2 x+1/2,y,-z+1/2 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.1484 0.1585 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' P 0.1023 0.0942 6.4345 1.9067 4.1791 27.1570 1.7800 0.5260 1.4908 68.1645 1.1149 'International Tables Vol C 4.2.6.8 and 6.1.1.4' S 0.1246 0.1234 6.9053 1.4679 5.2034 22.2151 1.4379 0.2536 1.5863 56.1720 0.8669 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 8 _chemical_formula_sum 'C9 H14 Cl3 N6 O1 P1 S3' _chemical_formula_moiety 'C9 H12 N6 P S3, 3(Cl), (H2 O)' _chemical_compound_source ? _chemical_formula_weight 455.78 _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 3 _cell_measurement_theta_max 25 _cell_measurement_temperature 150 _exptl_crystal_description planar _exptl_crystal_colour colorless _exptl_crystal_size_min 0.08 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_max 0.50 _exptl_crystal_density_diffrn 1.659 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 1840 _exptl_absorpt_coefficient_mu 0.943 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [c.f. r.h. blessing, acta cryst. (1995), a51, 33-38] ; _exptl_absorpt_correction_T_min 0.72 _exptl_absorpt_correction_T_max 0.93 _diffrn_measurement_device_type 'Stoe IPDS' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method '\f scans' # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'IPDS (Stoe & Cie, 1996)' _computing_cell_refinement 'IPDS (Stoe & Cie, 1996)' _computing_data_reduction 'XRED (Stoe & Cie 1996)' _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time ? _diffrn_standards_interval_count ? _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 150 _diffrn_reflns_number 36255 _reflns_number_total 3472 _diffrn_reflns_av_R_equivalents 0.070 # Number of reflections with Friedels Law is 3472 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 3588 _diffrn_reflns_theta_min 2.372 _diffrn_reflns_theta_max 26.001 _diffrn_measured_fraction_theta_max 0.967 _diffrn_reflns_theta_full 25.221 _diffrn_measured_fraction_theta_full 0.974 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 25 _reflns_limit_h_min 0 _reflns_limit_h_max 18 _reflns_limit_k_min 0 _reflns_limit_k_max 13 _reflns_limit_l_min 0 _reflns_limit_l_max 25 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.57 _refine_diff_density_max 2.06 _refine_ls_number_reflns 1861 _refine_ls_number_restraints 0 _refine_ls_number_parameters 186 #_refine_ls_R_factor_ref 0.0588 _refine_ls_wR_factor_ref 0.0708 _refine_ls_goodness_of_fit_ref 1.1169 #_reflns_number_all 3472 _refine_ls_R_factor_all 0.0953 _refine_ls_wR_factor_all 0.0941 # The I/u(I) cutoff below was used for refinement as # well as the _gt R-factors: _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 1861 _refine_ls_R_factor_gt 0.0588 _refine_ls_wR_factor_gt 0.0708 _refine_ls_shift/su_max 0.000328 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment constr # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 1.23 0.686 0.594 ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens Cl1 Cl 0.30196(12) 0.38734(15) 0.89493(8) 0.0300 1.0000 Uani . . . . . . Cl2 Cl 0.29952(12) 0.37348(16) 0.60574(8) 0.0332 1.0000 Uani . . . . . . Cl3 Cl 0.4028(2) 0.6995(2) 0.96952(10) 0.0783 1.0000 Uani . . . . . . O1 O 0.4021(4) 0.5883(6) 0.5496(3) 0.0495 1.0000 Uani . . . . . . S1 S 0.35074(11) 0.67098(17) 0.70282(8) 0.0298 1.0000 Uani . . . . . . S2 S 0.60548(11) 0.61155(14) 0.83290(8) 0.0239 1.0000 Uani . . . . . . S3 S 0.59356(11) 0.62545(15) 0.66611(8) 0.0246 1.0000 Uani . . . . . . N1 N 0.3245(4) 0.7224(5) 0.8181(3) 0.0323 1.0000 Uani . . . . . . N2 N 0.2518(4) 0.8480(5) 0.7492(3) 0.0322 1.0000 Uani . . . . . . N3 N 0.5873(4) 0.4651(5) 0.9213(3) 0.0258 1.0000 Uani . . . . . . N4 N 0.6760(4) 0.6221(6) 0.9509(3) 0.0340 1.0000 Uani . . . . . . N5 N 0.5814(4) 0.4774(5) 0.5782(3) 0.0283 1.0000 Uani . . . . . . N6 N 0.6622(4) 0.6391(6) 0.5481(3) 0.0366 1.0000 Uani . . . . . . C1 C 0.3019(4) 0.7576(6) 0.7588(4) 0.0292 1.0000 Uani . . . . . . C2 C 0.3774(5) 0.6322(6) 0.8193(3) 0.0321 1.0000 Uani . . . . . . C3 C 0.4026(4) 0.5889(6) 0.7625(3) 0.0235 1.0000 Uani . . . . . . C4 C 0.6260(4) 0.5644(6) 0.9100(3) 0.0235 1.0000 Uani . . . . . . C5 C 0.5407(4) 0.4208(6) 0.8707(3) 0.0230 1.0000 Uani . . . . . . C6 C 0.5429(4) 0.4867(6) 0.8178(3) 0.0219 1.0000 Uani . . . . . . C7 C 0.6159(5) 0.5811(6) 0.5894(3) 0.0253 1.0000 Uani . . . . . . C8 C 0.5345(4) 0.4318(7) 0.6282(3) 0.0281 1.0000 Uani . . . . . . C9 C 0.5339(4) 0.4973(6) 0.6808(3) 0.0218 1.0000 Uani . . . . . . P1 P 0.47051(10) 0.46035(14) 0.75044(9) 0.0200 1.0000 Uani . . . . . . H7 H 0.2410 0.8692 0.7105 0.0384 1.0000 Uiso R . . . . . H11 H 0.3058 0.7559 0.8522 0.0383 1.0000 Uiso R . . . . . H14 H 0.2307 0.8840 0.7817 0.0383 1.0000 Uiso R . . . . . H15 H 0.5923 0.4298 0.9577 0.0322 1.0000 Uiso R . . . . . H16 H 0.7031 0.6834 0.9381 0.0403 1.0000 Uiso R . . . . . H17 H 0.6878 0.7015 0.5606 0.0422 1.0000 Uiso R . . . . . H18 H 0.6665 0.6148 0.5094 0.0424 1.0000 Uiso R . . . . . H19 H 0.6760 0.6017 0.9902 0.0404 1.0000 Uiso R . . . . . H20 H 0.5926 0.4394 0.5440 0.0335 1.0000 Uiso R . . . . . H21 H 0.3970 0.6012 0.8580 0.0391 1.0000 Uiso R . . . . . H51 H 0.5101 0.3513 0.8730 0.0292 1.0000 Uiso R . . . . . H81 H 0.5047 0.3619 0.6256 0.0342 1.0000 Uiso R . . . . . 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 Cl1 0.0300(10) 0.0321(10) 0.0278(8) -0.0003(7) -0.0024(7) -0.0080(7) Cl2 0.0338(10) 0.0372(11) 0.0285(9) 0.0039(7) 0.0038(7) 0.0089(8) Cl3 0.161(3) 0.0380(13) 0.0362(11) 0.0118(10) -0.0138(15) -0.0190(16) O1 0.055(4) 0.048(4) 0.045(3) -0.004(3) 0.004(3) 0.000(3) S1 0.0256(9) 0.0363(10) 0.0277(8) -0.0010(8) 0.0003(7) 0.0054(8) S2 0.0240(9) 0.0231(9) 0.0245(8) 0.0042(7) -0.0034(6) -0.0064(7) S3 0.0266(9) 0.0232(9) 0.0241(8) -0.0030(6) 0.0044(7) -0.0075(7) N1 0.0323(7) 0.0323(7) 0.0323(7) 0.0008(7) 0.0008(7) 0.0000(7) N2 0.0322(7) 0.0322(7) 0.0322(7) 0.0008(7) 0.0008(7) 0.0000(7) N3 0.029(3) 0.023(3) 0.025(3) 0.010(2) 0.001(2) 0.001(3) N4 0.039(4) 0.037(4) 0.026(3) 0.000(3) -0.006(3) 0.000(3) N5 0.024(3) 0.032(4) 0.029(3) -0.010(3) 0.009(2) -0.002(3) N6 0.047(4) 0.037(4) 0.026(3) -0.005(3) 0.005(3) -0.012(3) C1 0.013(3) 0.029(4) 0.046(4) -0.001(3) -0.003(3) 0.002(3) C2 0.0321(8) 0.0321(8) 0.0321(8) 0.0026(8) 0.0026(8) -0.0035(8) C3 0.0235(8) 0.0235(8) 0.0235(8) 0.0026(8) 0.0026(8) -0.0035(8) C4 0.022(3) 0.026(4) 0.022(3) 0.002(3) 0.001(3) 0.007(3) C5 0.015(3) 0.016(4) 0.037(4) 0.003(3) 0.006(3) 0.001(3) C6 0.013(3) 0.019(4) 0.033(3) 0.001(3) 0.008(3) 0.000(3) C7 0.021(3) 0.025(4) 0.030(4) -0.001(3) 0.000(3) -0.002(3) C8 0.021(4) 0.025(4) 0.038(4) -0.011(3) 0.005(3) -0.003(3) C9 0.016(3) 0.018(4) 0.032(3) -0.001(3) -0.002(3) 0.001(2) P1 0.0138(7) 0.0174(8) 0.0289(7) 0.0005(8) 0.0013(7) -0.0024(6) _refine_ls_extinction_method None loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag S1 . C1 . 1.709(7) yes S1 . C3 . 1.753(6) yes S2 . C4 . 1.731(6) yes S2 . C6 . 1.757(7) yes S3 . C7 . 1.719(7) yes S3 . C9 . 1.765(7) yes N1 . C1 . 1.350(9) yes N1 . C2 . 1.315(9) yes N1 . H11 . 0.860 no N2 . C1 . 1.307(9) yes N2 . H7 . 0.862 no N2 . H14 . 0.860 no N3 . C4 . 1.313(9) yes N3 . C5 . 1.369(9) yes N3 . H15 . 0.867 no N4 . C4 . 1.320(9) yes N4 . H16 . 0.863 no N4 . H19 . 0.857 no N5 . C7 . 1.331(9) yes N5 . C8 . 1.367(9) yes N5 . H20 . 0.858 no N6 . C7 . 1.297(9) yes N6 . H17 . 0.861 no N6 . H18 . 0.861 no C2 . C3 . 1.345(9) yes C2 . H21 . 0.933 no C3 . P1 . 1.825(7) yes C5 . C6 . 1.347(9) yes C5 . H51 . 0.930 no C6 . P1 . 1.805(7) yes C8 . C9 . 1.337(9) yes C8 . H81 . 0.929 no C9 . P1 . 1.793(7) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag C1 . S1 . C3 . 91.3(3) yes C4 . S2 . C6 . 90.1(3) yes C7 . S3 . C9 . 90.5(3) yes C1 . N1 . C2 . 114.3(6) yes C1 . N1 . H11 . 122.8 no C2 . N1 . H11 . 122.9 no C1 . N2 . H7 . 118.9 no C1 . N2 . H14 . 118.9 no H7 . N2 . H14 . 122.3 no C4 . N3 . C5 . 114.6(6) yes C4 . N3 . H15 . 122.4 no C5 . N3 . H15 . 123.0 no C4 . N4 . H16 . 119.2 no C4 . N4 . H19 . 118.8 no H16 . N4 . H19 . 121.7 no C7 . N5 . C8 . 114.6(6) yes C7 . N5 . H20 . 122.4 no C8 . N5 . H20 . 122.7 no C7 . N6 . H17 . 118.3 no C7 . N6 . H18 . 119.8 no H17 . N6 . H18 . 121.9 no S1 . C1 . N1 . 110.1(5) yes S1 . C1 . N2 . 127.9(6) yes N1 . C1 . N2 . 121.9(7) yes N1 . C2 . C3 . 116.8(7) yes N1 . C2 . H21 . 120.9 no C3 . C2 . H21 . 122.2 no S1 . C3 . C2 . 107.5(5) yes S1 . C3 . P1 . 126.5(3) yes C2 . C3 . P1 . 125.8(5) yes S2 . C4 . N4 . 123.0(6) yes S2 . C4 . N3 . 111.5(5) yes N4 . C4 . N3 . 125.5(6) yes N3 . C5 . C6 . 114.3(6) yes N3 . C5 . H51 . 122.6 no C6 . C5 . H51 . 123.1 no S2 . C6 . C5 . 109.4(5) yes S2 . C6 . P1 . 127.1(4) yes C5 . C6 . P1 . 122.1(5) yes S3 . C7 . N5 . 111.0(5) yes S3 . C7 . N6 . 124.8(6) yes N5 . C7 . N6 . 124.1(6) yes N5 . C8 . C9 . 114.4(6) yes N5 . C8 . H81 . 122.8 no C9 . C8 . H81 . 122.8 no S3 . C9 . C8 . 109.4(5) yes S3 . C9 . P1 . 127.8(4) yes C8 . C9 . P1 . 122.5(5) yes C3 . P1 . C6 . 95.2(3) yes C3 . P1 . C9 . 102.3(3) yes C6 . P1 . C9 . 105.9(3) yes loop_ _geom_hbond_atom_site_label_D _geom_hbond_site_symmetry_D _geom_hbond_atom_site_label_H _geom_hbond_site_symmetry_H _geom_hbond_atom_site_label_A _geom_hbond_site_symmetry_A _geom_hbond_angle_DHA _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_publ_flag N5 . H20 . O1 2_666 156 0.86 1.99 2.791(9) yes _database_code_depnum_ccdc_archive 'CCDC 945999'