# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Haukka, Matti' _publ_contact_author_email matti.haukka@uef.fi _publ_section_title ; Concerted halogen and hydrogen bonding in RuI2(H2dcbpy)(CO)2]...2...CH3OH)...I2...[RuI2(H2dcbpy)(CO)2] ; loop_ _publ_author_name 'Matti Tuikka' 'Mika Niskanen' 'Pipsa Hirva' 'Kari Rissanen' 'Arto Valkonen' 'Matti Haukka' # Attachment '- Haukka.cif' #Concerted halogen and hydrogen bonding in RuI2(H2dcbpy)(CO)2]...I2...CH3OH) #...I2...[RuI2(H2dcbpy)(CO)2] # by Matti Tuikka, Mika Niskanen, Pipsa Hirva, Kari Rissanen, Arto Valkonen, #and Matti Haukka data_1 _database_code_depnum_ccdc_archive 'CCDC 796685' #TrackingRef '- Haukka.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C15 H12 I2 N2 O6 Ru, C H4 O, 2(I2)' _chemical_formula_sum 'C15 H12 I6 N2 O7 Ru' _chemical_formula_weight 1194.74 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ru Ru -1.2594 0.8363 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.5481(2) _cell_length_b 11.2104(3) _cell_length_c 16.1242(4) _cell_angle_alpha 96.7880(10) _cell_angle_beta 103.1250(10) _cell_angle_gamma 90.9920(10) _cell_volume 1318.05(6) _cell_formula_units_Z 2 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 9268 _cell_measurement_theta_min 2.38 _cell_measurement_theta_max 39.22 _exptl_crystal_description plate _exptl_crystal_colour purple _exptl_crystal_size_max 0.24 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.010 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1068 _exptl_absorpt_coefficient_mu 7.658 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.2587 _exptl_absorpt_correction_T_max 0.5794 _exptl_absorpt_process_details 'SADABS (Sheldrick, 2008)' _publ_section_exptl_refinement ; The OH hydrogen atoms were located from the difference Fourier map but constrained to ride on their parent atom, with U~iso~ = 1.5 U~eq~(parent atom). Other hydrogen atoms were positioned geometrically and were also constrained to ride on their parent atoms, with C---H = 0.95-0.98 \%A, and U~iso~ = 1.2-1.5 U~eq~(parent atom). The highest peak is located 0.66 \%A from atom I1 and the deepest hole is located 0.46 \%A from atom I5. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'curved graphite crystal' _diffrn_measurement_device_type 'Bruker KAPPA APEX II DUO CCD' _diffrn_measurement_device '62mm x 62mm CCD camera on \k-goniostat' _diffrn_detector_area_resol_mean 16 # 8 for binned mode _diffrn_measurement_method '\f scans and \w scans with \k offset' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 83823 _diffrn_reflns_av_R_equivalents 0.0299 _diffrn_reflns_av_sigmaI/netI 0.0162 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 1.83 _diffrn_reflns_theta_max 32.50 _reflns_number_total 9551 _reflns_number_gt 8568 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 (Bruker AXS, 2010)' _computing_cell_refinement 'SAINT (Bruker AXS, 2009)' _computing_data_reduction 'SAINT (Bruker AXS, 2009)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Diamond v.3.2e (Brandenburg, 2010)' _computing_publication_material 'SHELXL-97 (Sheldrick, 2008)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0159P)^2^+2.1056P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 9551 _refine_ls_number_parameters 281 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0238 _refine_ls_R_factor_gt 0.0187 _refine_ls_wR_factor_ref 0.0416 _refine_ls_wR_factor_gt 0.0401 _refine_ls_goodness_of_fit_ref 1.069 _refine_ls_restrained_S_all 1.069 _refine_ls_shift/su_max 0.001 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group I1 I 0.298364(19) 0.445777(13) 0.332661(9) 0.01614(3) Uani 1 1 d . . . I2 I 0.72305(2) 0.080520(13) 0.427823(10) 0.01731(3) Uani 1 1 d . . . I3 I 0.277435(19) 0.443767(13) 0.129710(9) 0.01602(3) Uani 1 1 d . . . I4 I 0.25003(2) 0.411636(15) -0.043937(10) 0.02035(3) Uani 1 1 d . . . I5 I 0.19264(2) 0.369881(16) -0.269513(10) 0.02408(4) Uani 1 1 d . . . I6 I -0.02172(2) 0.227156(14) -0.409254(10) 0.01813(3) Uani 1 1 d . . . Ru1 Ru 0.52538(2) 0.268927(15) 0.378674(10) 0.01065(3) Uani 1 1 d . . . O1 O 0.4114(2) 0.27692(18) 0.54729(11) 0.0239(4) Uani 1 1 d . . . O2 O 0.8139(2) 0.46622(16) 0.45739(11) 0.0216(3) Uani 1 1 d . . . O3 O 0.8358(2) 0.25018(17) -0.00369(11) 0.0205(3) Uani 1 1 d . . . H3O H 0.8258 0.2371 -0.0557 0.031 Uiso 1 1 d R . . O4 O 0.5782(2) 0.13751(16) -0.05516(10) 0.0178(3) Uani 1 1 d . . . O5 O -0.2549(2) -0.08215(16) 0.16210(11) 0.0187(3) Uani 1 1 d . . . H5O H -0.3501 -0.1084 0.1231 0.028 Uiso 1 1 d R . . O6 O -0.1495(2) -0.04527(17) 0.04766(11) 0.0204(3) Uani 1 1 d . . . O7 O -0.1526(2) 0.23008(16) -0.16676(11) 0.0190(3) Uani 1 1 d . . . H7O H -0.0650 0.2743 -0.1796 0.029 Uiso 1 1 d R . . N1 N 0.5969(2) 0.24675(16) 0.25847(11) 0.0114(3) Uani 1 1 d . . . N2 N 0.3195(2) 0.14711(16) 0.30282(12) 0.0125(3) Uani 1 1 d . . . C1 C 0.4514(3) 0.2757(2) 0.48377(15) 0.0160(4) Uani 1 1 d . . . C2 C 0.7091(3) 0.3897(2) 0.43062(14) 0.0148(4) Uani 1 1 d . . . C3 C 0.7466(3) 0.29578(19) 0.24137(14) 0.0135(4) Uani 1 1 d . . . H3 H 0.8317 0.3417 0.2870 0.016 Uiso 1 1 calc R . . C4 C 0.7822(3) 0.2823(2) 0.16032(14) 0.0141(4) Uani 1 1 d . . . H4 H 0.8885 0.3191 0.1503 0.017 Uiso 1 1 calc R . . C5 C 0.6585(3) 0.21349(19) 0.09363(13) 0.0125(3) Uani 1 1 d . . . C6 C 0.6857(3) 0.19613(19) 0.00391(14) 0.0138(4) Uani 1 1 d . . . C7 C 0.5049(3) 0.16007(19) 0.11078(13) 0.0120(3) Uani 1 1 d . . . H7 H 0.4203 0.1115 0.0665 0.014 Uiso 1 1 calc R . . C8 C 0.4770(3) 0.17876(18) 0.19373(13) 0.0112(3) Uani 1 1 d . . . C9 C 0.3173(3) 0.12823(18) 0.21781(13) 0.0107(3) Uani 1 1 d . . . C10 C 0.1716(3) 0.06730(19) 0.15849(13) 0.0126(4) Uani 1 1 d . . . H10 H 0.1698 0.0574 0.0990 0.015 Uiso 1 1 calc R . . C11 C 0.0285(3) 0.02113(18) 0.18791(13) 0.0117(3) Uani 1 1 d . . . C12 C -0.1328(3) -0.03995(19) 0.12420(14) 0.0131(4) Uani 1 1 d . . . C13 C 0.0351(3) 0.0354(2) 0.27506(14) 0.0138(4) Uani 1 1 d . . . H13 H -0.0595 0.0018 0.2963 0.017 Uiso 1 1 calc R . . C14 C 0.1819(3) 0.0994(2) 0.33060(14) 0.0153(4) Uani 1 1 d . . . H14 H 0.1858 0.1101 0.3903 0.018 Uiso 1 1 calc R . . C15 C -0.3198(3) 0.2150(2) -0.23176(17) 0.0231(5) Uani 1 1 d . . . H15A H -0.3746 0.2931 -0.2375 0.035 Uiso 1 1 calc R . . H15B H -0.4042 0.1597 -0.2154 0.035 Uiso 1 1 calc R . . H15C H -0.2944 0.1818 -0.2867 0.035 Uiso 1 1 calc 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 I1 0.01786(6) 0.01636(6) 0.01392(6) 0.00039(5) 0.00359(5) 0.00437(5) I2 0.01973(6) 0.01645(6) 0.01759(6) 0.00346(5) 0.00713(5) 0.00480(5) I3 0.01621(6) 0.01497(6) 0.01608(6) 0.00165(5) 0.00212(5) 0.00220(5) I4 0.02069(7) 0.02403(7) 0.01532(6) 0.00268(5) 0.00220(5) -0.00220(5) I5 0.02950(8) 0.02630(8) 0.01658(7) 0.00512(6) 0.00432(6) 0.00218(6) I6 0.01795(6) 0.02045(7) 0.01850(7) 0.00809(5) 0.00618(5) 0.00519(5) Ru1 0.01084(6) 0.01185(7) 0.00905(6) -0.00064(5) 0.00294(5) -0.00077(5) O1 0.0247(8) 0.0306(10) 0.0175(8) -0.0018(7) 0.0096(7) -0.0034(7) O2 0.0216(8) 0.0221(8) 0.0187(8) 0.0011(7) 0.0012(6) -0.0069(7) O3 0.0187(7) 0.0276(9) 0.0160(7) -0.0035(7) 0.0095(6) -0.0090(7) O4 0.0147(7) 0.0247(8) 0.0137(7) -0.0018(6) 0.0054(6) -0.0043(6) O5 0.0146(7) 0.0257(9) 0.0156(7) 0.0012(6) 0.0041(6) -0.0084(6) O6 0.0174(7) 0.0299(9) 0.0130(7) -0.0004(6) 0.0037(6) -0.0071(7) O7 0.0191(7) 0.0205(8) 0.0187(8) 0.0010(6) 0.0081(6) -0.0033(6) N1 0.0116(7) 0.0111(7) 0.0114(7) -0.0004(6) 0.0035(6) -0.0013(6) N2 0.0136(7) 0.0123(8) 0.0122(8) 0.0001(6) 0.0054(6) -0.0003(6) C1 0.0137(9) 0.0164(10) 0.0165(9) -0.0017(8) 0.0028(7) -0.0021(7) C2 0.0148(9) 0.0178(10) 0.0116(9) 0.0016(7) 0.0030(7) 0.0018(7) C3 0.0127(8) 0.0138(9) 0.0137(9) -0.0003(7) 0.0036(7) -0.0027(7) C4 0.0129(8) 0.0160(9) 0.0144(9) 0.0012(7) 0.0055(7) -0.0021(7) C5 0.0135(8) 0.0119(9) 0.0130(9) 0.0007(7) 0.0057(7) -0.0001(7) C6 0.0146(9) 0.0136(9) 0.0144(9) 0.0012(7) 0.0063(7) -0.0002(7) C7 0.0130(8) 0.0123(9) 0.0114(8) -0.0004(7) 0.0051(7) -0.0016(7) C8 0.0112(8) 0.0106(8) 0.0123(8) 0.0002(7) 0.0044(7) -0.0015(6) C9 0.0114(8) 0.0097(8) 0.0118(8) 0.0005(6) 0.0049(7) -0.0013(6) C10 0.0130(8) 0.0126(9) 0.0124(8) -0.0006(7) 0.0045(7) -0.0007(7) C11 0.0120(8) 0.0110(8) 0.0122(8) 0.0010(7) 0.0033(7) -0.0005(7) C12 0.0121(8) 0.0127(9) 0.0144(9) 0.0010(7) 0.0034(7) -0.0017(7) C13 0.0140(8) 0.0153(9) 0.0130(9) 0.0016(7) 0.0050(7) -0.0022(7) C14 0.0165(9) 0.0194(10) 0.0113(9) 0.0011(7) 0.0065(7) -0.0021(8) C15 0.0223(11) 0.0244(12) 0.0225(11) 0.0038(9) 0.0042(9) 0.0024(9) _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 I1 Ru1 2.7028(2) . yes I1 I3 3.2376(2) . yes I2 Ru1 2.6987(2) . yes I2 I6 3.1442(2) 1_656 yes I3 I4 2.7401(2) . yes I4 I5 3.5371(2) . yes I5 I6 2.7672(2) . yes I6 I2 3.1442(2) 1_454 yes Ru1 C1 1.895(2) . yes Ru1 C2 1.897(2) . yes Ru1 N2 2.1082(18) . yes Ru1 N1 2.1155(17) . yes O1 C1 1.130(3) . ? O2 C2 1.132(3) . ? O3 C6 1.313(3) . yes O3 H3O 0.8203 . ? O4 C6 1.217(3) . yes O5 C12 1.325(3) . yes O5 H5O 0.8613 . ? O6 C12 1.206(3) . yes O7 C15 1.438(3) . ? O7 H7O 0.8954 . ? N1 C3 1.346(3) . ? N1 C8 1.360(3) . ? N2 C14 1.346(3) . ? N2 C9 1.358(3) . ? C3 C4 1.385(3) . ? C3 H3 0.9500 . ? C4 C5 1.395(3) . ? C4 H4 0.9500 . ? C5 C7 1.393(3) . ? C5 C6 1.497(3) . ? C7 C8 1.393(3) . ? C7 H7 0.9500 . ? C8 C9 1.472(3) . ? C9 C10 1.390(3) . ? C10 C11 1.389(3) . ? C10 H10 0.9500 . ? C11 C13 1.385(3) . ? C11 C12 1.498(3) . ? C13 C14 1.384(3) . ? C13 H13 0.9500 . ? C14 H14 0.9500 . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? 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 Ru1 I1 I3 104.045(6) . . yes Ru1 I2 I6 95.256(6) . 1_656 yes I4 I3 I1 172.802(7) . . yes I3 I4 I5 177.370(7) . . yes I6 I5 I4 137.789(7) . . yes I5 I6 I2 176.214(7) . 1_454 yes C1 Ru1 C2 89.16(9) . . yes C1 Ru1 N2 98.52(8) . . ? C2 Ru1 N2 170.85(8) . . ? C1 Ru1 N1 175.14(8) . . ? C2 Ru1 N1 95.37(8) . . ? N2 Ru1 N1 77.12(7) . . yes C1 Ru1 I2 86.97(7) . . ? C2 Ru1 I2 96.32(7) . . ? N2 Ru1 I2 89.08(5) . . ? N1 Ru1 I2 90.81(5) . . ? C1 Ru1 I1 89.49(7) . . ? C2 Ru1 I1 88.19(7) . . ? N2 Ru1 I1 86.93(5) . . ? N1 Ru1 I1 92.37(5) . . ? I2 Ru1 I1 174.226(8) . . yes C6 O3 H3O 100.9 . . ? C12 O5 H5O 108.4 . . ? C15 O7 H7O 114.4 . . ? C3 N1 C8 118.61(18) . . ? C3 N1 Ru1 125.58(14) . . ? C8 N1 Ru1 115.80(13) . . ? C14 N2 C9 118.92(18) . . ? C14 N2 Ru1 124.84(14) . . ? C9 N2 Ru1 115.77(13) . . ? O1 C1 Ru1 177.7(2) . . ? O2 C2 Ru1 175.4(2) . . ? N1 C3 C4 122.94(19) . . ? N1 C3 H3 118.5 . . ? C4 C3 H3 118.5 . . ? C3 C4 C5 118.53(19) . . ? C3 C4 H4 120.7 . . ? C5 C4 H4 120.7 . . ? C7 C5 C4 119.15(19) . . ? C7 C5 C6 119.05(18) . . ? C4 C5 C6 121.80(18) . . ? O4 C6 O3 124.2(2) . . yes O4 C6 C5 122.63(19) . . ? O3 C6 C5 113.13(18) . . ? C8 C7 C5 119.10(19) . . ? C8 C7 H7 120.4 . . ? C5 C7 H7 120.4 . . ? N1 C8 C7 121.64(18) . . ? N1 C8 C9 115.19(17) . . ? C7 C8 C9 123.17(18) . . ? N2 C9 C10 121.58(18) . . ? N2 C9 C8 115.26(17) . . ? C10 C9 C8 123.15(18) . . ? C11 C10 C9 118.73(19) . . ? C11 C10 H10 120.6 . . ? C9 C10 H10 120.6 . . ? C13 C11 C10 119.59(19) . . ? C13 C11 C12 121.24(18) . . ? C10 C11 C12 119.14(18) . . ? O6 C12 O5 125.1(2) . . yes O6 C12 C11 122.89(19) . . ? O5 C12 C11 112.01(18) . . ? C14 C13 C11 118.84(19) . . ? C14 C13 H13 120.6 . . ? C11 C13 H13 120.6 . . ? N2 C14 C13 122.2(2) . . ? N2 C14 H14 118.9 . . ? C13 C14 H14 118.9 . . ? O7 C15 H15A 109.5 . . ? O7 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? O7 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? 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 _geom_hbond_publ_flag O3 H3O O7 0.82 1.83 2.634(2) 167.5 1_655 yes O5 H5O O4 0.86 1.82 2.664(2) 166.3 2 yes O7 H7O I5 0.90 2.93 3.7983(17) 162.8 . yes O7 H7O I4 0.90 3.09 3.6609(17) 123.8 . yes _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 32.50 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 1.448 _refine_diff_density_min -1.023 _refine_diff_density_rms 0.129 # start Validation Reply Form _vrf_PUBL431_GLOBAL ; PROBLEM: Short Inter HL..A Contact I1..I3 3.24 Ang. RESPONSE: This is due to the strong halogen bond. Not an error ; _vrf_PUBL780_GLOBAL ; PROBLEM: Coordinates do not Form a Properly Connected Set RESPONSE: The coordinates are organized in such way that the halogen bonds are emphasized. ; # end Validation Reply Form