+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ + SHELXL-97 - CRYSTAL STRUCTURE REFINEMENT - WinGX VERSION + + Copyright(C) George M. Sheldrick 1993-7 Release 97-2 + + 2008lsh052 started at 15:43:12 on 21-Jul-2008 + +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ TITL 2008lsh052 in P2(1)/n CELL 0.71073 4.7808 11.9344 14.6859 90.000 96.820 90.000 ZERR 4.00 0.0001 0.0005 0.0005 0.000 0.002 0.000 LATT 1 SYMM 1/2 - X, 1/2 + Y, 1/2 - Z SFAC C H N O BR UNIT 32 32 4 4 4 V = 831.99 F(000) = 424.0 Mu = 4.88 mm-1 Cell Wt = 856.26 Rho = 1.709 MERG 2 OMIT -3.00 55.00 FMAP 2 PLAN 5 ACTA SIZE 0.4 0.08 0.04 EQIV $1 x-1, y, z HTAB N1 O1_$1 HTAB BOND $H L.S. 6 TEMP -153.00 WGHT 0.0206 0.6348 FVAR 0.64854 C1 1 0.549418 0.059863 0.140026 11.00000 0.01151 0.01396 = 0.01817 -0.00006 0.00020 -0.00136 C2 1 0.465759 0.019300 0.221402 11.00000 0.01407 0.01574 = 0.01870 -0.00107 0.00290 -0.00156 C3 1 0.550428 -0.084891 0.256225 11.00000 0.01883 0.02089 = 0.02288 0.00496 0.00308 -0.00158 AFIX 43 H3 2 0.485436 -0.111939 0.310810 11.00000 -1.20000 AFIX 0 C4 1 0.731112 -0.149203 0.210471 11.00000 0.02258 0.01650 = 0.02935 0.00363 0.00001 0.00200 AFIX 43 H4 2 0.792226 -0.220286 0.234223 11.00000 -1.20000 AFIX 0 C5 1 0.823101 -0.109980 0.129947 11.00000 0.01676 0.01886 = 0.02576 -0.00497 0.00018 0.00378 AFIX 43 H5 2 0.949135 -0.153719 0.099301 11.00000 -1.20000 AFIX 0 C6 1 0.730438 -0.006648 0.094299 11.00000 0.01516 0.02023 = 0.01568 -0.00185 0.00156 0.00189 AFIX 43 H6 2 0.790256 0.019078 0.038528 11.00000 -1.20000 AFIX 0 C7 1 0.610139 0.240639 0.064851 11.00000 0.01471 0.01672 = 0.01625 -0.00001 0.00339 0.00020 C8 1 0.459127 0.345503 0.029487 11.00000 0.01859 0.01979 = 0.02745 0.00548 0.00768 0.00231 AFIX 137 H8A 2 0.475851 0.402577 0.077805 11.00000 -1.50000 H8B 2 0.259716 0.328561 0.011346 11.00000 -1.50000 H8C 2 0.543546 0.373606 -0.023701 11.00000 -1.50000 AFIX 0 N1 3 0.448470 0.163567 0.102755 11.00000 0.01004 0.01680 = 0.01721 0.00155 0.00363 0.00163 O1 4 0.863551 0.228054 0.061332 11.00000 0.01334 0.02432 = 0.03337 0.00479 0.00790 0.00110 BR1 5 0.232356 0.108842 0.288415 11.00000 0.02073 0.02234 = 0.02083 -0.00045 0.00983 0.00045 H1N 2 0.278387 0.175980 0.103186 11.00000 0.02181 HKLF 4 Covalent radii and connectivity table for 2008lsh052 in P2(1)/n C 0.770 H 0.320 N 0.700 O 0.660 BR 1.140 C1 - C2 C6 N1 C2 - C3 C1 Br1 C3 - C2 C4 C4 - C3 C5 C5 - C4 C6 C6 - C5 C1 C7 - O1 N1 C8 C8 - C7 N1 - C7 C1 O1 - C7 Br1 - C2 Operators for generating equivalent atoms: $1 x-1, y, z 11305 Reflections read, of which 379 rejected -6 =< h =< 6, -15 =< k =< 15, -18 =< l =< 19, Max. 2-theta = 55.00 0 Systematic absence violations Inconsistent equivalents etc. h k l Fo^2 Sigma(Fo^2) N Esd of mean(Fo^2) 4 6 9 -1.23 2.11 2 18.53 1 Inconsistent equivalents 1899 Unique reflections, of which 0 suppressed R(int) = 0.0357 R(sigma) = 0.0283 Friedel opposites merged Maximum memory for data reduction = 1201 / 19150 Default effective X-H distances for T = -153.0 C AFIX m = 1 2 3 4 4[N] 3[N] 15[B] 8[O] 9 9[N] 16 d(X-H) = 1.00 0.99 0.98 0.95 0.88 0.91 1.12 0.84 0.95 0.88 0.95 Note that these distances are chosen to give the best fit to the X-ray data and so avoid the introduction of systematic error. The true internuclear distances are longer and do not vary with temperature ! The apparent variation with temperature is caused by libration. Least-squares cycle 1 Maximum vector length = 511 Memory required = 1486 / 137102 wR2 = 0.0563 before cycle 1 for 1899 data and 105 / 105 parameters GooF = S = 1.080; Restrained GooF = 1.080 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0206 * P )^2 + 0.63 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.64713 0.00087 -1.623 OSF Mean shift/esd = 0.268 Maximum = -1.623 for OSF Max. shift = 0.007 A for H8A Max. dU =-0.001 for H1N Least-squares cycle 2 Maximum vector length = 511 Memory required = 1486 / 137102 wR2 = 0.0561 before cycle 2 for 1899 data and 105 / 105 parameters GooF = S = 1.076; Restrained GooF = 1.076 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0206 * P )^2 + 0.63 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.64666 0.00086 -0.544 OSF Mean shift/esd = 0.090 Maximum = -0.544 for OSF Max. shift = 0.006 A for H8A Max. dU = 0.000 for H1N Least-squares cycle 3 Maximum vector length = 511 Memory required = 1486 / 137102 wR2 = 0.0560 before cycle 3 for 1899 data and 105 / 105 parameters GooF = S = 1.075; Restrained GooF = 1.075 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0206 * P )^2 + 0.63 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.64667 0.00086 0.006 OSF Mean shift/esd = 0.005 Maximum = 0.232 for tors H8A Max. shift = 0.004 A for H8C Max. dU = 0.000 for H1N Least-squares cycle 4 Maximum vector length = 511 Memory required = 1486 / 137102 wR2 = 0.0560 before cycle 4 for 1899 data and 105 / 105 parameters GooF = S = 1.076; Restrained GooF = 1.076 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0206 * P )^2 + 0.63 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.64668 0.00086 0.009 OSF Mean shift/esd = 0.003 Maximum = 0.134 for tors H8A Max. shift = 0.002 A for H8C Max. dU = 0.000 for H1N Least-squares cycle 5 Maximum vector length = 511 Memory required = 1486 / 137102 wR2 = 0.0561 before cycle 5 for 1899 data and 105 / 105 parameters GooF = S = 1.076; Restrained GooF = 1.076 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0206 * P )^2 + 0.63 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.64668 0.00086 0.001 OSF Mean shift/esd = 0.002 Maximum = 0.077 for tors H8A Max. shift = 0.001 A for H8C Max. dU = 0.000 for H1N Least-squares cycle 6 Maximum vector length = 511 Memory required = 1486 / 137102 wR2 = 0.0561 before cycle 6 for 1899 data and 105 / 105 parameters GooF = S = 1.076; Restrained GooF = 1.076 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0206 * P )^2 + 0.63 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.64668 0.00086 0.002 OSF Mean shift/esd = 0.001 Maximum = 0.044 for tors H8A Max. shift = 0.001 A for H8C Max. dU = 0.000 for H1N Largest correlation matrix elements 0.568 U33 Br1 / OSF 0.559 U11 Br1 / OSF 0.544 U22 Br1 / OSF Idealized hydrogen atom generation before cycle 7 Name x y z AFIX d(X-H) shift Bonded to Conformation determined by H3 0.4855 -0.1119 0.3107 43 0.950 0.000 C3 C2 C4 H4 0.7923 -0.2201 0.2343 43 0.950 0.000 C4 C3 C5 H5 0.9486 -0.1537 0.0993 43 0.950 0.000 C5 C4 C6 H6 0.7901 0.0189 0.0386 43 0.950 0.000 C6 C5 C1 H8A 0.4796 0.4031 0.0773 137 0.980 0.000 C8 C7 H8A H8B 0.2591 0.3289 0.0126 137 0.980 0.000 C8 C7 H8A H8C 0.5411 0.3726 -0.0245 137 0.980 0.000 C8 C7 H8A 2008lsh052 in P2(1)/n ATOM x y z sof U11 U22 U33 U23 U13 U12 Ueq C1 0.54930 0.05979 0.13999 1.00000 0.01127 0.01361 0.01757 -0.00017 0.00010 -0.00117 0.01428 0.00342 0.00039 0.00017 0.00013 0.00000 0.00090 0.00098 0.00098 0.00080 0.00069 0.00073 0.00039 C2 0.46571 0.01928 0.22140 1.00000 0.01376 0.01584 0.01845 -0.00116 0.00271 -0.00181 0.01595 0.00353 0.00040 0.00017 0.00014 0.00000 0.00092 0.00101 0.00101 0.00080 0.00073 0.00074 0.00040 C3 0.55053 -0.08484 0.25612 1.00000 0.01827 0.02084 0.02229 0.00518 0.00277 -0.00190 0.02044 0.00389 0.00044 0.00018 0.00015 0.00000 0.00105 0.00112 0.00110 0.00087 0.00081 0.00080 0.00045 H3 0.48551 -0.11192 0.31069 1.00000 0.02453 0.00000 0.00000 C4 0.73103 -0.14909 0.21051 1.00000 0.02166 0.01620 0.02983 0.00401 -0.00036 0.00234 0.02284 0.00395 0.00043 0.00019 0.00015 0.00000 0.00109 0.00109 0.00125 0.00092 0.00087 0.00082 0.00047 H4 0.79233 -0.22012 0.23433 1.00000 0.02741 0.00000 0.00000 C5 0.82275 -0.10995 0.12997 1.00000 0.01647 0.01840 0.02574 -0.00524 0.00024 0.00360 0.02039 0.00380 0.00045 0.00017 0.00016 0.00000 0.00102 0.00106 0.00112 0.00088 0.00081 0.00079 0.00044 H5 0.94864 -0.15372 0.09929 1.00000 0.02446 0.00000 0.00000 C6 0.73020 -0.00678 0.09438 1.00000 0.01495 0.01999 0.01569 -0.00132 0.00157 0.00178 0.01690 0.00360 0.00041 0.00018 0.00014 0.00000 0.00094 0.00109 0.00098 0.00082 0.00073 0.00076 0.00041 H6 0.79007 0.01890 0.03861 1.00000 0.02028 0.00000 0.00000 C7 0.61002 0.24064 0.06486 1.00000 0.01497 0.01642 0.01539 -0.00050 0.00328 0.00030 0.01547 0.00354 0.00040 0.00017 0.00013 0.00000 0.00098 0.00102 0.00097 0.00079 0.00073 0.00075 0.00040 C8 0.45933 0.34546 0.02949 1.00000 0.01835 0.01923 0.02731 0.00537 0.00767 0.00223 0.02123 0.00409 0.00044 0.00018 0.00015 0.00000 0.00102 0.00111 0.00117 0.00092 0.00083 0.00082 0.00045 H8A 0.47962 0.40310 0.07734 1.00000 0.03185 0.00000 0.00000 H8B 0.25910 0.32894 0.01259 1.00000 0.03185 0.00000 0.00000 H8C 0.54115 0.37259 -0.02451 1.00000 0.03185 0.00000 0.00000 N1 0.44876 0.16365 0.10278 1.00000 0.00959 0.01619 0.01732 0.00187 0.00342 0.00173 0.01422 0.00300 0.00035 0.00015 0.00011 0.00000 0.00082 0.00089 0.00087 0.00069 0.00061 0.00064 0.00034 O1 0.86364 0.22806 0.06134 1.00000 0.01274 0.02413 0.03323 0.00457 0.00772 0.00096 0.02296 0.00277 0.00029 0.00013 0.00011 0.00000 0.00073 0.00085 0.00087 0.00069 0.00059 0.00059 0.00034 Br1 0.23236 0.10884 0.28842 1.00000 0.02053 0.02209 0.02065 -0.00047 0.00981 0.00045 0.02050 0.00038 0.00004 0.00002 0.00001 0.00000 0.00013 0.00013 0.00013 0.00009 0.00008 0.00008 0.00008 H1N 0.27937 0.17635 0.10363 1.00000 0.02036 0.04306 0.00528 0.00209 0.00155 0.00000 0.00619 Final Structure Factor Calculation for 2008lsh052 in P2(1)/n Total number of l.s. parameters = 105 Maximum vector length = 511 Memory required = 1381 / 24017 wR2 = 0.0561 before cycle 7 for 1899 data and 0 / 105 parameters GooF = S = 1.076; Restrained GooF = 1.076 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0206 * P )^2 + 0.63 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 R1 = 0.0244 for 1686 Fo > 4sig(Fo) and 0.0306 for all 1899 data wR2 = 0.0561, GooF = S = 1.076, Restrained GooF = 1.076 for all data Occupancy sum of asymmetric unit = 11.00 for non-hydrogen and 8.00 for hydrogen atoms Principal mean square atomic displacements U 0.0182 0.0141 0.0106 C1 0.0191 0.0161 0.0127 C2 0.0271 0.0192 0.0150 C3 0.0321 0.0223 0.0141 C4 0.0301 0.0179 0.0132 C5 0.0210 0.0154 0.0143 C6 0.0167 0.0164 0.0134 C7 0.0315 0.0168 0.0154 C8 0.0191 0.0148 0.0087 N1 0.0357 0.0223 0.0109 O1 0.0272 0.0221 0.0122 Br1 Analysis of variance for reflections employed in refinement K = Mean[Fo^2] / Mean[Fc^2] for group Fc/Fc(max) 0.000 0.021 0.041 0.065 0.088 0.114 0.147 0.181 0.235 0.318 1.000 Number in group 195. 191. 196. 182. 186. 191. 190. 193. 185. 190. GooF 1.046 1.081 1.082 1.157 1.253 1.042 0.999 0.889 1.000 1.177 K 1.460 0.958 1.004 0.984 0.980 0.988 0.996 1.009 1.011 0.990 Resolution(A) 0.77 0.80 0.83 0.87 0.91 0.97 1.05 1.15 1.32 1.64 inf Number in group 193. 187. 190. 191. 190. 191. 190. 188. 188. 191. GooF 1.087 0.976 1.057 1.035 0.913 0.867 0.937 0.995 1.142 1.579 K 0.973 0.993 0.988 0.997 1.011 1.017 1.017 1.018 1.006 0.975 R1 0.075 0.062 0.047 0.038 0.029 0.023 0.021 0.018 0.018 0.021 Recommended weighting scheme: WGHT 0.0177 0.7142 Note that in most cases convergence will be faster if fixed weights (e.g. the default WGHT 0.1) are retained until the refinement is virtually complete, and only then should the above recommended values be used. Most Disagreeable Reflections (* if suppressed or used for Rfree) h k l Fo^2 Fc^2 Delta(F^2)/esd Fc/Fc(max) Resolution(A) 0 6 1 1359.90 1585.70 4.44 0.247 1.97 0 2 8 700.25 585.32 4.29 0.150 1.74 1 4 3 184.34 245.96 4.18 0.097 2.19 1 2 2 23346.85 25961.60 4.02 1.000 3.19 -4 5 13 251.50 338.88 3.66 0.114 0.82 5 1 5 88.82 141.38 3.53 0.074 0.87 -4 1 14 154.36 210.76 3.35 0.090 0.83 -2 2 2 14.17 3.30 3.34 0.011 2.18 -1 1 6 2933.68 3223.09 3.31 0.352 2.24 -3 12 8 141.00 218.01 3.19 0.092 0.78 2 2 2 568.59 490.89 3.14 0.138 2.05 1 0 1 10684.45 12330.97 3.13 0.689 4.36 -2 3 5 174.01 217.23 3.12 0.091 1.76 2 1 10 1451.34 1298.16 3.06 0.224 1.18 -1 0 5 80.12 108.88 3.01 0.065 2.63 -4 5 14 47.84 4.64 3.00 0.013 0.79 4 5 6 43.50 72.18 2.95 0.053 0.94 1 12 8 -1.18 25.92 2.95 0.032 0.85 -3 3 1 1489.63 1652.01 2.94 0.252 1.48 -2 2 4 694.59 616.34 2.88 0.154 1.99 -4 11 6 341.24 429.70 2.86 0.129 0.78 2 7 11 33.80 8.83 2.86 0.018 0.93 -4 7 10 193.74 247.32 2.85 0.098 0.85 2 7 1 4.97 24.91 2.84 0.031 1.37 -1 1 3 4132.05 4464.46 2.76 0.415 3.46 1 5 1 796.93 706.78 2.74 0.165 2.09 4 11 0 183.74 241.26 2.74 0.096 0.80 -1 4 4 152.27 187.37 2.73 0.085 2.14 -3 5 9 22.80 5.43 2.73 0.014 1.08 1 2 7 197.14 157.04 2.70 0.078 1.75 1 5 3 45.01 28.90 2.69 0.033 1.92 3 9 7 116.06 151.16 2.69 0.076 0.89 -3 13 2 221.45 298.54 2.66 0.107 0.79 2 3 5 123.64 95.21 2.62 0.061 1.60 -1 6 7 16.77 2.05 2.60 0.009 1.41 2 5 3 539.71 609.02 2.58 0.153 1.55 0 8 16 189.33 263.77 2.54 0.101 0.78 -3 4 4 79.20 59.23 2.53 0.048 1.35 -3 2 3 1212.05 1106.06 2.51 0.206 1.51 -3 5 13 12.96 37.96 2.49 0.038 0.90 2 3 3 57.69 41.73 2.48 0.040 1.81 -2 3 6 3924.45 4202.48 2.47 0.402 1.65 3 1 2 24.03 12.36 2.47 0.022 1.50 4 7 7 348.43 425.33 2.44 0.128 0.85 -3 1 3 767.65 844.76 2.39 0.180 1.55 0 10 7 98.49 126.14 2.39 0.070 1.04 1 12 6 419.93 492.92 2.39 0.138 0.90 -2 5 8 279.96 240.53 2.38 0.096 1.29 2 1 16 122.91 197.66 2.38 0.087 0.82 -4 1 15 923.77 1056.06 2.36 0.202 0.80 Bond lengths and angles C1 - Distance Angles C2 1.3916 (0.0028) C6 1.4019 (0.0028) 118.03 (0.18) N1 1.4155 (0.0026) 121.13 (0.18) 120.82 (0.18) C1 - C2 C6 C2 - Distance Angles C3 1.3854 (0.0029) C1 1.3916 (0.0028) 121.77 (0.19) Br1 1.9017 (0.0020) 118.54 (0.16) 119.69 (0.15) C2 - C3 C1 C3 - Distance Angles C2 1.3854 (0.0029) C4 1.3851 (0.0031) 119.37 (0.20) H3 0.9500 120.31 120.31 C3 - C2 C4 C4 - Distance Angles C3 1.3851 (0.0031) C5 1.3902 (0.0031) 120.20 (0.20) H4 0.9500 119.90 119.90 C4 - C3 C5 C5 - Distance Angles C4 1.3902 (0.0031) C6 1.3893 (0.0029) 119.96 (0.20) H5 0.9500 120.02 120.02 C5 - C4 C6 C6 - Distance Angles C5 1.3893 (0.0029) C1 1.4019 (0.0028) 120.63 (0.19) H6 0.9500 119.68 119.68 C6 - C5 C1 C7 - Distance Angles O1 1.2290 (0.0024) N1 1.3604 (0.0025) 123.00 (0.19) C8 1.5049 (0.0028) 121.42 (0.18) 115.56 (0.17) C7 - O1 N1 C8 - Distance Angles C7 1.5049 (0.0028) H8A 0.9800 109.47 H8B 0.9800 109.47 109.47 H8C 0.9800 109.47 109.47 109.47 C8 - C7 H8A H8B N1 - Distance Angles C7 1.3604 (0.0025) C1 1.4155 (0.0026) 124.51 (0.17) H1N 0.8254 (0.0247) 119.13 (1.73) 116.35 (1.73) N1 - C7 C1 O1 - Distance Angles C7 1.2290 (0.0024) O1 - Br1 - Distance Angles C2 1.9017 (0.0020) Br1 - Specified hydrogen bonds (with esds except fixed and riding H) D-H H...A D...A <(DHA) 0.83(2) 2.10(3) 2.895(2) 161(2) N1-H1N...O1_$1 Hydrogen bonds with H..A < r(A) + 2.000 Angstroms and 110 deg. D-H d(D-H) d(H..A)