+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ + SHELXL-97 - CRYSTAL STRUCTURE REFINEMENT - WinGX VERSION + + Copyright(C) George M. Sheldrick 1993-7 Release 97-2 + + 2008lsh018 started at 14:45:28 on 05-Jul-2008 + +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ TITL 2008lsh018 in Pbca CELL 0.71073 9.3819 9.2804 20.7436 90.000 90.000 90.000 ZERR 8.00 0.0002 0.0002 0.0005 0.000 0.000 0.000 LATT 1 SYMM 1/2 - X, - Y, 1/2 + Z SYMM - X, 1/2 + Y, 1/2 - Z SYMM 1/2 + X, 1/2 - Y, - Z SFAC C H N O BR UNIT 72 80 8 8 8 V = 1806.10 F(000) = 912.0 Mu = 4.50 mm-1 Cell Wt = 1824.72 Rho = 1.678 MERG 2 OMIT -3.00 55.00 OMIT 1 2 3 FMAP 2 PLAN 5 ACTA EQIV $1 x+1/2, y, -z+1/2 HTAB N1 O1_$1 HTAB SIZE 0.4 0.1 0.1 BOND $H L.S. 6 TEMP -153.00 WGHT 0.0124 2.5876 FVAR 0.45809 C1 1 0.291948 0.340395 0.352179 11.00000 0.02226 0.02131 = 0.02139 -0.00549 -0.00092 0.00055 C2 1 0.157313 0.313772 0.377759 11.00000 0.01842 0.02973 = 0.02556 -0.00212 -0.00275 0.00054 AFIX 43 H2 2 0.075957 0.359660 0.359815 11.00000 -1.20000 AFIX 0 C3 1 0.141949 0.220065 0.429545 11.00000 0.02383 0.03008 = 0.02387 -0.00384 0.00121 -0.00362 AFIX 43 H3 2 0.050005 0.200775 0.446682 11.00000 -1.20000 AFIX 0 C4 1 0.260595 0.155118 0.456005 11.00000 0.03440 0.01991 = 0.01952 -0.00127 -0.00092 -0.00105 C5 1 0.395140 0.180152 0.431297 11.00000 0.02712 0.03068 = 0.02634 -0.00181 -0.00497 0.00592 AFIX 43 H5 2 0.476054 0.134280 0.449654 11.00000 -1.20000 AFIX 0 C6 1 0.410676 0.273181 0.379302 11.00000 0.01927 0.03309 = 0.02695 -0.00237 0.00191 0.00191 AFIX 43 H6 2 0.502811 0.291159 0.362090 11.00000 -1.20000 AFIX 0 C7 1 0.221312 0.487609 0.257386 11.00000 0.02149 0.02299 = 0.02184 -0.00257 -0.00113 0.00040 C8 1 0.284488 0.591648 0.208841 11.00000 0.02382 0.02802 = 0.02665 0.00283 0.00035 -0.00138 AFIX 23 H8A 2 0.344684 0.662677 0.231790 11.00000 -1.20000 H8B 2 0.346341 0.537713 0.178627 11.00000 -1.20000 AFIX 0 C9 1 0.171182 0.670810 0.170875 11.00000 0.02933 0.02931 = 0.02958 0.00343 -0.00167 0.00146 AFIX 137 H9A 2 0.112024 0.601027 0.147607 11.00000 -1.50000 H9B 2 0.216814 0.736019 0.139973 11.00000 -1.50000 H9C 2 0.111332 0.726650 0.200457 11.00000 -1.50000 AFIX 0 N1 3 0.316730 0.437343 0.301040 11.00000 0.01415 0.02795 = 0.02363 0.00151 0.00054 -0.00084 O1 4 0.095854 0.452177 0.256569 11.00000 0.01683 0.03697 = 0.03108 0.00543 -0.00307 -0.00246 BR1 5 0.237902 0.031780 0.528310 11.00000 0.04404 0.02918 = 0.02328 0.00307 0.00116 0.00335 H1N 2 0.397911 0.456018 0.293163 11.00000 0.01770 HKLF 4 1.0 0.00 1.00 0.00 1.00 0.00 0.00 0.00 0.00 -1.00 Covalent radii and connectivity table for 2008lsh018 in Pbca C 0.770 H 0.320 N 0.700 O 0.660 BR 1.140 C1 - C2 C6 N1 C2 - C3 C1 C3 - C4 C2 C4 - C3 C5 Br1 C5 - C4 C6 C6 - C5 C1 C7 - O1 N1 C8 C8 - C9 C7 C9 - C8 N1 - C7 C1 O1 - C7 Br1 - C4 Operators for generating equivalent atoms: $1 x+1/2, y, -z+1/2 14951 Reflections read, of which 1200 rejected -12 =< h =< 9, -11 =< k =< 11, -25 =< l =< 26, Max. 2-theta = 54.95 0 Systematic absence violations 0 Inconsistent equivalents 2052 Unique reflections, of which 0 suppressed R(int) = 0.0329 R(sigma) = 0.0262 Friedel opposites merged Maximum memory for data reduction = 1355 / 20501 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 = 1670 / 147308 wR2 = 0.0646 before cycle 1 for 2052 data and 114 / 114 parameters GooF = S = 1.087; Restrained GooF = 1.087 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0124 * P )^2 + 2.59 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.45760 0.00068 -0.719 OSF Mean shift/esd = 0.176 Maximum = -1.114 for U22 Br1 Max. shift = 0.002 A for H9A Max. dU =-0.001 for H1N Least-squares cycle 2 Maximum vector length = 511 Memory required = 1670 / 147308 wR2 = 0.0644 before cycle 2 for 2052 data and 114 / 114 parameters GooF = S = 1.085; Restrained GooF = 1.085 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0124 * P )^2 + 2.59 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.45735 0.00067 -0.374 OSF Mean shift/esd = 0.057 Maximum = -0.374 for OSF Max. shift = 0.001 A for H9A Max. dU = 0.000 for H1N Least-squares cycle 3 Maximum vector length = 511 Memory required = 1670 / 147308 wR2 = 0.0644 before cycle 3 for 2052 data and 114 / 114 parameters GooF = S = 1.086; Restrained GooF = 1.086 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0124 * P )^2 + 2.59 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.45735 0.00067 0.003 OSF Mean shift/esd = 0.001 Maximum = 0.009 for U13 C6 Max. shift = 0.000 A for H1N Max. dU = 0.000 for C6 Least-squares cycle 4 Maximum vector length = 511 Memory required = 1670 / 147308 wR2 = 0.0644 before cycle 4 for 2052 data and 114 / 114 parameters GooF = S = 1.086; Restrained GooF = 1.086 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0124 * P )^2 + 2.59 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.45736 0.00067 0.003 OSF Mean shift/esd = 0.001 Maximum = 0.003 for OSF Max. shift = 0.000 A for H1N Max. dU = 0.000 for C7 Least-squares cycle 5 Maximum vector length = 511 Memory required = 1670 / 147308 wR2 = 0.0644 before cycle 5 for 2052 data and 114 / 114 parameters GooF = S = 1.086; Restrained GooF = 1.086 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0124 * P )^2 + 2.59 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.45736 0.00067 0.001 OSF Mean shift/esd = 0.000 Maximum = -0.001 for z Br1 Max. shift = 0.000 A for H1N Max. dU = 0.000 for N1 Least-squares cycle 6 Maximum vector length = 511 Memory required = 1670 / 147308 wR2 = 0.0644 before cycle 6 for 2052 data and 114 / 114 parameters GooF = S = 1.086; Restrained GooF = 1.086 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0124 * P )^2 + 2.59 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 0.45736 0.00067 0.000 OSF Mean shift/esd = 0.000 Maximum = -0.001 for z Br1 Max. shift = 0.000 A for H1N Max. dU = 0.000 for H1N Largest correlation matrix elements 0.564 U33 Br1 / OSF 0.549 U11 Br1 / OSF 0.547 U22 Br1 / OSF Idealized hydrogen atom generation before cycle 7 Name x y z AFIX d(X-H) shift Bonded to Conformation determined by H2 0.0760 0.3595 0.3598 43 0.950 0.000 C2 C3 C1 H3 0.0500 0.2008 0.4467 43 0.950 0.000 C3 C4 C2 H5 0.4761 0.1346 0.4497 43 0.950 0.000 C5 C4 C6 H6 0.5027 0.2911 0.3620 43 0.950 0.000 C6 C5 C1 H8A 0.3447 0.6627 0.2318 23 0.990 0.000 C8 C9 C7 H8B 0.3463 0.5377 0.1786 23 0.990 0.000 C8 C9 C7 H9A 0.1118 0.6010 0.1477 137 0.980 0.000 C9 C8 H9A H9B 0.2168 0.7358 0.1399 137 0.980 0.000 C9 C8 H9A H9C 0.1115 0.7269 0.2004 137 0.980 0.000 C9 C8 H9A 2008lsh018 in Pbca ATOM x y z sof U11 U22 U33 U23 U13 U12 Ueq C1 0.29193 0.34040 0.35223 1.00000 0.02203 0.02084 0.02112 -0.00516 -0.00091 0.00015 0.02133 0.00369 0.00023 0.00024 0.00011 0.00000 0.00107 0.00108 0.00104 0.00090 0.00084 0.00087 0.00045 C2 0.15735 0.31369 0.37776 1.00000 0.01829 0.02925 0.02503 -0.00203 -0.00292 0.00066 0.02419 0.00389 0.00023 0.00025 0.00012 0.00000 0.00103 0.00119 0.00117 0.00097 0.00089 0.00089 0.00048 H2 0.07599 0.35949 0.35977 1.00000 0.02903 0.00000 0.00000 C3 0.14196 0.22005 0.42954 1.00000 0.02371 0.02967 0.02352 -0.00383 0.00119 -0.00355 0.02563 0.00394 0.00025 0.00025 0.00012 0.00000 0.00110 0.00123 0.00119 0.00096 0.00092 0.00093 0.00050 H3 0.05003 0.20083 0.44670 1.00000 0.03076 0.00000 0.00000 C4 0.26060 0.15507 0.45595 1.00000 0.03413 0.01983 0.01924 -0.00162 -0.00078 -0.00096 0.02440 0.00389 0.00025 0.00025 0.00010 0.00000 0.00123 0.00106 0.00102 0.00092 0.00096 0.00093 0.00047 C5 0.39512 0.18028 0.43128 1.00000 0.02719 0.03049 0.02570 -0.00188 -0.00476 0.00594 0.02779 0.00415 0.00026 0.00026 0.00012 0.00000 0.00118 0.00125 0.00122 0.00102 0.00096 0.00098 0.00051 H5 0.47608 0.13457 0.44968 1.00000 0.03335 0.00000 0.00000 C6 0.41056 0.27316 0.37930 1.00000 0.01935 0.03241 0.02647 -0.00229 0.00192 0.00183 0.02608 0.00406 0.00024 0.00025 0.00012 0.00000 0.00105 0.00127 0.00122 0.00103 0.00095 0.00092 0.00050 H6 0.50267 0.29105 0.36205 1.00000 0.03129 0.00000 0.00000 C7 0.22146 0.48762 0.25738 1.00000 0.02111 0.02270 0.02156 -0.00294 -0.00086 0.00066 0.02179 0.00376 0.00023 0.00023 0.00011 0.00000 0.00111 0.00105 0.00106 0.00088 0.00085 0.00085 0.00045 C8 0.28447 0.59165 0.20883 1.00000 0.02363 0.02753 0.02662 0.00229 0.00043 -0.00136 0.02593 0.00413 0.00024 0.00026 0.00011 0.00000 0.00113 0.00116 0.00113 0.00101 0.00092 0.00095 0.00048 H8A 0.34468 0.66269 0.23176 1.00000 0.03112 0.00000 0.00000 H8B 0.34630 0.53773 0.17860 1.00000 0.03112 0.00000 0.00000 C9 0.17113 0.67084 0.17086 1.00000 0.02918 0.02891 0.02941 0.00335 -0.00166 0.00125 0.02917 0.00436 0.00026 0.00027 0.00012 0.00000 0.00121 0.00126 0.00125 0.00108 0.00102 0.00099 0.00052 H9A 0.11176 0.60105 0.14771 1.00000 0.04375 0.00000 0.00000 H9B 0.21676 0.73581 0.13986 1.00000 0.04375 0.00000 0.00000 H9C 0.11149 0.72693 0.20044 1.00000 0.04375 0.00000 0.00000 N1 0.31666 0.43732 0.30104 1.00000 0.01411 0.02758 0.02341 0.00141 0.00060 -0.00112 0.02170 0.00333 0.00020 0.00021 0.00009 0.00000 0.00088 0.00102 0.00095 0.00078 0.00076 0.00074 0.00040 O1 0.09576 0.45221 0.25657 1.00000 0.01657 0.03657 0.03082 0.00533 -0.00306 -0.00262 0.02799 0.00277 0.00016 0.00017 0.00008 0.00000 0.00076 0.00090 0.00089 0.00078 0.00065 0.00066 0.00037 Br1 0.23791 0.03181 0.52831 1.00000 0.04396 0.02895 0.02310 0.00309 0.00115 0.00334 0.03200 0.00044 0.00003 0.00003 0.00001 0.00000 0.00017 0.00016 0.00014 0.00009 0.00010 0.00011 0.00010 H1N 0.39806 0.45605 0.29319 1.00000 0.01642 0.04171 0.00273 0.00250 0.00116 0.00000 0.00598 Final Structure Factor Calculation for 2008lsh018 in Pbca Total number of l.s. parameters = 114 Maximum vector length = 511 Memory required = 1556 / 24017 wR2 = 0.0644 before cycle 7 for 2052 data and 0 / 114 parameters GooF = S = 1.086; Restrained GooF = 1.086 for 0 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0124 * P )^2 + 2.59 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 R1 = 0.0294 for 1700 Fo > 4sig(Fo) and 0.0419 for all 2052 data wR2 = 0.0644, GooF = S = 1.086, Restrained GooF = 1.086 for all data Occupancy sum of asymmetric unit = 12.00 for non-hydrogen and 10.00 for hydrogen atoms Principal mean square atomic displacements U 0.0263 0.0219 0.0158 C1 0.0303 0.0250 0.0172 C2 0.0330 0.0225 0.0214 C3 0.0342 0.0212 0.0178 C4 0.0368 0.0258 0.0207 C5 0.0333 0.0265 0.0185 C6 0.0254 0.0209 0.0191 C7 0.0295 0.0255 0.0228 C8 0.0326 0.0301 0.0248 C9 0.0281 0.0231 0.0140 N1 0.0404 0.0278 0.0158 O1 0.0448 0.0294 0.0218 Br1 Analysis of variance for reflections employed in refinement K = Mean[Fo^2] / Mean[Fc^2] for group Fc/Fc(max) 0.000 0.013 0.027 0.043 0.058 0.078 0.101 0.138 0.183 0.287 1.000 Number in group 212. 198. 214. 197. 211. 205. 200. 203. 207. 205. GooF 1.126 1.193 1.241 1.137 1.028 1.093 1.069 0.943 0.942 1.043 K 2.009 1.041 0.945 0.951 0.968 0.980 0.983 0.999 1.014 0.998 Resolution(A) 0.77 0.80 0.83 0.87 0.91 0.97 1.05 1.15 1.31 1.63 inf Number in group 208. 202. 207. 203. 205. 208. 202. 208. 202. 207. GooF 1.297 1.136 1.229 1.178 0.934 1.056 0.924 0.786 0.887 1.288 K 0.979 0.995 1.009 1.005 1.013 1.010 1.011 1.009 1.005 0.987 R1 0.139 0.101 0.082 0.064 0.041 0.036 0.026 0.018 0.016 0.020 Recommended weighting scheme: WGHT 0.0040 2.6733 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) 2 0 4 33892.68 37758.47 3.71 0.862 3.48 3 1 8 25.72 0.48 3.41 0.003 1.95 2 9 12 -2.33 74.27 3.40 0.038 0.87 8 0 10 796.52 988.93 3.27 0.140 1.02 1 2 9 2341.79 2055.52 3.17 0.201 2.02 7 1 21 375.90 528.34 3.10 0.102 0.79 10 2 7 11.96 81.78 3.08 0.040 0.88 4 6 21 561.62 790.19 3.00 0.125 0.78 1 1 12 26.43 1.75 2.99 0.006 1.67 4 7 20 253.59 431.02 2.95 0.092 0.77 1 10 8 339.85 469.19 2.95 0.096 0.87 0 4 17 294.83 425.72 2.94 0.092 1.08 4 1 1 2004.10 1767.14 2.92 0.187 2.26 0 2 7 206.56 137.00 2.91 0.052 2.50 8 1 18 129.37 43.37 2.89 0.029 0.82 5 9 11 -9.66 35.38 2.88 0.026 0.81 1 4 7 17492.48 16298.91 2.87 0.567 1.79 5 10 8 99.12 192.54 2.85 0.062 0.79 3 8 8 27.74 1.53 2.77 0.005 1.00 8 5 16 125.49 258.31 2.73 0.071 0.79 6 10 1 219.79 316.50 2.73 0.079 0.80 5 7 16 89.80 14.24 2.68 0.017 0.83 9 1 11 39.75 100.51 2.67 0.044 0.91 1 9 4 -9.16 19.43 2.63 0.020 1.01 7 6 15 433.39 561.06 2.62 0.105 0.82 0 2 10 370.98 473.05 2.58 0.097 1.89 6 4 17 -6.51 41.62 2.56 0.029 0.89 5 3 2 2426.19 2192.46 2.56 0.208 1.59 1 8 20 -29.28 59.37 2.53 0.034 0.77 5 1 3 710.50 839.71 2.53 0.129 1.78 8 8 2 63.66 128.17 2.53 0.050 0.82 3 1 25 -14.63 36.19 2.53 0.027 0.80 10 1 5 1503.92 1301.06 2.51 0.160 0.91 7 3 9 243.82 323.50 2.50 0.080 1.09 4 10 3 324.51 433.49 2.50 0.092 0.86 2 4 25 902.87 1105.81 2.46 0.148 0.77 4 1 6 1815.99 1626.33 2.45 0.179 1.90 2 7 12 133.42 194.94 2.44 0.062 1.03 4 2 21 120.14 192.94 2.43 0.062 0.89 8 0 20 961.97 1338.13 2.42 0.162 0.78 9 1 1 1305.55 1144.41 2.42 0.150 1.03 6 9 0 460.09 359.10 2.41 0.084 0.86 11 2 1 58.60 108.12 2.41 0.046 0.84 10 5 9 515.75 382.15 2.40 0.087 0.79 4 11 2 127.84 15.27 2.40 0.017 0.79 7 2 21 387.57 242.46 2.40 0.069 0.78 8 0 8 101.17 51.03 2.39 0.032 1.07 6 6 13 2505.89 2241.85 2.36 0.210 0.91 6 2 0 14674.14 13797.87 2.36 0.521 1.48 6 9 5 47.07 6.28 2.34 0.011 0.84 Bond lengths and angles C1 - Distance Angles C2 1.3915 (0.0031) C6 1.3941 (0.0031) 119.43 (0.21) N1 1.4108 (0.0030) 123.31 (0.20) 117.21 (0.20) C1 - C2 C6 C2 - Distance Angles C3 1.3892 (0.0035) C1 1.3915 (0.0031) 120.00 (0.21) H2 0.9500 120.00 120.00 C2 - C3 C1 C3 - Distance Angles C4 1.3794 (0.0033) C2 1.3892 (0.0035) 119.79 (0.22) H3 0.9500 120.10 120.10 C3 - C4 C2 C4 - Distance Angles C3 1.3794 (0.0033) C5 1.3819 (0.0033) 121.05 (0.21) Br1 1.8991 (0.0023) 119.13 (0.18) 119.81 (0.17) C4 - C3 C5 C5 - Distance Angles C4 1.3819 (0.0033) C6 1.3880 (0.0035) 119.22 (0.21) H5 0.9500 120.39 120.39 C5 - C4 C6 C6 - Distance Angles C5 1.3880 (0.0035) C1 1.3941 (0.0031) 120.50 (0.22) H6 0.9500 119.75 119.75 C6 - C5 C1 C7 - Distance Angles O1 1.2243 (0.0026) N1 1.3550 (0.0030) 123.47 (0.21) C8 1.5151 (0.0032) 122.53 (0.21) 113.99 (0.19) C7 - O1 N1 C8 - Distance Angles C9 1.5136 (0.0032) C7 1.5151 (0.0032) 112.40 (0.19) H8A 0.9900 109.12 109.12 H8B 0.9900 109.12 109.12 107.85 C8 - C9 C7 H8A C9 - Distance Angles C8 1.5136 (0.0032) H9A 0.9800 109.47 H9B 0.9800 109.47 109.47 H9C 0.9800 109.47 109.47 109.47 C9 - C8 H9A H9B N1 - Distance Angles C7 1.3550 (0.0030) C1 1.4108 (0.0030) 127.91 (0.20) H1N 0.8000 (0.0253) 114.73 (1.76) 116.66 (1.75) N1 - C7 C1 O1 - Distance Angles C7 1.2243 (0.0026) O1 - Br1 - Distance Angles C4 1.8991 (0.0023) Br1 - Specified hydrogen bonds (with esds except fixed and riding H) D-H H...A D...A <(DHA) 0.80(3) 2.12(3) 2.882(2) 158(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)