+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ + SHELXL-97 - CRYSTAL STRUCTURE REFINEMENT - WinGX VERSION + + Copyright(C) George M. Sheldrick 1993-7 Release 97-2 + + shelxl started at 18:07:12 on 31-Mar-2009 + +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ TITL 2008lsh105 in Pca2(1) CELL 0.71073 15.6207 5.3929 8.6541 90.000 90.000 90.000 ZERR 4.00 0.0004 0.0001 0.0002 0.000 0.000 0.000 LATT -1 SYMM - X, - Y, 1/2 + Z SYMM 1/2 + X, - Y, Z SYMM 1/2 - X, Y, 1/2 + Z SFAC C H N CL UNIT 28 40 4 4 V = 729.03 F(000) = 304.0 Mu = 0.43 mm-1 Cell Wt = 574.44 Rho = 1.308 MERG 2 OMIT -3.00 55.00 OMIT 0 1 0 OMIT 1 1 2 OMIT 1 1 -2 OMIT 8 0 0 OMIT 7 1 0 OMIT 1 1 0 FMAP 2 PLAN 5 SIZE 0.10 0.20 0.50 ACTA EQIV $1 -x+1, -y+1, z-1/2 EQIV $2 x, y+1, z HTAB N1 Cl1_$1 HTAB N1 Cl1 HTAB N1 Cl1_$2 HTAB BOND $H L.S. 6 TEMP -153.00 WGHT 0.0193 0.1731 FVAR 0.50689 C1 1 0.337618 0.821731 0.660232 11.00000 0.01316 0.01420 = 0.01111 -0.00088 0.00166 0.00387 C2 1 0.311368 1.017758 0.566912 11.00000 0.01922 0.01210 = 0.01262 -0.00165 -0.00064 0.00143 C3 1 0.223313 1.038908 0.540641 11.00000 0.02141 0.01733 = 0.01564 -0.00011 -0.00275 0.00421 AFIX 43 H3 2 0.202595 1.171599 0.478878 11.00000 -1.20000 AFIX 0 C4 1 0.165660 0.871289 0.602417 11.00000 0.01620 0.02530 = 0.01899 0.00018 -0.00107 0.00515 AFIX 43 H4 2 0.106169 0.890513 0.583032 11.00000 -1.20000 AFIX 0 C5 1 0.194164 0.675825 0.692269 11.00000 0.01862 0.02185 = 0.02047 0.00164 0.00341 -0.00309 AFIX 43 H5 2 0.154517 0.559190 0.732844 11.00000 -1.20000 AFIX 0 C6 1 0.280960 0.650962 0.722841 11.00000 0.02019 0.01498 = 0.01513 0.00229 0.00123 0.00090 AFIX 43 H6 2 0.301266 0.519033 0.785675 11.00000 -1.20000 AFIX 0 C9 1 0.373281 1.194943 0.492153 11.00000 0.02285 0.01598 = 0.01721 0.00446 -0.00068 -0.00036 AFIX 137 H9A 2 0.395541 1.121423 0.396705 11.00000 -1.50000 H9B 2 0.420808 1.228158 0.563115 11.00000 -1.50000 H9C 2 0.343791 1.350574 0.467977 11.00000 -1.50000 AFIX 0 N1 3 0.429563 0.795154 0.695008 11.00000 0.01607 0.01149 = 0.01277 0.00187 0.00013 0.00102 CL1 4 0.474604 0.296723 0.877867 11.00000 0.01578 0.01305 = 0.01629 0.00157 -0.00324 0.00008 H1N 2 0.459872 0.774585 0.608930 11.00000 0.02385 H2N 2 0.442321 0.663155 0.754440 11.00000 0.03559 H3N 2 0.451198 0.932372 0.749279 11.00000 0.02748 HKLF 4 1 0 0 1 1 0 0 0 1 0 Covalent radii and connectivity table for 2008lsh105 in Pca2(1) C 0.770 H 0.320 N 0.700 CL 0.990 C1 - C6 C2 N1 C2 - C1 C3 C9 C3 - C4 C2 C4 - C3 C5 C5 - C4 C6 C6 - C1 C5 C9 - C2 N1 - C1 Cl1 - no bonds found Operators for generating equivalent atoms: $1 -x+1, -y+1, z-1/2 $2 x, y+1, z Floating origin restraints generated 6849 Reflections read, of which 602 rejected -20 =< h =< 18, -6 =< k =< 6, -9 =< l =< 11, Max. 2-theta = 54.94 0 Systematic absence violations 0 Inconsistent equivalents 1476 Unique reflections, of which 0 suppressed R(int) = 0.0238 R(sigma) = 0.0282 Friedel opposites not merged Maximum memory for data reduction = 1269 / 14772 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 = 1514 / 124835 wR2 = 0.0566 before cycle 1 for 1476 data and 95 / 95 parameters GooF = S = 0.202; Restrained GooF = 0.202 for 1 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0193 * P )^2 + 0.17 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 1.60138 0.00266 411.483 OSF Mean shift/esd = 4.773 Maximum = 411.483 for OSF Max. shift = 0.036 A for H1N Max. dU =-0.005 for H1N Least-squares cycle 2 Maximum vector length = 511 Memory required = 1514 / 124835 wR2 = 0.0539 before cycle 2 for 1476 data and 95 / 95 parameters GooF = S = 1.129; Restrained GooF = 1.129 for 1 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0193 * P )^2 + 0.17 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 1.60267 0.00248 0.520 OSF Mean shift/esd = 0.222 Maximum = -0.809 for x C5 Max. shift = 0.014 A for H1N Max. dU = 0.002 for H1N Least-squares cycle 3 Maximum vector length = 511 Memory required = 1514 / 124835 wR2 = 0.0534 before cycle 3 for 1476 data and 95 / 95 parameters GooF = S = 1.120; Restrained GooF = 1.119 for 1 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0193 * P )^2 + 0.17 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 1.60282 0.00245 0.061 OSF Mean shift/esd = 0.225 Maximum = -0.854 for x C5 Max. shift = 0.018 A for H1N Max. dU = 0.003 for H1N Least-squares cycle 4 Maximum vector length = 511 Memory required = 1514 / 124835 wR2 = 0.0532 before cycle 4 for 1476 data and 95 / 95 parameters GooF = S = 1.115; Restrained GooF = 1.115 for 1 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0193 * P )^2 + 0.17 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 1.60281 0.00244 -0.004 OSF Mean shift/esd = 0.021 Maximum = 0.152 for x H1N Max. shift = 0.004 A for H1N Max. dU =-0.001 for H2N Least-squares cycle 5 Maximum vector length = 511 Memory required = 1514 / 124835 wR2 = 0.0532 before cycle 5 for 1476 data and 95 / 95 parameters GooF = S = 1.115; Restrained GooF = 1.114 for 1 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0193 * P )^2 + 0.17 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 1.60280 0.00244 -0.003 OSF Mean shift/esd = 0.008 Maximum = -0.048 for z N1 Max. shift = 0.001 A for H2N Max. dU = 0.000 for H2N Least-squares cycle 6 Maximum vector length = 511 Memory required = 1514 / 124835 wR2 = 0.0532 before cycle 6 for 1476 data and 95 / 95 parameters GooF = S = 1.114; Restrained GooF = 1.114 for 1 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0193 * P )^2 + 0.17 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 N value esd shift/esd parameter 1 1.60280 0.00244 -0.001 OSF Mean shift/esd = 0.002 Maximum = -0.014 for U11 H2N Max. shift = 0.000 A for H2N Max. dU = 0.000 for H2N Largest correlation matrix elements 0.539 U11 Cl1 / OSF 0.518 U33 Cl1 / OSF 0.505 U22 Cl1 / OSF Idealized hydrogen atom generation before cycle 7 Name x y z AFIX d(X-H) shift Bonded to Conformation determined by H3 0.2026 1.1716 0.4789 43 0.950 0.000 C3 C4 C2 H4 0.1062 0.8905 0.5830 43 0.950 0.000 C4 C3 C5 H5 0.1545 0.5592 0.7328 43 0.950 0.000 C5 C4 C6 H6 0.3013 0.5190 0.7857 43 0.950 0.000 C6 C1 C5 H9A 0.3955 1.1215 0.3967 137 0.980 0.000 C9 C2 H9A H9B 0.4208 1.2281 0.5631 137 0.980 0.000 C9 C2 H9A H9C 0.3438 1.3506 0.4680 137 0.980 0.000 C9 C2 H9A 2008lsh105 in Pca2(1) ATOM x y z sof U11 U22 U33 U23 U13 U12 Ueq C1 0.33762 0.82173 0.66023 1.00000 0.01313 0.01421 0.01110 -0.00089 0.00166 0.00388 0.01281 0.00255 0.00009 0.00028 0.00017 0.00000 0.00063 0.00072 0.00064 0.00048 0.00054 0.00050 0.00030 C2 0.31137 1.01775 0.56692 1.00000 0.01922 0.01209 0.01260 -0.00167 -0.00064 0.00142 0.01464 0.00239 0.00009 0.00025 0.00017 0.00000 0.00063 0.00062 0.00056 0.00053 0.00051 0.00050 0.00026 C3 0.22331 1.03891 0.54064 1.00000 0.02140 0.01734 0.01562 -0.00010 -0.00274 0.00422 0.01812 0.00251 0.00009 0.00028 0.00017 0.00000 0.00069 0.00068 0.00067 0.00057 0.00050 0.00051 0.00029 H3 0.20259 1.17160 0.47889 1.00000 0.02174 0.00000 0.00000 C4 0.16567 0.87128 0.60242 1.00000 0.01617 0.02530 0.01898 0.00016 -0.00109 0.00515 0.02015 0.00283 0.00010 0.00033 0.00017 0.00000 0.00071 0.00083 0.00078 0.00069 0.00056 0.00062 0.00034 H4 0.10618 0.89050 0.58302 1.00000 0.02418 0.00000 0.00000 C5 0.19416 0.67583 0.69227 1.00000 0.01860 0.02185 0.02045 0.00164 0.00343 -0.00311 0.02030 0.00258 0.00009 0.00028 0.00018 0.00000 0.00067 0.00079 0.00076 0.00059 0.00058 0.00053 0.00032 H5 0.15451 0.55920 0.73284 1.00000 0.02436 0.00000 0.00000 C6 0.28096 0.65097 0.72284 1.00000 0.02018 0.01497 0.01510 0.00229 0.00121 0.00092 0.01675 0.00247 0.00009 0.00027 0.00016 0.00000 0.00064 0.00066 0.00063 0.00060 0.00053 0.00052 0.00028 H6 0.30127 0.51904 0.78567 1.00000 0.02010 0.00000 0.00000 C9 0.37328 1.19494 0.49216 1.00000 0.02283 0.01596 0.01721 0.00446 -0.00069 -0.00035 0.01867 0.00266 0.00010 0.00026 0.00018 0.00000 0.00070 0.00073 0.00067 0.00054 0.00058 0.00055 0.00030 H9A 0.39552 1.12145 0.39668 1.00000 0.02800 0.00000 0.00000 H9B 0.42082 1.22810 0.56310 1.00000 0.02800 0.00000 0.00000 H9C 0.34379 1.35059 0.46802 1.00000 0.02800 0.00000 0.00000 N1 0.42956 0.79516 0.69501 1.00000 0.01604 0.01151 0.01277 0.00188 0.00013 0.00102 0.01344 0.00201 0.00007 0.00022 0.00014 0.00000 0.00053 0.00067 0.00060 0.00048 0.00047 0.00041 0.00025 Cl1 0.47460 0.29672 0.87787 1.00000 0.01577 0.01304 0.01628 0.00157 -0.00323 0.00008 0.01503 0.00053 0.00002 0.00005 0.00005 0.00000 0.00015 0.00017 0.00015 0.00018 0.00015 0.00009 0.00010 H1N 0.45990 0.77457 0.60883 1.00000 0.02404 0.03363 0.00125 0.00354 0.00249 0.00000 0.00480 H2N 0.44230 0.66324 0.75444 1.00000 0.03566 0.03613 0.00127 0.00412 0.00238 0.00000 0.00553 H3N 0.45122 0.93256 0.74936 1.00000 0.02750 0.03391 0.00115 0.00377 0.00207 0.00000 0.00466 Final Structure Factor Calculation for 2008lsh105 in Pca2(1) Total number of l.s. parameters = 95 Maximum vector length = 511 Memory required = 1421 / 25046 wR2 = 0.0532 before cycle 7 for 1476 data and 2 / 95 parameters GooF = S = 1.115; Restrained GooF = 1.114 for 1 restraints Weight = 1 / [ sigma^2(Fo^2) + ( 0.0193 * P )^2 + 0.17 * P ] where P = ( Max ( Fo^2, 0 ) + 2 * Fc^2 ) / 3 R1 = 0.0215 for 1456 Fo > 4sig(Fo) and 0.0219 for all 1476 data wR2 = 0.0532, GooF = S = 1.115, Restrained GooF = 1.114 for all data Flack x parameter = -0.0791 with esd 0.0546 Expected values are 0 (within 3 esd's) for correct and +1 for inverted absolute structure. Note that this rough estimate ignores correlation with other parameters; if the above value differs significantly from zero, it is ESSENTIAL to test the inverted structure or refine x as a full-matrix parameter using TWIN and BASF Occupancy sum of asymmetric unit = 9.00 for non-hydrogen and 10.00 for hydrogen atoms Principal mean square atomic displacements U 0.0176 0.0124 0.0085 C1 0.0196 0.0137 0.0106 C2 0.0247 0.0162 0.0135 C3 0.0276 0.0192 0.0136 C4 0.0238 0.0227 0.0144 C5 0.0208 0.0167 0.0127 C6 0.0231 0.0208 0.0121 C9 0.0164 0.0139 0.0101 N1 0.0195 0.0139 0.0117 Cl1 Analysis of variance for reflections employed in refinement K = Mean[Fo^2] / Mean[Fc^2] for group Fc/Fc(max) 0.000 0.055 0.090 0.118 0.149 0.179 0.217 0.259 0.309 0.428 1.000 Number in group 149. 150. 146. 145. 151. 144. 148. 148. 150. 145. GooF 1.062 1.239 1.172 1.237 0.995 0.974 0.831 1.098 1.188 1.271 K 0.955 0.959 0.972 0.981 0.993 0.998 0.999 1.010 1.012 1.002 Resolution(A) 0.77 0.81 0.85 0.89 0.95 1.00 1.08 1.19 1.35 1.67 inf Number in group 152. 146. 148. 144. 149. 147. 147. 149. 146. 148. GooF 1.061 1.090 1.076 0.911 0.891 0.941 0.953 0.836 1.402 1.696 K 0.979 0.996 1.001 1.006 1.010 1.015 1.022 1.012 1.006 0.988 R1 0.038 0.032 0.030 0.022 0.020 0.019 0.016 0.014 0.020 0.022 Recommended weighting scheme: WGHT 0.0192 0.1742 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) 8 6 0 14.49 26.55 4.30 0.082 0.82 2 3 0 0.72 4.11 4.25 0.032 1.75 0 0 2 1098.02 1248.62 3.74 0.563 4.33 6 3 0 94.36 115.68 3.71 0.171 1.48 5 2 0 1.93 5.52 3.71 0.037 2.04 4 5 -5 56.95 77.24 3.45 0.140 0.89 2 0 6 273.93 311.47 3.44 0.281 1.42 4 3 2 52.10 65.54 3.36 0.129 1.53 8 1 0 121.92 103.53 3.30 0.162 1.84 8 3 -8 18.38 31.10 3.27 0.089 0.84 5 1 -2 380.58 422.14 3.08 0.327 2.29 4 3 -2 51.15 62.73 2.98 0.126 1.53 8 0 1 655.91 719.76 2.92 0.427 1.90 2 0 1 1414.50 1572.31 2.88 0.631 5.80 3 1 4 64.42 76.60 2.86 0.139 1.87 11 4 -6 188.57 233.32 2.81 0.243 0.81 6 0 -2 108.23 125.06 2.79 0.178 2.23 7 2 2 139.92 158.80 2.71 0.201 1.60 4 2 0 54.66 65.29 2.70 0.129 2.22 15 1 0 69.81 58.06 2.70 0.121 1.02 2 0 -1 1431.49 1601.17 2.69 0.637 5.80 3 5 -6 37.66 53.17 2.68 0.116 0.85 2 4 9 14.10 20.08 2.62 0.071 0.78 8 0 -1 661.05 722.19 2.62 0.428 1.90 8 1 2 65.82 55.44 2.62 0.119 1.69 3 1 3 865.03 932.31 2.61 0.486 2.29 4 6 -2 17.23 24.18 2.59 0.078 0.86 7 2 -2 134.93 152.27 2.58 0.196 1.60 4 3 -7 28.38 36.74 2.57 0.097 0.99 6 1 2 384.90 352.73 2.56 0.299 2.06 8 0 -7 23.87 32.06 2.56 0.090 1.04 5 1 2 394.91 430.50 2.56 0.330 2.29 9 1 0 2735.40 2562.44 2.51 0.806 1.65 6 0 2 118.38 136.74 2.50 0.186 2.23 8 1 -9 4.78 9.45 2.47 0.049 0.85 11 1 -7 55.49 68.04 2.45 0.131 0.92 0 0 -2 1127.72 1254.86 2.45 0.564 4.33 1 1 5 574.79 618.49 2.44 0.396 1.64 7 1 4 541.82 584.09 2.43 0.385 1.49 8 1 -2 64.73 55.00 2.40 0.118 1.69 13 2 -6 52.54 66.39 2.38 0.130 0.87 3 1 -4 65.01 76.38 2.37 0.139 1.87 0 3 2 733.48 796.03 2.35 0.449 1.66 15 3 -3 33.66 44.86 2.33 0.107 0.86 2 1 -6 118.89 104.06 2.33 0.162 1.37 4 0 -1 1958.44 2118.34 2.31 0.733 3.56 8 0 -2 2060.06 1919.01 2.31 0.698 1.78 3 6 -2 9.70 14.46 2.31 0.061 0.87 12 0 1 280.64 256.33 2.31 0.255 1.29 3 4 8 13.01 17.65 2.30 0.067 0.83 Bond lengths and angles C1 - Distance Angles C6 1.3874 (0.0021) C2 1.3920 (0.0020) 122.87 (0.13) N1 1.4745 (0.0018) 118.50 (0.13) 118.63 (0.13) C1 - C6 C2 C2 - Distance Angles C1 1.3920 (0.0020) C3 1.3989 (0.0019) 116.48 (0.13) C9 1.5056 (0.0019) 122.83 (0.13) 120.66 (0.13) C2 - C1 C3 C3 - Distance Angles C4 1.3834 (0.0022) C2 1.3989 (0.0019) 121.60 (0.14) H3 0.9500 119.20 119.20 C3 - C4 C2 C4 - Distance Angles C3 1.3834 (0.0022) C5 1.3834 (0.0022) 120.38 (0.14) H4 0.9500 119.81 119.81 C4 - C3 C5 C5 - Distance Angles C4 1.3834 (0.0022) C6 1.3879 (0.0020) 119.67 (0.13) H5 0.9500 120.16 120.16 C5 - C4 C6 C6 - Distance Angles C1 1.3874 (0.0021) C5 1.3879 (0.0020) 118.99 (0.14) H6 0.9500 120.51 120.51 C6 - C1 C5 C9 - Distance Angles C2 1.5056 (0.0019) H9A 0.9800 109.47 H9B 0.9800 109.47 109.47 H9C 0.9800 109.47 109.47 109.47 C9 - C2 H9A H9B N1 - Distance Angles C1 1.4745 (0.0018) H1N 0.8906 (0.0216) 111.07 (1.25) H2N 0.9001 (0.0219) 114.12 (1.30) 105.21 (1.75) H3N 0.9406 (0.0201) 112.08 (1.12) 109.00 (1.72) 104.92 (1.75) N1 - C1 H1N H2N Specified hydrogen bonds (with esds except fixed and riding H) D-H H...A D...A <(DHA) 0.89(2) 2.28(2) 3.1653(13) 174.1(17) N1-H1N...Cl1_$1 0.90(2) 2.30(2) 3.1976(12) 172.7(18) N1-H2N...Cl1 0.94(2) 2.29(2) 3.2118(12) 167.8(15) N1-H3N...Cl1_$2 Hydrogen bonds with H..A < r(A) + 2.000 Angstroms and 110 deg. D-H d(D-H) d(H..A)