Small Molecule Crystallography Lab Department of Chemistry and Biochemistry University of Oklahoma 101 Stephenson Parkway Norman, OK

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1 Small Molecule Crystallography Lab Department of Chemistry and Biochemistry University of Oklahoma 101 Stephenson Parkway Norman, OK Sample: KP-XI-furan-enzymatic alcohol Lab ID: User: Kaushik Panigrahi Formula: C 12 H 17 F 2 O 5 P Date: May 14, 2012 For Prof. David Berkowitz

2 Table of Contents Figure 1. Thermal Ellipsoid Plot of Structure.. 3 Figure 2. Packing Diagram 4 Comments.. 5 Experimental.. 5 Acknowledgements... 6 References. 6 Table 1. Crystal Data 7 Table 2. Atom Coordinates 8 Table 3. Bond Distances and Angles.. 9 Table 4. Anisotropic Displacement Parameters.. 11 Table 5. Hydrogen Atom Parameters 12 Table 6. Torsion Angles.. 13 Table 7. Hydrogen Bond Details 14 KP-XI-furan-enzymatic-alcohol Page 2

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5 Comment The displacement ellipsoids were drawn at the 50% probability level. Experimental A colorless block-shaped crystal of dimensions 0.42 x 0.38 x 0.32 mm was selected for structural analysis. Intensity data for this compound were collected using a diffractometer with a Bruker APEX ccd area detector (1) and graphite-monochromated Mo K radiation ( = Å). The sample was cooled to 100(2) K. Cell parameters were determined from a non-linear least squares fit of 5538 peaks in the range 2.29 < < A total of data were measured in the range 2.22 < < using and oscillation frames. The data were corrected for absorption by the empirical method (2) giving minimum and maximum transmission factors of and The data were merged to form a set of 2622 independent data with R(int) = and a coverage of 99.7 %. The orthorhombic space group P was determined by systematic absences and statistical tests and verified by subsequent refinement. The structure was solved by direct methods and refined by full-matrix least-squares methods on F 2 (3). The positions of hydrogens bonded to carbons were initially determined by geometry and refined by a riding model. The hydrogen bonded to O4 was located on a difference map, and its position was refined independently. Non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atom displacement parameters were set to 1.2 (1.5 for methyl) times the isotropic equivalent displacement parameters of the bonded atoms. A total of 185 parameters were refined against 0 restraints and 2622 data to give wr(f 2 ) = and S = for weights of w = 1/[ 2 (F 2 ) + ( P) P], where P = [F o 2 + 2F c 2 ] / 3. The final R(F) was for the 2579 observed, [F > 4 (F)], data. The largest shift/s.u. was in the final refinement cycle. The final difference map had maxima and minima of and e/å 3, respectively. The absolute structure was determined by refinement of the Flack parameter(4). KP-XI-furan-enzymatic-alcohol Page 5

6 Acknowledgment The authors thank the National Science Foundation (grant CHE ) and the University of Oklahoma for funds to purchase of the X-ray instrument and computers. This structure was determined by Douglas R. Powell. References (1) (a) Data Collection: SMART Software Reference Manual (2007). Bruker-AXS, 5465 E. Cheryl Parkway, Madison, WI USA. (b) Data Reduction: SAINT Software Reference Manual (2007). Bruker-AXS, 5465 E. Cheryl Parkway, Madison, WI USA. (2) G. M. Sheldrick (2001). SADABS. Program for Empirical Absorption Correction of Area Detector Data. University of Göttingen, Germany. (3) G. M. Sheldrick (2008). Acta Cryst., A64, (4) H. D. Flack (1983). Acta Cryst. A39, KP-XI-furan-enzymatic-alcohol Page 6

7 Table 1. Crystal data and structure refinement for Empirical formula Formula weight Crystal system C 12 H 17 F 2 O 5 P orthorhombic Space group P Unit cell dimensions a = (7) Å = 90 Volume (3) Å 3 Z, Z' 4, 1 Density (calculated) Mg/m 3 Wavelength Temperature F(000) 648 b = (13) Å = 90 c = (3) Å = Å 100(2) K Absorption coefficient mm -1 Absorption correction Semi-empirical from equivalents Max. and min. transmission and Theta range for data collection 2.22 to Reflections collected Independent reflections 2622 [R(int) = ] Data / restraints / parameters 2622 / 0 / 185 wr(f 2 all data) wr2 = R(F obsd data) R1 = Goodness-of-fit on F Observed data [I > 2 (I)] 2579 Absolute structure parameter 0.00(8) Largest and mean shift / s.u and Largest diff. peak and hole and e/å wr2 = { [w(f 2 o - F 2 c ) 2 ] / [w(f 2 o ) 2 ] } 1/2 R1 = F o - F c / F o KP-XI-furan-enzymatic-alcohol Page 7

8 Table 2. Atomic coordinates and equivalent isotropic displacement parameters for U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) P(1) (7) (4) (14) (11) F(1) (19) (10) (4) (2) F(2) (18) (10) (3) (2) O(1) (2) (12) (4) (3) O(2) (2) (12) (4) (3) O(3) (2) (11) (4) (3) O(4) (2) (12) (4) (2) O(5) (2) (11) (4) (3) C(1) (4) (2) (7) (5) C(2) (4) (2) (7) (4) C(3) (3) (16) (6) (3) C(4) (3) (18) (7) (4) C(5) (3) (16) (6) (3) C(6) (3) (15) (5) (3) C(7) (3) (17) (6) (3) C(8) (3) (16) (6) (3) C(9) (3) (16) (6) (3) C(10) (3) (17) (6) (3) C(11) (3) (18) (6) (4) C(12) (3) (17) (6) (3) KP-XI-furan-enzymatic-alcohol Page 8

9 Table 3. Bond lengths [Å] and angles [ ] for P(1)-O(1) (12) P(1)-O(3) (12) P(1)-O(2) (12) P(1)-C(5) (16) F(1)-C(5) (19) F(2)-C(5) (18) O(2)-C(1) 1.468(2) O(3)-C(3) 1.461(2) O(4)-C(6) 1.414(2) O(4)-H(4O) 0.88(2) O(5)-C(10) 1.358(2) O(5)-C(11) 1.366(2) C(1)-C(2) 1.494(3) C(1)-H(1A) C(1)-H(1B) C(2)-H(2A) C(2)-H(2B) C(2)-H(2C) C(3)-C(4) 1.503(2) O(1)-P(1)-O(3) (7) O(1)-P(1)-O(2) (7) O(3)-P(1)-O(2) (6) O(1)-P(1)-C(5) (7) O(3)-P(1)-C(5) (7) O(2)-P(1)-C(5) (7) C(1)-O(2)-P(1) (11) C(3)-O(3)-P(1) (11) C(6)-O(4)-H(4O) 112.8(13) C(10)-O(5)-C(11) (13) O(2)-C(1)-C(2) (16) O(2)-C(1)-H(1A) C(2)-C(1)-H(1A) O(2)-C(1)-H(1B) C(2)-C(1)-H(1B) H(1A)-C(1)-H(1B) C(1)-C(2)-H(2A) C(1)-C(2)-H(2B) H(2A)-C(2)-H(2B) C(1)-C(2)-H(2C) H(2A)-C(2)-H(2C) H(2B)-C(2)-H(2C) C(3)-H(3A) C(3)-H(3B) C(4)-H(4A) C(4)-H(4B) C(4)-H(4C) C(5)-C(6) 1.534(2) C(6)-C(7) 1.496(2) C(6)-H(6) C(7)-C(8) 1.335(2) C(7)-H(7) C(8)-C(9) 1.456(2) C(8)-H(8) C(9)-C(10) 1.354(2) C(9)-C(12) 1.442(2) C(10)-H(10) C(11)-C(12) 1.341(2) C(11)-H(11) C(12)-H(12) O(3)-C(3)-C(4) (13) O(3)-C(3)-H(3A) C(4)-C(3)-H(3A) O(3)-C(3)-H(3B) C(4)-C(3)-H(3B) H(3A)-C(3)-H(3B) C(3)-C(4)-H(4A) C(3)-C(4)-H(4B) H(4A)-C(4)-H(4B) C(3)-C(4)-H(4C) H(4A)-C(4)-H(4C) H(4B)-C(4)-H(4C) F(2)-C(5)-F(1) (12) F(2)-C(5)-C(6) (13) F(1)-C(5)-C(6) (13) F(2)-C(5)-P(1) (10) F(1)-C(5)-P(1) (10) C(6)-C(5)-P(1) (11) O(4)-C(6)-C(7) (13) O(4)-C(6)-C(5) (12) C(7)-C(6)-C(5) (12) O(4)-C(6)-H(6) KP-XI-furan-enzymatic-alcohol Page 9

10 C(7)-C(6)-H(6) C(12)-C(9)-C(8) (15) C(5)-C(6)-H(6) C(9)-C(10)-O(5) (14) C(8)-C(7)-C(6) (15) C(9)-C(10)-H(10) C(8)-C(7)-H(7) O(5)-C(10)-H(10) C(6)-C(7)-H(7) C(12)-C(11)-O(5) (15) C(7)-C(8)-C(9) (15) C(12)-C(11)-H(11) C(7)-C(8)-H(8) O(5)-C(11)-H(11) C(9)-C(8)-H(8) C(11)-C(12)-C(9) (15) C(10)-C(9)-C(12) (15) C(11)-C(12)-H(12) C(10)-C(9)-C(8) (15) C(9)-C(12)-H(12) KP-XI-furan-enzymatic-alcohol Page 10

11 Table 4. Anisotropic displacement parameters (Å 2 x 10 3 ) for The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 P(1) 18(1) 18(1) 18(1) 0(1) -3(1) 1(1) F(1) 33(1) 18(1) 35(1) -1(1) -12(1) -5(1) F(2) 30(1) 29(1) 20(1) -2(1) 3(1) 7(1) O(1) 20(1) 25(1) 28(1) -1(1) -1(1) 0(1) O(2) 31(1) 23(1) 23(1) 0(1) -10(1) 1(1) O(3) 25(1) 20(1) 21(1) -1(1) 0(1) -1(1) O(4) 21(1) 21(1) 21(1) -1(1) 0(1) -3(1) O(5) 27(1) 20(1) 27(1) 5(1) -1(1) -3(1) C(1) 53(1) 26(1) 33(1) 6(1) -20(1) 5(1) C(2) 29(1) 46(1) 27(1) 3(1) -8(1) 5(1) C(3) 24(1) 21(1) 26(1) -3(1) -5(1) -4(1) C(4) 33(1) 23(1) 28(1) -2(1) -3(1) 1(1) C(5) 18(1) 17(1) 23(1) -2(1) -1(1) 1(1) C(6) 19(1) 18(1) 19(1) 1(1) 0(1) -1(1) C(7) 19(1) 23(1) 19(1) 0(1) 0(1) 2(1) C(8) 16(1) 21(1) 17(1) -3(1) 0(1) -1(1) C(9) 19(1) 19(1) 17(1) -1(1) -2(1) -2(1) C(10) 22(1) 23(1) 21(1) -2(1) -2(1) -2(1) C(11) 21(1) 23(1) 28(1) 0(1) -3(1) 2(1) C(12) 19(1) 21(1) 23(1) 1(1) 1(1) -2(1) KP-XI-furan-enzymatic-alcohol Page 11

12 Table 5. Hydrogen coordinates and isotropic displacement parameters for x y z U(eq) H(4O) 0.096(4) 0.438(2) (7) H(1A) H(1B) H(2A) H(2B) H(2C) H(3A) H(3B) H(4A) H(4B) H(4C) H(6) H(7) H(8) H(10) H(11) H(12) KP-XI-furan-enzymatic-alcohol Page 12

13 Table 6. Torsion angles [ ] for O(1)-P(1)-O(2)-C(1) (16) O(3)-P(1)-O(2)-C(1) 60.59(15) C(5)-P(1)-O(2)-C(1) (14) O(1)-P(1)-O(3)-C(3) (14) O(2)-P(1)-O(3)-C(3) (12) C(5)-P(1)-O(3)-C(3) (13) P(1)-O(2)-C(1)-C(2) (14) P(1)-O(3)-C(3)-C(4) 96.10(15) O(1)-P(1)-C(5)-F(2) (10) O(3)-P(1)-C(5)-F(2) 42.87(11) O(2)-P(1)-C(5)-F(2) (11) O(1)-P(1)-C(5)-F(1) (12) O(3)-P(1)-C(5)-F(1) (10) O(2)-P(1)-C(5)-F(1) 50.60(12) O(1)-P(1)-C(5)-C(6) 46.90(13) O(3)-P(1)-C(5)-C(6) (12) O(2)-P(1)-C(5)-C(6) (11) F(2)-C(5)-C(6)-O(4) (15) F(1)-C(5)-C(6)-O(4) (12) P(1)-C(5)-C(6)-O(4) 50.69(15) F(2)-C(5)-C(6)-C(7) 54.95(17) F(1)-C(5)-C(6)-C(7) (16) P(1)-C(5)-C(6)-C(7) (11) O(4)-C(6)-C(7)-C(8) (16) C(5)-C(6)-C(7)-C(8) (17) C(6)-C(7)-C(8)-C(9) (14) C(7)-C(8)-C(9)-C(10) (17) C(7)-C(8)-C(9)-C(12) -1.6(3) C(12)-C(9)-C(10)-O(5) 0.31(18) C(8)-C(9)-C(10)-O(5) (14) C(11)-O(5)-C(10)-C(9) -0.13(18) C(10)-O(5)-C(11)-C(12) -0.13(18) O(5)-C(11)-C(12)-C(9) 0.31(18) C(10)-C(9)-C(12)-C(11) -0.37(17) C(8)-C(9)-C(12)-C(11) (15) KP-XI-furan-enzymatic-alcohol Page 13

14 Table 7. Hydrogen bonds for 12042[Å and ]. D-H...A d(d-h) d(h...a) d(d...a) <(DHA) O(4)-H(4O)...O(1)#1 0.88(2) 1.88(2) (17) 161.2(19) Symmetry transformations used to generate equivalent atoms: #1 x-1, y, z KP-XI-furan-enzymatic-alcohol Page 14