Structure k24e		
BC - pHP - Tos		

Crystal Structure Report 

for 

C15H14SO5

Professor Rich Givens 

Beth Cope

February 4, 2007

 Contents 
	
Figure 1.  50% Probability Ellipsoid Drawing of Molecule ... …....    3
Figure 2.  Packing Diagram ..........................................……….…	 12
Comments .............................................................…………….…	15
Experimental .........................................................……………….	15
Acknowledgements .....................................................…………..	16
References ...........................................................………………..	16
Table 1.  Crystal Data ...............................................…………….	17
Table 2.  Atom Coordinates for Nonhydrogen Atoms......………… 18
Table 3.  Bond Lengths ……………….................................…..….	19
Table 4.  Bond Angles …………………................................…….. 	20
Table 5.  Nonhydrogen Anisotropic Displacement Parameters ..   21
Table 6.  Hydrogen Atom Parameters .................................…....	 22
Table 7.  Torsion Angles .............................................…….…….	 23
Table 8.  Hydrogen Bond Geometries .................................…….	 25

Appendix: 
Table 9.  Structure Factors ..........................................…………..	 1

Comments
	The asymmetric unit contains one C15H14SO5 molecule.  All displacement ellipsoids are drawn at the 50% probability level.

Brief  Experimental Description to be Included as Text or as a Footnote at Time of Publication
	Colorless needle-shaped crystals of C15H14SO5 are, at 296(2) K, monoclinic, space group P21/c – C2h5 (No. 14) (1) with a = 5.6756(4) Å, b = 14.2907(8) Å, c = 17.744(1) Å,  = 99.153(5), V = 1420.9(2) Å3 and Z =  4 molecules {dcalcd = 1.432 g/cm3; a(CuK) = 2.209 mm-1}.   A full hemisphere of diffracted intensities (3134 5-second frames with an  or  scan width of 0.80) was measured for a two-domain specimen using monochromated CuK radiation (= 1.54178 Å) on a Bruker Proteum SMART 6000 Single Crystal Diffraction System (2).  X-rays were provided by a Bruker-Nonius FR591 rotating anode operating at 5kW with a 3.0 x 3.0 mm focal cup.  The beam was collimated and focused with double-diffracting confocal multilayer optics (Montel mirrors).  Lattice constants were determined with the Bruker SAINT software package using peak centers for 6721 reflections.  A total of 11299 integrated reflection intensities having 2(CuK)< 137.53 were produced using the Bruker program SAINT(3); 2540 of these were unique and gave Rint = 0.069 with a coverage which was 94.9% complete. The data were corrected empirically (4) for variable absorption effects using equivalent reflections; the relative transmission factors ranged from 0.830 to 1.000.  The Bruker software package SHELXTL was used to solve the structure using “direct methods” techniques.  All stages of weighted full-matrix least-squares refinement were conducted using Fo2 data with the SHELXTL Version 6.10 software package(5). 
	The crystal initially appeared to utilize the C-centered orthorhombic space group C2221 – D25  (No. 20) with a = 5.6756(4) Å, b = 35.036(2) Å and c = 14.2907(8) Å .  Merging the intensity data according to orthorhombic D2h-mmm Laue symmetry gave Rsym = 0.088. When the structure could not be solved in this orthorhombic space group, the symmetry was reduced to monoclinic C21 [a nonstandard centered setting of P21 – C22 (No. 4) with c as the unique axis].  The structure was solved in this space group to give an asymmetric unit that contained two crystallographically-independent molecules.  When properly translated and transformed in the unit cell, these two molecules were seen to be rigorously related by the symmetry operations of space group P21/c when the C-centered orthorhombic unit cell was transformed to the corresponding primitive monoclinic cell.  The data frames were reintegrated based on the primitive monoclinic unit cell and final lattice constants were obtained.  However, the structural model containing one independent C15H14SO5 molecule in space group P21/c would not refine below R1 = 0.28.  Incorporation of 2-domain (54/46) pseudomerohedral twinning by a twofold rotation about the orthorhombic a axis, reduced R1  to 0.07.  
	The final structural model utilized space group P21/c and incorporated anisotropic thermal parameters for all nonhydrogen atoms and isotropic thermal parameters for all hydrogen atoms.  All hydrogen atoms were located in a difference Fourier and included in the structural model as independent isotropic atoms whose parameters were allowed to vary in least-squares refinement cycles.  A total of 248 parameters were refined using no restraints, 2540 data and weights of w = 1/ [2(F2) + (0.0725 P)2+  1.0148 P] where P = [Fo2 + 2Fc2] / 3.  Final agreement factors at convergence are:  R1(unweighted, based on F) = 0.066 for 2312 independent absorption-corrected “observed” reflections having 2(CuK)<  137.53 and I>2(I);  R1(unweighted, based on F) = 0.071 and wR2(weighted, based on F2) = 0.163 for all 2540 independent absorption-corrected reflections having 2(CuK)< 137.53.  The largest shift/s.u. was 0.000 in the final refinement cycle.  The final difference map had maxima and minima of 0.45 and -0.35 e-/Å3, respectively.  
   
 Acknowledgment
	The authors thank the EMSL facility at the Pacific Northwest National Laboratory in Richland, Washington for providing access to the x-ray instrument and computers used to collect the data used to solve and refine this crystal structure.  

References

(1)	 International Tables for Crystallography, Vol A, 4th ed., Kluwer:  Boston (1996). 
(2)	Data Collection:  SMART Software Reference Manual (1998). Bruker-AXS, 5465 E. Cheryl Parkway, Madison, WI  53711-5373  USA.   
(3)	Data Reduction:  SAINT Software Reference Manual (1998). Bruker-AXS, 6300 Enterprise Dr., Madison, WI 53719-1173, USA. 
(4)	G. M. Sheldrick (2002).  SADABS.  Program for Empirical Absorption Correction of Area Detector Data.  University of Göttingen, Germany. 
(5)	G. M. Sheldrick (2000). SHELXTL Version 6.10 Reference Manual. Bruker-AXS, 5465 E. Cheryl Parkway, Madison, WI  53711-5373 USA.  

Table 1.  Crystal data and structure refinement for C15H14SO5.
Empirical formula 	C15H14SO5
Formula weight 	306.32
Temperature 	296(2) K
Wavelength 	1.54178 Å
Crystal system 	Monoclinic
Space group 	P21/c – C2h5 (No. 14)
Unit cell dimensions	a = 5.6756(4) Å	 = 90.000°
	b = 14.2907(8) Å	 = 99.153(5)°
	c = 17.7440(11) Å	  = 90.000°
Volume	1420.86(16) Å3
Z	4
Density (calculated)	1.432 Mg/m3
Absorption coefficient	2.209 mm-1
F(000)	640
Crystal size	0.40 x 0.05 x 0.03 mm3
Theta range for data collection	2.52° to 68.76°
Index ranges	-6  h  6, -17  k  15, -21  l  19
Reflections collected	11299
Independent reflections	2540 [Rint = 0.069]
Completeness to theta = 68.76°	94.9 % 
Absorption correction	Empirical
Max. and min. transmission	1.000 and 0.830
Refinement method	Full-matrix least-squares on F2
Data / restraints / parameters	2540 / 0 / 248
Goodness-of-fit on F2	1.209
Final R indices [I>2sigma(I)]	R1 = 0.066, wR2 = 0.161
R indices (all data)	R1 = 0.071, wR2 = 0.163
Extinction coefficient	0.002(1)
Largest diff. peak and hole	0.45 and -0.35 e-/Å3
------------------------------------------------------------------------------------------------------------------------
R1 =  ||Fo| - |Fc|| /  |Fo| 
wR2 = {  [w(Fo2 - Fc2)2] /  [w(Fo2)2] }1/2 

Table 2.  Atomic coordinates  ( x 104) and equivalent  isotropic displacement parameters (Å2x 103)
for C15H14SO5.  U(eq) is defined as one third of  the trace of the orthogonalized Uij tensor.
________________________________________________________________________________ 
	x	y	z	U(eq)
________________________________________________________________________________  
S	3126(2)	6514(1)	350(1)	44(1)
O(1)	2008(7)	5913(2)	947(2)	53(1)
O(2)	51(7)	4959(2)	1914(2)	56(1)
O(3)	5629(7)	6530(3)	566(3)	68(1)
O(4)	2227(9)	6189(3)	-393(2)	66(1)
O(5)	3670(8)	807(3)	2528(2)	55(1)
C(1)	2778(10)	4962(3)	1034(3)	43(1)
C(2)	1550(9)	4526(3)	1649(2)	42(1)
C(3)	2220(8)	3557(3)	1888(2)	38(1)
C(4)	802(10)	3086(4)	2338(3)	46(1)
C(5)	1269(9)	2176(4)	2570(3)	44(1)
C(6)	3165(9)	1717(3)	2336(2)	40(1)
C(7)	4622(9)	2167(3)	1902(3)	43(1)
C(8)	4144(10)	3079(4)	1677(3)	45(1)
C(9)	1851(9)	7596(3)	519(3)	42(1)
C(10)	3060(11)	8217(4)	1044(3)	46(1)
C(11)	1990(10)	9042(4)	1186(3)	49(1)
C(12)	-313(11)	9264(4)	826(3)	52(1)
C(13)	-1422(11)	8644(4)	299(4)	55(1)
C(14)	-392(11)	7806(4)	135(3)	52(1)
C(15)	-1580(18)	10138(6)	1022(5)	73(2)
________________________________________________________________________________ 
Table 3.   Bond lengths [Å] for C15H14SO5.
___________________________________________________________________________ 

S-O(3) 	1.411(4)
S-O(4) 	1.415(4)
S-O(1) 	1.574(3)
S-C(9) 	1.753(5)
O(1)-C(1) 	1.428(6)
O(2)-C(2) 	1.207(6)
O(5)-C(6) 	1.362(6)
O(5)-H(5O) 	0.80(5)
C(1)-C(2) 	1.518(7)
C(1)-H(1A) 	0.97(5)
C(1)-H(1B) 	1.00(5)
C(2)-C(3) 	1.480(7)
C(3)-C(8) 	1.389(7)
C(3)-C(4) 	1.395(7)
C(4)-C(5) 	1.377(8)
C(4)-H(4) 	0.86(6)
C(5)-C(6) 	1.380(7)
C(5)-H(5) 	0.99(5)
C(6)-C(7) 	1.376(7)
C(7)-C(8) 	1.377(7)
C(7)-H(7) 	0.90(5)
C(8)-H(8) 	0.93(6)
C(9)-C(14) 	1.378(8)
C(9)-C(10) 	1.387(7)
C(10)-C(11) 	1.368(8)
C(10)-H(10) 	0.95(6)
C(11)-C(12) 	1.398(8)
C(11)-H(11) 	1.04(6)
C(12)-C(13) 	1.367(8)
C(12)-C(15) 	1.509(9)
C(13)-C(14) 	1.384(8)
C(13)-H(13) 	0.79(5)
C(14)-H(14) 	0.89(7)
C(15)-H(15A) 	1.10(10)
C(15)-H(15B) 	0.84(12)
C(15)-H(15C) 	0.90(10)

_______________________________________________________________________________ 

Table 4.   Bond  angles [°] for C15H14SO5.
___________________________________________________________________________ 

O(3)-S-O(4)	117.1(3)
O(3)-S-O(1)	108.8(2)
O(4)-S-O(1)	108.9(2)
O(3)-S-C(9)	111.4(3)
O(4)-S-C(9)	110.6(2)
O(1)-S-C(9)	98.4(2)
C(1)-O(1)-S	116.4(3)
C(6)-O(5)-H(5O)	109(4)
O(1)-C(1)-C(2)	107.5(4)
O(1)-C(1)-H(1A)	108(3)
C(2)-C(1)-H(1A)	117(3)
O(1)-C(1)-H(1B)	120(3)
C(2)-C(1)-H(1B)	106(3)
H(1A)-C(1)-H(1B)	98(4)
O(2)-C(2)-C(3)	122.2(4)
O(2)-C(2)-C(1)	120.2(5)
C(3)-C(2)-C(1)	117.6(4)
C(8)-C(3)-C(4)	117.9(5)
C(8)-C(3)-C(2)	124.1(4)
C(4)-C(3)-C(2)	118.1(4)
C(5)-C(4)-C(3)	121.7(5)
C(5)-C(4)-H(4)	119(3)
C(3)-C(4)-H(4)	119(3)
C(4)-C(5)-C(6)	118.8(5)
C(4)-C(5)-H(5)	121(3)
C(6)-C(5)-H(5)	119(3)
O(5)-C(6)-C(7)	117.7(5)
O(5)-C(6)-C(5)	121.5(5)
C(7)-C(6)-C(5)	120.8(4)
C(6)-C(7)-C(8)	119.8(5)
C(6)-C(7)-H(7)	117(3)
C(8)-C(7)-H(7)	123(3)
C(7)-C(8)-C(3)	120.9(5)
C(7)-C(8)-H(8)	117(4)
C(3)-C(8)-H(8)	122(4)
C(14)-C(9)-C(10)	120.9(5)
C(14)-C(9)-S	118.8(4)
C(10)-C(9)-S	120.3(4)
C(11)-C(10)-C(9)	119.2(5)
C(11)-C(10)-H(10)	121(4)
C(9)-C(10)-H(10)	119(4)
C(10)-C(11)-C(12)	121.5(5)
C(10)-C(11)-H(11)	120(3)
C(12)-C(11)-H(11)	119(3)
C(13)-C(12)-C(11)	117.4(5)
C(13)-C(12)-C(15)	120.7(6)
C(11)-C(12)-C(15)	121.9(6)
C(12)-C(13)-C(14)	122.8(6)
C(12)-C(13)-H(13)	121(4)
C(14)-C(13)-H(13)	116(4)
C(9)-C(14)-C(13)	118.1(5)
C(9)-C(14)-H(14)	118(4)
C(13)-C(14)-H(14)	123(4)
C(12)-C(15)-H(15A)	117(5)
C(12)-C(15)-H(15B)	109(8)
H(15A)-C(15)-H(15B)	97(9)
C(12)-C(15)-H(15C)	112(6)
H(15A)-C(15)-H(15C)	103(7)
H(15B)-C(15)-H(15C)	118(9)

_______________________________________________________________________________ 

Table 5.   Anisotropic displacement parameters  (Å2x 103) for C15H14SO5.  The anisotropic
displacement factor exponent takes the form:  -22[ h2 a*2U11 + ...  + 2 h k a* b* U12 ]
______________________________________________________________________________ 
	U11	U22 	U33	U23	U13	U12
______________________________________________________________________________ 
S	51(1) 	33(1)	51(1) 	3(1)	20(1) 	-4(1)
O(1)	70(3) 	31(2)	65(2) 	8(2)	31(2) 	6(2)
O(2)	67(3) 	42(2)	68(2) 	1(2)	33(2) 	16(2)
O(3)	45(2) 	53(2)	111(3) 	2(2)	24(2) 	-4(2)
O(4)	92(3) 	56(2)	53(2) 	-6(2)	22(2) 	3(2)
O(5)	58(3) 	41(2)	68(2) 	12(2)	14(2) 	-3(2)
C(1)	50(3) 	27(2)	54(3) 	-2(2)	18(2) 	2(2)
C(2)	52(3) 	35(2)	39(2) 	-3(2)	9(2) 	0(2)
C(3)	45(3) 	34(2)	35(2) 	0(2)	6(2) 	-2(2)
C(4)	48(3) 	44(3)	50(3) 	-3(2)	23(2) 	2(2)
C(5)	44(3) 	44(3)	47(2) 	4(2)	14(2) 	-5(2)
C(6)	43(3) 	34(2)	40(2) 	2(2)	2(2) 	-2(2)
C(7)	38(3) 	40(3)	54(3) 	0(2)	10(2) 	5(2)
C(8)	46(3) 	39(3)	54(3) 	2(2)	16(2) 	-3(2)
C(9)	44(3) 	39(3)	43(2) 	10(2)	11(2) 	-5(2)
C(10)	51(3) 	40(3)	47(3) 	2(2)	3(2) 	-4(2)
C(11)	58(3) 	40(3)	53(3) 	-8(2)	14(2) 	-7(2)
C(12)	62(4) 	42(3)	55(3) 	8(2)	23(3) 	1(3)
C(13)	43(3) 	53(3)	67(3) 	10(3)	3(3) 	8(3)
C(14)	56(3) 	44(3)	54(3) 	-2(2)	3(3) 	-11(3)
C(15)	88(5) 	53(4)	82(5) 	-1(3)	31(4) 	18(4)
______________________________________________________________________________ 
Table 6.   Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103)
for C15H14SO5.
________________________________________________________________________________ 
	x 	y 	z 	U(eq)
________________________________________________________________________________ 
 
H(5O)	2640(100)	610(40)	2740(30)	34(14)
H(1A)	4510(90)	4950(30)	1120(20)	29(11)
H(1B)	2500(100)	4520(40)	590(30)	50(14)
H(4)	-440(100)	3370(40)	2460(30)	41(13)
H(5)	140(90)	1820(40)	2840(30)	42(13)
H(7)	5850(90)	1840(30)	1770(20)	31(11)
H(8)	5220(110)	3370(40)	1410(30)	58(16)
H(10)	4600(110)	8060(40)	1300(30)	56(16)
H(11)	2900(110)	9510(40)	1570(30)	50(14)
H(13)	-2720(100)	8740(30)	80(30)	36(14)
H(14)	-1030(130)	7430(50)	-240(40)	71(19)
H(15A)	-2830(180)	10470(60)	560(50)	120(30)
H(15B)	-2600(200)	10000(80)	1300(60)	160(50)
H(15C)	-550(180)	10600(70)	1180(50)	120(40)
________________________________________________________________________________ 
Table 7.  Torsion angles [°] for C15H14SO5.
_______________________________________________________________________________ 
O(3)-S-O(1)-C(1)	-59.2(4)
O(4)-S-O(1)-C(1)	69.5(4)
C(9)-S-O(1)-C(1)	-175.3(4)
S-O(1)-C(1)-C(2)	178.3(3)
O(1)-C(1)-C(2)-O(2)	6.3(7)
O(1)-C(1)-C(2)-C(3)	-175.1(4)
O(2)-C(2)-C(3)-C(8)	-171.0(5)
C(1)-C(2)-C(3)-C(8)	10.5(7)
O(2)-C(2)-C(3)-C(4)	10.7(7)
C(1)-C(2)-C(3)-C(4)	-167.9(5)
C(8)-C(3)-C(4)-C(5)	-0.1(7)
C(2)-C(3)-C(4)-C(5)	178.4(5)
C(3)-C(4)-C(5)-C(6)	-1.3(8)
C(4)-C(5)-C(6)-O(5)	-178.0(4)
C(4)-C(5)-C(6)-C(7)	2.3(7)
O(5)-C(6)-C(7)-C(8)	178.2(5)
C(5)-C(6)-C(7)-C(8)	-2.0(8)
C(6)-C(7)-C(8)-C(3)	0.6(8)
C(4)-C(3)-C(8)-C(7)	0.4(7)
C(2)-C(3)-C(8)-C(7)	-178.0(5)
O(3)-S-C(9)-C(14)	159.8(4)
O(4)-S-C(9)-C(14)	27.7(5)
O(1)-S-C(9)-C(14)	-86.2(4)
O(3)-S-C(9)-C(10)	-21.8(5)
O(4)-S-C(9)-C(10)	-153.9(4)
O(1)-S-C(9)-C(10)	92.2(4)
C(14)-C(9)-C(10)-C(11)	0.8(7)
S-C(9)-C(10)-C(11)	-177.6(4)
C(9)-C(10)-C(11)-C(12)	1.3(7)
C(10)-C(11)-C(12)-C(13)	-2.8(7)
C(10)-C(11)-C(12)-C(15)	175.4(6)
C(11)-C(12)-C(13)-C(14)	2.3(8)
C(15)-C(12)-C(13)-C(14)	-175.9(6)
C(10)-C(9)-C(14)-C(13)	-1.3(7)
S-C(9)-C(14)-C(13)	177.1(4)
C(12)-C(13)-C(14)-C(9)	-0.3(8)
________________________________________________________________________________ 

Table 8.  Hydrogen bonds for C15H14SO5 [Å and °].
____________________________________________________________________________ 
D-H...A	d(D-H)	d(H...A)	d(D...A)	<(DHA)
____________________________________________________________________________ 
 O(5)-H(5O)...O(2)#1	0.80(5)	1.97(6)	2.752(5)	168(5)
____________________________________________________________________________ 
Symmetry transformations used to generate equivalent atoms:  #1:  -x, y-1/2, -z+1/2.