Structure k27b		
Sample pHP - pH		

Crystal Structure Report 

for 

C15H12O4

Professor Rich Givens 

Beth Cope

January 27, 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 .................................…….	 24

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

Comments
	The asymmetric unit contains one C15H12O4 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 crystals of C15H12O4 are, at 100(2) K, orthorhombic, space group P212121 – D24 (No. 19) (1) with a = 8.470(1) Å, b = 9.844(1) Å, c = 14.474(2) Å, V = 1206.8(3) Å3 and Z =  4 molecules {dcalcd = 1.410 g/cm3; a(MoK) = 0.103 mm-1}.   A full hemisphere of diffracted intensities (1850 10-second frames with a  scan width of 0.30) was measured for a single-domain specimen using graphite-monochromated MoK radiation (= 0.71073 Å) on a Bruker SMART APEX CCD Single Crystal Diffraction System (2).  X-rays were provided by a fine-focus sealed x-ray tube operated at 50kV and 30mA.  Lattice constants were determined with the Bruker SAINT software package using peak centers for 1901 reflections.  A total of 14702 integrated reflection intensities having 2((MoK)< 61.14 were produced using the Bruker program SAINT(3); 3686 of these were unique and gave Rint = 0.056 with a coverage which was 99.9% complete. The data were corrected empirically for variable absorption effects using equivalent reflections; the relative transmission factors ranged from 0.877 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(4). 
	The final structural model 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 220 parameters were refined using no restraints, 3686 data and weights of w = 1/ [2(F2) + (0.0648 P)2 + 0.2445 P], where P = [Fo2 + 2Fc2] / 3.  Final agreement factors at convergence are:  R1(unweighted, based on F) = 0.066 for 2836 independent absorption-corrected “observed” reflections having 2(MoK)<  61.14 and I>2(I);  R1(unweighted, based on F) = 0.089 and wR2(weighted, based on F2) = 0.148 for all 3686 independent absorption-corrected reflections having 2(MoK)< 61.14.  The largest shift/s.u. was 0.000 in the final refinement cycle.  The final difference map had maxima and minima of 0.39 and -0.32 e-/Å3, respectively.  Since the “Flack” parameter refined to a final value of 0.0(14), the absolute structure could not be reliably determined experimentally using anomalous dispersion of the x-rays.

   
 Acknowledgment
	The authors thank the National Science Foundation (grant CHE-0079282) and the University of Kansas for funds to purchase the  x-ray instrument and computers.  

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 (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 C15H12O4.
Empirical formula 	C15H12O4
Formula weight 	256.25
Temperature 	100(2) K
Wavelength 	0.71073 Å
Crystal system 	Orthorhombic
Space group 	P212121 – D24 (No. 19)
Unit cell dimensions	a =  8.470(1) Å	α = 90.000°
	b =  9.844(1) Å	β = 90.000°
	c = 14.474(2) Å	γ  = 90.000°
Volume	1206.8(3) Å3
Z	4
Density (calculated)	1.410 Mg/m3
Absorption coefficient	0.103 mm-1
F(000)	536
Crystal size	0.38 x 0.10 x 0.06 mm3
Theta range for data collection	2.50° to 30.57°
Index ranges	-12 ≤ h ≤ 12, -14 ≤ k ≤ 14, -20 ≤ l ≤ 20
Reflections collected	14702
Independent reflections	3686 [Rint = 0.056]
Completeness to theta = 30.57°	99.9 % 
Absorption correction	Empirical
Max. and min. transmission	1.000 and 0.877
Refinement method	Full-matrix least-squares on F2
Data / restraints / parameters	3686 / 0 / 220
Goodness-of-fit on F2	1.059
Final R indices [I>2sigma(I)]	R1 = 0.066, wR2 = 0.138
R indices (all data)	R1 = 0.089, wR2 = 0.148
Absolute structure parameter	0.0(14)
Largest diff. peak and hole	0.39 and -0.32 e-/Å3
________________________________________________________________________________
R1 =  ||Fo| - |Fc|| /  |Fo| 
wR2 = {  [w(Fo2 - Fc2)2] /  [w(Fo2)2] }1
Table 2.  Atomic coordinates  ( x 104) and equivalent  isotropic displacement parameters (Å2 x 103)
for C15H12O4. U(eq) is defined as one third of  the trace of the orthogonalized Uij tensor.
________________________________________________________________________________ 
	x	y	z	U(eq)
________________________________________________________________________________  
O(1)	272(2)	2447(2)	1206(1)	28(1)
O(2)	1937(2)	4199(2)	1413(1)	34(1)
O(3)	-1523(2)	4245(2)	2047(1)	30(1)
O(4)	-1518(2)	3811(2)	6427(1)	30(1)
C(1)	1191(3)	3468(2)	900(2)	26(1)
C(2)	157(3)	2343(3)	2192(2)	27(1)
C(3)	-888(3)	3447(2)	2574(2)	22(1)
C(4)	-1098(3)	3522(2)	3587(2)	21(1)
C(5)	-2051(3)	4532(2)	3967(2)	23(1)
C(6)	-2211(3)	4657(2)	4914(2)	23(1)
C(7)	-1402(3)	3767(2)	5497(1)	21(1)
C(8)	-450(3)	2756(3)	5125(2)	27(1)
C(9)	-297(3)	2630(2)	4182(2)	25(1)
C(10)	1175(3)	3584(2)	-124(2)	24(1)
C(11)	2028(3)	4629(3)	-522(2)	29(1)
C(12)	2007(3)	4800(3)	-1473(2)	33(1)
C(13)	1154(3)	3917(3)	-2026(2)	29(1)
C(14)	306(3)	2855(3)	-1626(2)	29(1)
C(15)	312(3)	2686(2)	-674(2)	24(1)
________________________________________________________________________________ 
Table 3.   Bond lengths [Å] for C15H12O4.
________________________________________________________________________________ 

O(1)-C(1) 	1.346(3)
O(1)-C(2) 	1.433(3)
O(2)-C(1) 	1.212(3)
O(3)-C(3) 	1.221(3)
O(4)-C(7) 	1.351(3)
O(4)-H(4O) 	0.97(5)
C(1)-C(10) 	1.487(3)
C(2)-C(3) 	1.508(3)
C(2)-H(2A) 	1.00(3)
C(2)-H(2B) 	0.97(3)
C(3)-C(4) 	1.478(3)
C(4)-C(5) 	1.394(3)
C(4)-C(9) 	1.404(3)
C(5)-C(6) 	1.382(3)
C(5)-H(5) 	0.94(3)
C(6)-C(7) 	1.396(3)
C(6)-H(6) 	0.91(3)
C(7)-C(8) 	1.390(3)
C(8)-C(9) 	1.377(3)
C(8)-H(8) 	1.00(3)
C(9)-H(9) 	0.96(3)
C(10)-C(11) 	1.383(3)
C(10)-C(15) 	1.397(3)
C(11)-C(12) 	1.388(3)
C(11)-H(11) 	0.90(3)
C(12)-C(13) 	1.384(4)
C(12)-H(12) 	0.98(3)
C(13)-C(14) 	1.394(4)
C(13)-H(13) 	0.99(2)
C(14)-C(15) 	1.387(3)
C(14)-H(14) 	1.07(4)
C(15)-H(15) 	0.90(3)
________________________________________________________________________________ 

Table 4.   Bond angles [°] for C15H12O4.
________________________________________________________________________________ 

C(1)-O(1)-C(2)	114.8(2)
C(7)-O(4)-H(4O)	114(3)
O(2)-C(1)-O(1)	123.0(2)
O(2)-C(1)-C(10)	124.7(2)
O(1)-C(1)-C(10)	112.3(2)
O(1)-C(2)-C(3)	110.7(2)
O(1)-C(2)-H(2A)	108(1)
C(3)-C(2)-H(2A)	112(2)
O(1)-C(2)-H(2B)	105(2)
C(3)-C(2)-H(2B)	112(2)
H(2A)-C(2)-H(2B)	109(2)
O(3)-C(3)-C(4)	122.4(2)
O(3)-C(3)-C(2)	119.5(2)
C(4)-C(3)-C(2)	118.1(2)
C(5)-C(4)-C(9)	118.9(2)
C(5)-C(4)-C(3)	119.8(2)
C(9)-C(4)-C(3)	121.2(2)
C(6)-C(5)-C(4)	120.8(2)
C(6)-C(5)-H(5)	118(2)
C(4)-C(5)-H(5)	121(2)
C(5)-C(6)-C(7)	119.7(2)
C(5)-C(6)-H(6)	117(2)
C(7)-C(6)-H(6)	123(2)
O(4)-C(7)-C(8)	116.8(2)
O(4)-C(7)-C(6)	123.2(2)
C(8)-C(7)-C(6)	120.0(2)
C(9)-C(8)-C(7)	120.2(2)
C(9)-C(8)-H(8)	122(2)
C(7)-C(8)-H(8)	118(2)
C(8)-C(9)-C(4)	120.4(2)
C(8)-C(9)-H(9)	120(2)
C(4)-C(9)-H(9)	119(2)
C(11)-C(10)-C(15)	120.4(2)
C(11)-C(10)-C(1)	117.9(2)
C(15)-C(10)-C(1)	121.7(2)
C(10)-C(11)-C(12)	119.8(2)
C(10)-C(11)-H(11)	121(2)
C(12)-C(11)-H(11)	119(2)
C(13)-C(12)-C(11)	120.3(3)
C(13)-C(12)-H(12)	123(2)
C(11)-C(12)-H(12)	117(2)
C(12)-C(13)-C(14)	120.0(2)
C(12)-C(13)-H(13)	122(1)
C(14)-C(13)-H(13)	117(1)
C(15)-C(14)-C(13)	120.0(2)
C(15)-C(14)-H(14)	119(2)
C(13)-C(14)-H(14)	121(2)
C(14)-C(15)-C(10)	119.5(2)
C(14)-C(15)-H(15)	122(2)
C(10)-C(15)-H(15)	119(2)

________________________________________________________________________________: 

 Table 5.   Anisotropic displacement parameters  (Å2 x 103) for C15H12O4. The anisotropic
displacement factor exponent takes the form:  -22[ h2 a*2U11 + ...  + 2 h k a* b* U12 ]
______________________________________________________________________________ 
	U11	U22 	U33	U23	U13	U12
______________________________________________________________________________ 
O(1)	43(1) 	25(1)	16(1) 	-1(1)	-1(1) 	0(1)
O(2)	39(1) 	42(1)	20(1) 	0(1)	-5(1) 	-9(1)
O(3)	38(1) 	30(1)	22(1) 	5(1)	-7(1) 	5(1)
O(4)	35(1) 	38(1)	18(1) 	-4(1)	-1(1) 	6(1)
C(1)	31(1) 	28(1)	19(1) 	1(1)	-1(1) 	0(1)
C(2)	39(1) 	26(1)	17(1) 	1(1)	-3(1) 	1(1)
C(3)	25(1) 	22(1)	19(1) 	2(1)	-2(1) 	-3(1)
C(4)	23(1) 	23(1)	17(1) 	2(1)	0(1) 	0(1)
C(5)	25(1) 	21(1)	24(1) 	3(1)	-2(1) 	0(1)
C(6)	21(1) 	22(1)	26(1) 	0(1)	1(1) 	3(1)
C(7)	21(1) 	25(1)	17(1) 	2(1)	0(1) 	-1(1)
C(8)	31(1) 	31(1)	19(1) 	6(1)	1(1) 	6(1)
C(9)	30(1) 	24(1)	22(1) 	4(1)	1(1) 	6(1)
C(10)	26(1) 	29(1)	18(1) 	1(1)	-1(1) 	3(1)
C(11)	31(1) 	32(1)	24(1) 	-3(1)	-4(1) 	-2(1)
C(12)	34(1) 	41(2)	23(1) 	5(1)	4(1) 	0(1)
C(13)	28(1) 	43(1)	17(1) 	4(1)	0(1) 	5(1)
C(14)	29(1) 	38(1)	21(1) 	-3(1)	0(1) 	1(1)
C(15)	26(1) 	28(1)	20(1) 	-1(1)	0(1) 	2(1)
______________________________________________________________________________ 
Table 6.   Hydrogen coordinates ( x 104) and isotropic  displacement parameters (Å2 x 103)
for C15H12O4.
________________________________________________________________________________ 
	x 	y 	z 	U(eq)
________________________________________________________________________________ 
H(4O)	-2200(70)	4530(50)	6660(30)	130(20)
H(2A)	1250(30)	2380(30)	2457(17)	28(6)
H(2B)	-290(30)	1450(30)	2299(18)	30(7)
H(5)	-2670(40)	5100(30)	3590(20)	41(8)
H(6)	-2840(40)	5350(30)	5130(20)	39(8)
H(8)	110(30)	2140(30)	5560(20)	43(8)
H(9)	300(30)	1900(30)	3923(19)	36(8)
H(11)	2580(40)	5220(30)	-170(20)	36(8)
H(12)	2610(30)	5570(30)	-1722(19)	32(7)
H(13)	1300(30)	3890(20)	-2704(16)	17(6)
H(14)	-330(40)	2150(40)	-2050(20)	58(10)
H(15)	-240(30)	2020(30)	-399(17)	16(6)
________________________________________________________________________________ 
 Table 7.  Torsion angles [°] for C15H12O4.
________________________________________________________________________________ 
C(2)-O(1)-C(1)-O(2)	4.0(3)
C(2)-O(1)-C(1)-C(10)	-176.01(19)
C(1)-O(1)-C(2)-C(3)	74.5(3)
O(1)-C(2)-C(3)-O(3)	1.7(3)
O(1)-C(2)-C(3)-C(4)	-178.0(2)
O(3)-C(3)-C(4)-C(5)	0.0(3)
C(2)-C(3)-C(4)-C(5)	179.8(2)
O(3)-C(3)-C(4)-C(9)	-177.0(2)
C(2)-C(3)-C(4)-C(9)	2.7(3)
C(9)-C(4)-C(5)-C(6)	-0.1(3)
C(3)-C(4)-C(5)-C(6)	-177.2(2)
C(4)-C(5)-C(6)-C(7)	0.4(3)
C(5)-C(6)-C(7)-O(4)	-178.9(2)
C(5)-C(6)-C(7)-C(8)	-0.4(3)
O(4)-C(7)-C(8)-C(9)	178.8(2)
C(6)-C(7)-C(8)-C(9)	0.2(4)
C(7)-C(8)-C(9)-C(4)	0.1(4)
C(5)-C(4)-C(9)-C(8)	-0.1(3)
C(3)-C(4)-C(9)-C(8)	177.0(2)
O(2)-C(1)-C(10)-C(11)	-2.3(4)
O(1)-C(1)-C(10)-C(11)	177.6(2)
O(2)-C(1)-C(10)-C(15)	178.6(2)
O(1)-C(1)-C(10)-C(15)	-1.4(3)
C(15)-C(10)-C(11)-C(12)	1.1(4)
C(1)-C(10)-C(11)-C(12)	-178.0(2)
C(10)-C(11)-C(12)-C(13)	-0.9(4)
C(11)-C(12)-C(13)-C(14)	0.3(4)
C(12)-C(13)-C(14)-C(15)	0.3(4)
C(13)-C(14)-C(15)-C(10)	-0.2(4)
C(11)-C(10)-C(15)-C(14)	-0.5(4)
C(1)-C(10)-C(15)-C(14)	178.6(2)
________________________________________________________________________________ 
Table 8.  Hydrogen bonds for C15H12O4  [Å and °].
____________________________________________________________________________ 
D-H...A	d(D-H)	d(H...A)	d(D...A)	<(DHA)
____________________________________________________________________________ 
 O(4)-H(4O)...O(3)#1	0.97(5)	1.71(5)	2.687(2)	177(5)
____________________________________________________________________________ 
Symmetry transformations used to generate equivalent atoms:  #1:  -x-1/2, -y+1, z+1/2.