CRYSTAL STRUCTURE
Vol. 6, No. 3, March 1967 TABLE VI INTERMOLECULAR DISTANCES~ X,&X
Molecule
j
K( 1)-0(1 )
Distance, A
B(000) B (io0) E(100) E(110) B (TOO) A(000)
K(1)-0(2) K(1)-0(2) ~(1)-0(3 K ( 1)-OW K ( ~ ) - o(3
2.690 3.230 2.963 2.961 3.130 3.208
K(2)-0(1) A(000) 2.027 K(2)-0(1) D(Ol1) 3.180 K@)-W) A(000) 2.739 K(2)-0(2) B(iO1) 2.767 ~ ( 2 ~ x 3 ) C(OO1) 2.804 K(2)-0(3) E(111) 2.719 0(4)-0(4) D(OO1) 3.423 0 (4)-0 (6) B(iO0) 3.442 O(5)-0 (6 1 D(101) 3.499 0(5)-0(6) E(111) 3.365 0(6)-0(6) c(oio) 3.189 XI is in the molecule A and xj in the molecule specified after xj. The molecules are located as follows: A: x , y, z; B: '/z x, '/z - y , ' / z - Z; '2: X , '/2 y,Z; D: 3, 9, 2; E: -'/z - X, -1/2
+ Y,
-I/?
+
+
-
z.
OF
HYDROXYLAMINE-0-SULFONIC ACID 511
atoms form a distorted octahedron around the potassium ion K(2). The coordination polyhedron is completed by three other longer contacts, one a t 2.927 A and two at 3.180 A. However, in the case of K(1) there is only one oxygen atom less than 2.9 A away from the ion, a t 2.690 A. The next nearest oxygen atoms around K(1) are two a t 2.961 A and two a t 2.963 A. The coordination is completed by five additional oxygen atoms, two a t 3.130 A, two a t 3.208 A, and one a t 3.20 A. The complexity of the coordination polyhedra around the two ions is similar to that found in other potassium salts where the K .O distances range from 2.62 to 3.20 A. The coordination of oxygen atoms around the two cations cannot be explained on the basis of anion-anion contacts. A survey of the 0 . intermolecular distances tabulated in Table VI reveals only one distance (3.189 A) which could represent van der Waals contact. I n all other cases the 0.' - 0 distances are too long. Therefore, the crystal packing must be determined mainly by the cation-anion contacts. a
0
CONTRIBUTION FROM
THE CHEMISTRY DEPARTMENT, UNIVERSITY O F IOWA,IOWA CITY, IOWA
The Crystal Structure of Hydroxylamine-0-sulfonic Acid BY N. C. BAENZIGER, ROGER F. BELT,
AND
CAROL VALLEY GOEBEL
Received May 6 , 1966 The crystal structure of hydroxylamine-0-sulfonic acid (HsNOS03H) was determined from Weissenberg and precession singlecrystal X-ray diffraction patterns. The diffraction patterns indicated that the crystals were orthorhombic, but satisfactory agreement with the visually observed intensity data was obtained only by assuming that the crystals were monoclinic and twinned on (001) or (100). This assumption led to a structure in which the oxygen atoms are located in a distorted tetrahedral fashion about the sulfur atom at distances of 1.42, 1.46, 1.47, and 1.68 A (average error = 1 0 . 0 3 A); the oxygen atom involved in the long S-0 bond is also bonded to a nitrogen atom at 1.48 A. The structure is compatible with the zwitterion form of the acid found from previous nmrstudies of Richards andY0rke.I The crystal structure results should be considered corroborative rather than determinative of the zwitterion form.
Introduction The determination of the structure of hydroxylamine0-sulfonic acid, H2NOS03H, was begun some 10 years ago a t this laboratory in conjunction with a study of some hydroxylaminesulfonic acids and their salts. a The compounds are generally unstable, but HzNOSOgH was stable enough to form crystals. When i t became apparent that the structure of HzNOSO~H could not be solved without assuming crystal twinning, the computations proved too involved for more than a rough determination of the structure in 1956. Recently there has been some interest in related struct u r e ~ . ~ -On ~ this basis i t seemed worthwhile to under(1) R. E. Richards a n d R. W. Yorke, J . Chem. SOC.,2821 (1959). (2) R. F. Belt, Ph.D. Theisis, University of Iowa, 1956. (3) R. F. Belt a n d N. C. Baenziger, J . A m . Chem. Soc., 79, 316 (1957). (4) D. W. J. Cruickshank, J . Chem. Soc., 5486 (1961). ( 5 ) D. W. J. Cruickshank and D. W. Jones, Acto Cryst., 16, 877 (1903). (6) C. Pascard-Billy, i b i d . , IS, 829 (1965).
take a three-dimensional refinement of HzNOSOaH using the original intensity data and employing the more elegant computational methods offered by modern computers. Experimental Details Hydroxylamine-0-sulfonic acid was prepared by the method of Sommer, Schulz, and Nassau.' The powdery product was recrystallized from water under reduced pressure a t 0'. Single crystals were sealed in glass capillaries and examined by X-ray diffraction. The crystal constants are a = 6.395 0.017 A, b = 10.707 rt 0.010 A, c = 5.050 f 0.007 A, and p = 90.0 =t 0.2'. The X-ray density for four molecules per unit cell is 2.17 g/cmS which is in excellent agreement with the experimental value of 2.17 g/cm.a Intensity data were taken including Okl through 3kZ and hk0 Weissenberg films and hO1 precession films. The relative intensities were estimated visually using a calibrated strip. Lorentz (7) F. Sommer, 0. Schulz and M. Nassau, Z. Anovg. Allgem. Chem., 147, 142 (1925).
512 N.
c. BAENZIGER,ROGERF. BELT,
AND C A R O L VALLEY
Inorganic Chemistry
GOEBEL
TABLE I ATOMPARAMETERS ,-Two-dimensional
Y
2
--Three-dimensional
refinement (1‘365)--------. 2
Y
X
0,0892 (8) 0,769 (2)a 0,967 (2) 0,800 0.700 (4) 0.810 0.951 (3) 0.138 (2) 0.710 0.596 (4) 0.191 (2) 0.195 0,102 (2) 0,400 0.749 (5) 0.096 0.165 (2) 0.800 0,378 (5) 0.163 ... 0.324 0 I090 ... ... 0.118 ... 0.376 ... ... 0,236 ... 0.270 ... ... Standard deviations in last significant digit are given in parentheses. 0 Estimated position
0.091 0,980 0.143
0.766 0.710 0.939 0.581 0. i66 0.383
a
-
refinement (1956)-
X
0,700
B , Ai
0 693 (2) 0 Ti96 (5) 0 816 (5) 0 816 (6) 0 406 16) 0.728(7)
0 , 9 5 119) 0 . 6 (4) 0 . 6 (4) 1 . 0 (4) 1 . 2( 5 ) 1.116)
0,858 0 544 0 764
1.0 1.0 1.0
TABLE 11 CUMl”\l
LENGTHSAND A N G L E S IVI’III OTlIEl< ~ l I i U C ! T U l U S ”
o--s-0, S-0, A
deg
1.47 (3) 1.42 (2) 1.46 13) 1.464 (4) 1.437 (4) 1.439 (10)” 1.42
115 (5)
1 . 4 5 (3) 1.464 (12) 1.434 (12) 1.463 (9) 1.464 (11) 1.478 (13) 1.453 (5)2
s-OR,
114 (1) 118 ( 2 ) 113 114 115 111 112 114 112 112 (1j 112 fl) 115 (1) 112 113 114
1.003(7)
...
1.645 (5)
...
...
...
...
... ...
... ...
1. 5 i ;2 j
...
A I I . 0, ’1
2.83 ( 2 ) 3.04 12) 2 . 7 7 (3) I
.
.
I
