1894 [Ti(CrHHOS2)C13] AND [Pb(CrHx2OS2)2(NO3) 2] References AGHABORZORG, H., PALENIK, R. C. & PALENIK, G. J. (1986). Inorg. Chim. Acta, lll, L53-L54. International Tables for X-ray Crystallography (1974). Vol. IV. Birmingham: Kynoch Press. (Present distributor D. Reidel, Dordreeht, The Netherlands.) METZ, B. & WEISS, R. (1974) Inorg. Chem. 13, 2094-2098. MUSKER, W. K., OLMSTEAD, M. M. & KESSLER, R. M. (1984). Inorg. Chem. 23, 1764-1768. OLMSTEAD, M. M., MUSKER~ W. K. & KESSLER, R. M. (1984). Acta Cryst. C40, 1172-1175. SHANNON, R. D. (1976). Acta Cryst. A32, 751-767. SHELDRICK, G. M. (1981). Nicolet. SHELXTL Operations Manual. Revision 3. Nicolet XRD Corporation, Madison, WI, USA. Acta Cryst. (1987). C43, 1894-1896 Structures of Ethylenediammonium Monohydrogentetraoxophosphate(V) and Ethylenediamrnonium Monohydrogentetraoxoarsenate(V) BY M. T. AVERBUCH-POUCHOT AND A. DURIF Laboratoire de Cristallographie, Centre National de la Recherche Scientifique, Laboratoire associd d I'USTMG, 166X, 38042 Grenoble CEDEX, France (Received 8 March 1987; accepted 22 May 1987) Abstract. (I): C2H 2-t- 2-- 10N2 .HPO 4 , Mr= 158-09, mono- clinic, P21/a, a= 8.059 (3), b= 11.819 (5), c= 7.513(3)A, fl= 110.12(5), V=672(1)A 3, Z=4, D x = 1.562 Mg m -a, 2(Ag Kct) = 0.5608 A, /z = 0.198mm -l, F(000)=336, T=295K, final R-- 0.030 for 1286 unique reflexions. (II): CEH10N2+. - HAsO 2-, M r=202.04, monoclinic, P2Jc, a= 10.433 (9), b~8.163 (6), c= 8.062 (6)/~, fl= 90.33 (7) °, V= 687 (2) A 3, Z= 4, Dx= 1.953 Mg m -3, 2(Ag Kcz) = 0.5608 ,/k, /~ = 2.740mm -~, F(000) = 408, T= 295 K, final R = 0.038"for 1499 unique reflexions. In both cases planes of XO4 H2- tetrahedra alternate with planes of (CH2) 2- (NHa) 2+ groups. In the first type of planes, XO4H tetrahedra are associated in pairs forming X2OsH42 - NH "X2+ groups. (CH3)2( 312 groups are centrosymmetric for X = As, pseudocentrosymmetric for X = P. Introduction. During investigations of interactions of ethylenediamine with various kinds of acidic mono- phosphates or monoarsenates we very often observed the formation of very stable compounds corresponding to the formula H3J~rO4(CH2)2(NH2)2 (X= P, As). These compounds appeared later to be interesting starting materials for further syntheses. The present work is devoted to a detailed structural investigation of these two species. Experimental. (I) 2+ 2- C2H10N2 .HPO 4 . Single crystals are easily prepared by slow evaporation at room tem- perature of an aqueous solution of H3PO 4 and ethylene- diamine in stoichiometric ratio. Crystals appear as stout, multifaceted, monoclinic prisms. Crystal size: 0.24 x 0.24 x 0.30 mm. Density not measured. Philips 0108-2701/87/101894-03501.50 PW 1100 diffractometer, graphite monochromator. Systematic absences: hOl: h= 2n; 0k0: k=2n. 24 reflexion.s (10 < 0 < 14 °) for refining unit-cell dimen- sions. 09 scan. 2229 non-zero unique reflexions collec- ted (3 < 0 < 30°), +h,k,l, hmax = 13, kmax = 20, /max = 12. Scan width 1.40 °, scan speed 0.03 ° s -l, total background measuring time 10 s. Two intensity and orientation reference reflexions (652 and 652), no variation. Lorentz and polarization correction, no absorption correction. Structure solved by classical methods (Patterson and successive Fourier syntheses). H atoms from difference Fourier map. Anisotropic full- matrix least-squares refinement (on F), isotropic for H atoms. Unit weights. Final refinement cycles with 1286 reflexions corresponding to I > 6o r Final R = 0.030 (wR = 0:035). S = 0.655. Max. A/tr = 0.00. Max. peak height in the final, difference Fourier synthesis 0.39 e A -3. No extinction correction. R = 0.054 for the complete set of 2229 reflexions. Scattering factors for neutral atoms and f', f" from International Tables for X-ray Crystallography (1974). Enraf-Nonius (1977) SDP employed for all calculations. Computer used: PDP 11/70. (II) C2H~0N22+.HAsO 2-. The chemical preparation from H3AsO 4 and ethylenediamine is identical to that described for (I). The morphology of the crystals obtained is close to that of the phosphorus complex. Crystal size: 0.30 x 0-30 x 0.24mm. Density not measured. Philips PW 1100 diffractometer, graphite monochromator. Systematic absences: hOl: l=2n; 0k0: k -- 2n. 18 reflexions (10 < O < 12 °) for refining unit-cell dimensions, o9 scan. 2804 non-zero unique reflexions collected (3 < 0< 30°), +h,k,l, hmax = 16, kmax = 14, /max-----14. Scan width 1.30 °, scan speed © 1987 International Union of Crystallography t
`
`Merck Exhibit 2211, Page 1
`Mylan Pharmaceuticals Inc. v. Merck Sharp & Dohme Corp.
`IPR2020-00040
`
`

`

`M. T. AVERBUCH-POUCHOT AND A. DURIF 1895 0.03 ° s -~, total background measuring time 10 s. Two intensity and orientation reference reflexions (130 and 130) measured every 2 h without significant variation. Lorentz and polarization correction, no absorption correction. Structure solved by classical methods (Pat- terson and successive Fourier syntheses). H atoms from difference Fourier map. Anisotropic full-matrix least- squares refinement (on F), isotropic for H atoms. Unit weights. Final refinement cycles with 1499 reflexions corresponding to I> 9a r Final R =0.038 (wR = 0-043). S = 1.485. Max. A/a= 0.06 [B of H(2N2)I. c ~ -'~'~---~o~ ol2) Fig. 1. Projection along the a direction of the atomic arrangement of HPO4(NH3)2(CH2)2. bl ...... HI3N21 H(2N 1 ) Fig. 2. Projection along the e direction of the atomic arrangement of HAsO4(NH3)2(CH2)2. Table 1. Final atomic coordinates, Beqfor non-H atoms and Bisofor H atoms in HPO4(NH3)2(CH2) z x y z Beq/Blso(A 2) P 0.24191 (7) 0.13601 (5) 0.08489 (7) 1.126 (8) O(1) 0.9061 (2) 0-8820 (1) 0.8223 (2) 2.00 (3) O(2) 0.6426 (2) 0.9694 (I) 0.8584 (2) 1.67 (3) 0(3) 0.3473 (2) 0.6450 (2) 0.1307 (2) 1.72 (3) 0(4) 0.8422 (2) 0.2559 (1) 0.1652 (2) 1.97 (3) N(I) 0.2861 (2) 0.9430 (2) 0.7436 (3) 1.64 (4) N(2) 0.2211 (2) 0.8427 (2) 0.2487 (2) 1.58 (4) O(1) 0.2814 (3) 0.4394 (2) 0.4646 (3) 2.18 (5) 0(2) 0.2926 (3) 0.8410 (2) 0.4593 (3) 1-85 (5) H 0.042 (5) 0.166 (4) 0.183 (6) 6.6 (12) H(IC 1) 0.919 (5) 0.060 (4) 0.524 (6) 6.3 (11) H(2C 1) 0.738 (5) 0.494 (3) 0.484 (5) 4.1 (8) H(IC2) 0.726 (4) 0.227 (3) 0.493 (4) 3.3 (8) H(2C2) 0.073 (4) 0.338 (3) 0.499 (5) 4.2 (8) H(1NI) 0-749(3) 0.114(3) 0.219(4) 2.1 (6) H(2N1) 0.101 (4) 0.457 (3) 0.236 (5) 3-9 (8) H(3NI) 0.262 (4) 0.505 (3) 0.221 (4) 2-9 (7) H(IN2) 0.238 (4) 0.280 (3) 0.790 (4) 3.1 (7) H(2N2) 0.219 (4) 0.415 (3) 0.791 (5) 4.4 (9) H(3N2) 0.402 (4) 0.343 (3) 0.780 (5) 4.0 (8) Table 2. Final atomic coordinates, Beqfor non-H atoms and Buo for H atoms in HAsO4(NH3)E(CH2) z se. = ] Z, YA.aj~u. X y z Beq/Biso(A 2) As 0.24979 (5) 0.06941 (6) 0.09305 (6) 1.212 (9) O(1) 0.2323 (3) 0.8743 (4) 0.1546 (4) 1.60 (8) 0(2) 0.7903 (5) 0.5566 (5) 0.6155 (4) 2.9 (1) 0(3) 0.1847 (4) 0.3050 (5) 0.6909 (5) 2.4 (I) 0(4) 0.5991 (4) 0.6297 (5) 0.3887 (5) 2.3 (1) N(I) 0.0816 (4) 0.6939 (5) 0.9306 (5) 1.51 (9) N(2) 0.5379 (4) 0.1983 (6) 0.3905 (5) 1.8 (1) C(I) 0.9449 (5) 0.4517 (6) 0.9660 (6) 1.8 (1) C(2) 0.4375 (5) 0.5402 (6) 0.0247 (6) 1.9 (1) H 0.211 (6) 0.388 (8) 0.328 (8) 3. (1) H(1C1) 0.009 (10) 0.597 (14) 0.136 (12) 8. (3) H(2C1) 0.876 (8) 0.498 (11) 0.975 (10) 5. (2) H(1C2) 0.622 (11) 0.060 (5) 0.549 (13) 8. (3) H(2C2) 0.606 (6) 0.539 (8) 0.907 (8) 3. (1) H(1N1) -0.022 (6) 0.216 (8) 0.574 (8) 2. (1) H(2N1) 0.125 (6) 0.744 (8) 0.488 (7) 2. (1) H(3N1) 0.878 (6) 0.159 (7) 0.658 (7) 1. (1) H(IN2) 0.497 (9) 0.340 (11) 0.822 (10) 6. (2) H(ZN2) 0.607 (5) 0.287 (7) 0.861 (7) 1- (1) H(3N2) 0.485 (6) 0.254 (8) 0.454 (7) 2. (1) Max. peak height in final difference Fourier synthesis 1.97 e A -3. No extinction correction, R = 0.039 for the complete set of 2804 reflexions. Scattering factors for neutral atoms and f',f" from International Tables for X-ray Crystallography (1974). Enraf-Nonius (1977) SDP used for all calculations. Computer: PDP 11/70. Discussion. Examination of the results obtained from the crystal structure determinations shows clearly that these two compounds are not simple adducts, i.e., H3XO4.(NH2)2(CH2) 2, but have atomic arrangements built up by a stacking of HXO4 2- and (NH3)2(CH2)] +
`
`Merck Exhibit 2211, Page 2
`Mylan Pharmaceuticals Inc. v. Merck Sharp & Dohme Corp.
`IPR2020-00040
`
`

`

`1896 2-I- 2-- C2HloN 2 .HPO 4 AND C2HloN22+.HAsO4 2- Table 3. Main interatomic distances (A) and bond angles (o) in HPO4(NH3)2(CH2) 2 PO 4 tetrahedron P O(1) 0(2) 0(3) 0(4) O(1) 1.590 (2) 2.459 (3) 2.540 (3) 2.523 (3) 0(2) 104.3 (1) 1.525 (2) 2.532 (3) 2.535 (3) O(3) 108.8 (1) 111.8 (1) 1.533 (2) 2.512 (3) 0(4) 108.4 (1) 112.7 (1) 110.7 (1) 1.521 (2) P-O = 1.542 (2) NH3-(CH2)2-NH 3 group N(1)--C(1) 1.469 (4) N(1)-C(1)--C(2) 112.1 (3) C(1)-C(2) 1.507 (4) C(1)--C(2)-N(2) 109.6 (2) C(2)--N(2) 1.486 (4) Hydrogen bonds (O,N)-H H...O (O,N)--O L(O,N)--H...O O(I)-H-..O(4) 0.71 (6) 1.90 (6) 2.578 (3) 160 (7) N(1)-H(IN1)--.O(4) 0.82 (4) 1.93 (4) 2.747 (4) 173 (4) N(I)--H(2N1)...O(2) 0.88 (5) 1.85 (5) 2.719 (4) 167 (5) N(I)-H(3N1)...O(3) 0.91 (4) 2.00(5) 2.906 (4) 176 (4) N(2)-H(1N2)...O(3) 0.90 (4) 1.91 (5) 2.810(4) 178 (4) N(2)--H(2N2)...O(2) 1.08 (5) 1.65 (5) 2.720 (4) 176 (4) N(2)--H(3N2)...0(3) 0.94 (5) 1.90 (5) 2.836 (4) 172 (4) Table 4. Main interatomic distances (A) and bond angles (o) in HAsO4(NH3)2(CH2) 2 AsO 4 tetrahedron As O(1) 0(2) 0(3) 0(4) O(I) 1.678 (3) 2.647 (4) 2.775 (4) 2.751 (4) 0(2) 101.7 (2) 1.734 (3) 2.793 (5) 2.763 (5) 0(3) 111.9 (2) 110.2 (2) 1.672 (3) 2.763 (5) 0(4) 111.1 (2) 109.1 (2) 112.2 (2) 1.657 (3) As-O = 1.685 (3) NH3-(CH2)2--NH 3 groups C(1)-C(1) C(1)-N(1) C(1)--C (1)---N(1) Hydrogen bonds 1.496 (8) C(2)-C(2) 1.516 (9) 1.479 (5) C(2)-N(2) 1.482 (6) 111.3 (4) C(2)-C(2)-N(2) 110.6 (5) (O,N)-H H...O (O,N)-O/(O,N)--H...O O(2)-H...O(3) 0.64 (6) 2.03 (6) 2.634 (5) 158 (8) N(1)-H(1N1)...O(3) 0.64 (6) 2.14 (6) 2.744 (5) 157 (7) N(1)--H(2N1)...O(1) 0.82 (6) 1.99 (6) 2.805 (5) 170 (5) N(1)--H(3N1)...O(1) 0.88 (5) 1.92 (5) 2.788 (5) 168 (5) N(2)--H(1N2)...O(4) 0.76 (8) 1.98 (8) 2.718 (5) 162 (8) N(2)-H(2N2)...O(1) 0.77 (5) 2.14 (6) 2.820 (5) 148 (5) N(2)-H(3N2)...O(4) 0.88 (6) 1.81 (6) 2.686 (5) 170 (5) groups. In both structures one observes a layer arrangement: planes of HXOa tetrahedra alternate with planes of (CH2)2(NH3) 2+ groups, as depicted in Figs. 1 and 2. Another common feature for these two arrangements is the internal repartition of the HXO 2- tetrahedra in their planes; they are associated in pairs forming H2X208 clusters with rather short X-X distances (P--P = 4.847, As-As = 4.994 A). The two HXO a groups in such a cluster are linked by a double hydrogen bridge. In the case of the phosphorus compound the (NHa)2(CH2) 2 entities are strongly pseudocentro- symmetric while they are centrosymmetric in the arsenic compound. This implies the existence of two crystallographicaUy independent (NHa)2(CH2) 2 units. Tables 1 and 2* report the final atomic coordinates, while Tables 3 and 4 give the main interatomic distances, bond angles and details of the hydrogen-bond scheme. * Lists of structure factors, anisotropic thermal parameters and bond distances and angles involving H atoms have been deposited with the British Library Document Supply Centre as Supplemen- tary Publication No. SUP 44090 (27 pp.). Copies may be obtained through The Executive Secretary, International Union of Crystal- lography, 5 Abbey Square, Chester CH 1 2HU, England. References Enraf-Nonius (1977). Structure Determination Package. Enraf- Nonius, Delft, The Netherlands. International Tables for X-ray Crystallography (1974). Vol. IV. Birmingham: Kynoch Press. (Present distributor D. Reidel, Dordrecht.) Acta Cryst. (1987). C43, 1896-1898 / Structure of Disodium Ethylenediammonium Bis[monohydrogentetraoxophosphate(V)] Hexahydrate BY M. T. AVERBUCH-POUCHOT, A. DURIF AND J. C. GUITEL Laboratoire de Cristallographie, Centre National de la Recherche Scientifique, Laboratoire associ~ ~ I'USTMG, 166X, 38042 Grenoble CEDEX, France (Received 18 March 1987; accepted 22 May 1987) Abstract. C2H~oN2+.2Na+.2HPOe-.6H2 O, Mr = 408.15, monoclinic, P21/c , a -- 11.699 (9), b = 10.164 (9), c = 6.835 (4) A, fl= 105.00 (5) °, V= 785 (2) A 3, z = 2, D x = 1.727 Mg m -3, 2(Mo Kct) = 0108-2701/87/101896-03501.50 0.7107 A, a = 0.415 mm -1, F(000) = 428, T-- 295 K, final R=0.022 for 1823 independent reflexions. HPO 2- and (CH2)2(NHa) 2+ groups alternate in planes perpendicular to the a axis. In these planes, HPO 2- © 1987 International Union of Crystallography
`
`Merck Exhibit 2211, Page 3
`Mylan Pharmaceuticals Inc. v. Merck Sharp & Dohme Corp.
`IPR2020-00040
`
`