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P1: GVH/HGI P2: HDT

Journal of Chemical Crystallography (JOCC) PP466-372615 May 23, 2002 15:42 Style file version Nov. 07, 2000

Journal of Chemical Crystallography, Vol. 31, Nos. 9–10, October 2001 (°


C 2002)

Racemic γ -2-cis-6-diphenyl-trans-3-ethylpiperidin-4-one
oxime, a crystal structure with Z 0 = 8

S. Kumar,(1,2) K. Subramanian,(1) Antoine M.M. Schreurs,(3) Jan Kroon,(3)


and Thomas Steiner(4)∗

Received March 28, 2001

The crystal structure of the title compound contains eight molecules per asymmetric crys-
tal unit, each four of the two enantiomers (Pa, a = 19.7547(3) Å, b = 17.2606(2) Å,
c = 20.8149(4) Å, β = 114.2656(16)◦ , V = 6470.4(2) Å3 , Z = 16). The independent
molecules have significantly different conformations, and local pseudosymmetries are
obeyed only very roughly. The oxime groups form the typical hydrogen bonded
cyclic dimers, whereas the amine donors are not satisfied by any kind of hydrogen
bonds.

KEY WORDS: Oxime; hydrogen bonding; high Z0 ; X-ray crystal structure.

Introduction Experimental

The title compound, 1, belongs to a series The title compound was prepared following
of molecules that we are studying in the con- procedures for synthesis of N-nitrosopiperidines.3
text of specific intermolecular interactions.1 Crys- Determining the crystal structure proved to be
tals of 1 have very large unit cell constants, and nontrivial. The large unit cell constants suggest a
in structure solution it turned out that the asym- cell content of 16 molecules, and extinctions in-
metric unit contains eight symmetry-independent dicate space groups P2/a (No. 13) or Pa (No. 7).
molecules (Z 0 = 8). This is a very high value that Using a diffraction data set measured with Cu Kα
has in recent Z 0 statistics been found only for radiation at RT, the structure could be solved in ne-
0.014% of all crystal structures.2 Therefore, the ither of these space groups, and also neither in P-1
crystal structure of 1 deserves to be shown in some or P1. Therefore, a second data set was collected
detail. with Mo Kα radiation at 125 K (Nonius Kappa-
CCD). Attempts to solve the structure in P2/a
(1) Department of Physics, Anna University, Madras, India. and P-1 failed again, but finally it could be solved4
(2) Present address: Department of Biophysics, All India Institute of in Pa with eight symmetry-independent molecules
Medical Sciences, Ansari Nagar, New Delhi, India.
(3) Bijvoet Center for Biomolecular Research, Department of Crystal
(Z 0 = 8) (Table 1). In this structure model, one
and Structural Chemistry, Utrecht University, Padualaan, Utrecht, asymmetric unit contains four molecules of
The Netherlands. each of the two enantiomers of the racemic
(4) Institut für Chemie – Kristallographie, Freie Universität Berlin,
compound (labelled molecules A–D and E–H,
Takustraße 6, D-14195 Berlin, Germany.
∗ To whom correspondence should be addressed. E-mail: steiner@ respectively; interesting statistical data on such
chemie.fu-berlin.de. “noncentrosymmetric racemates” has recently

411
1074-1542/01/1000-0411/0 °
C 2002 Plenum Publishing Corporation
P1: GVH/HGI P2: HDT
Journal of Chemical Crystallography (JOCC) PP466-372615 May 23, 2002 15:42 Style file version Nov. 07, 2000

412 Kumar, Subramanian, Schreurs, Kroon, and Steiner

Table 2. Fractional Atomic Coordinates and Equivalent Isotropic


Displacement Parameters (Å2 ) of non-H Atoms in 1a

x/a y/b z/c Uiso

O4A 0.1085(3) 0.37467(18) 0.40804(18) 0.0611(11)


N4A 0.1081(3) 0.3564(2) 0.3408(2) 0.0543(12)
N1A 0.12969(17) 0.12900(16) 0.31053(16) 0.0227(6)
C2A 0.1465(3) 0.1889(2) 0.2695(2) 0.0422(11)
C3A 0.0938(3) 0.2559(3) 0.2552(2) 0.0433(11)
C4A 0.0948(3) 0.2829(3) 0.3246(3) 0.0489(12)
C5A 0.0841(3) 0.2209(3) 0.3706(3) 0.0521(13)
C6A 0.1343(3) 0.1578(2) 0.3778(2) 0.0435(12)
Scheme 1.
C12A 0.1447(3) 0.1521(2) 0.2019(2) 0.0326(9)
C22A 0.0806(3) 0.1250(3) 0.1486(3) 0.0467(12)
been published5 ). The structure model could C32A 0.0835(3) 0.0902(3) 0.0883(3) 0.0467(12)
also be refined with the Cu Kα data, which had C42A 0.1493(2) 0.0802(2) 0.0831(2) 0.0329(9)
C52A 0.2137(3) 0.1054(3) 0.1381(2) 0.0431(11)
previously been insufficient for structure solution.
C62A 0.2123(3) 0.1419(3) 0.1963(2) 0.0413(11)
In refinement,6 H atoms bonded to C were C13A 0.1113(3) 0.3215(3) 0.2111(2) 0.0458(12)
treated in the riding model using the default pa- C23A 0.1869(3) 0.3569(3) 0.2377(2) 0.0512(13)
C16A 0.1271(2) 0.0941(2) 0.4247(2) 0.0326(9)
rameters for C H bond lengths at the temper- C26A 0.1163(2) 0.0169(2) 0.40530(19) 0.0243(8)
ature of the measurement. Methyl groups were C36A 0.1113(2) −0.0385(2) 0.4512(2) 0.0301(8)
C46A 0.1149(2) −0.0185(3) 0.5165(2) 0.0398(10)
allowed to rotate. Amino and oxime H atoms C56A 0.1238(3) 0.0585(3) 0.5354(2) 0.0568(15)
were located in difference Fourier calculations and C66A 0.1304(4) 0.1134(3) 0.4910(3) 0.0632(17)
refined isotropically. The absolute structure could O4B 0.1161(2) 0.51027(16) 0.30510(15) 0.0387(7)
N4B 0.11829(19) 0.53022(17) 0.37262(17) 0.0274(7)
not be determined (and is not even of substan- N1B 0.14757(18) 0.76085(17) 0.41845(15) 0.0216(6)
tial interest in such a case). Therefore, the Flack C2B 0.1626(2) 0.70383(19) 0.47576(18) 0.0209(7)
C3B 0.1110(2) 0.6323(2) 0.44839(19) 0.0252(8)
x parameter has been removed. The final R value C4B 0.1132(2) 0.6031(2) 0.38068(19) 0.0235(7)
of 0.072 seems to be modest but is, in fact, typical C5B 0.1072(2) 0.6636(2) 0.32623(19) 0.0263(8)
for high-Z0 structures (Table 2). C6B 0.1615(2) 0.72976(19) 0.35952(18) 0.0216(7)
C12B 0.1531(2) 0.74327(19) 0.53607(18) 0.0232(7)
C22B 0.0837(2) 0.7722(2) 0.5281(2) 0.0275(8)
Table 1. Crystal Data and Experimental Details C32B 0.0737(3) 0.8056(2) 0.5843(2) 0.0370(10)
C42B 0.1330(3) 0.8139(2) 0.6489(2) 0.0375(10)
Crystal data C52B 0.2025(3) 0.7862(2) 0.6576(2) 0.0373(10)
CCDC no. CCDC-1003/6070 C62B 0.2127(2) 0.7519(2) 0.6015(2) 0.0324(9)
Compound C19 H22 N2 O C13B 0.1281(3) 0.5709(2) 0.5061(2) 0.0338(9)
Formula weight 294.39 C23B 0.0631(3) 0.5178(2) 0.4975(2) 0.0378(10)
C16B 0.1526(2) 0.79223(18) 0.30494(17) 0.0197(7)
Crystal system Monoclinic
C26B 0.1005(2) 0.8514(2) 0.29060(19) 0.0258(8)
Space group Pa
C36B 0.0918(2) 0.9062(2) 0.2381(2) 0.0310(9)
a, Å 19.7547(3) C46B 0.1351(2) 0.9015(2) 0.2005(2) 0.0321(9)
b, Å 17.2606(2) C56B 0.1855(2) 0.8408(2) 0.2127(2) 0.0318(9)
c, Å 20.8149(4) C66B 0.1944(2) 0.7872(2) 0.2654(2) 0.0266(8)
β,◦ 114.2656(16) O4C 0.40725(16) 0.13223(15) 0.22955(14) 0.0279(6)
V , Å3 6470.36(18) N4C 0.40871(17) 0.11445(17) 0.29666(15) 0.0231(6)
Z 16 N1C 0.37158(17) −0.11137(17) 0.32040(15) 0.0218(6)
Z0 8 C2C 0.35839(19) −0.0517(2) 0.36477(18) 0.0205(7)
Dcalc , g cm−3 1.209 C3C 0.4174(2) 0.0132(2) 0.38013(18) 0.0224(7)
Habit Block C4C 0.41658(19) 0.0424(2) 0.31087(18) 0.0219(7)
Crystal dimensions, mm 0.35 × 0.35 × 0.35 C5C 0.4218(2) −0.0196(2) 0.26238(19) 0.0236(7)
C6C 0.36200(19) −0.08151(19) 0.25110(18) 0.0199(7)
Data collection and structure refinement
C12C 0.3613(2) −0.0893(2) 0.43185(18) 0.0230(7)
Measured reflections 56391
C22C 0.4263(2) −0.1285(2) 0.47504(19) 0.0311(9)
Unique reflections 24297 C32C 0.4300(3) −0.1619(2) 0.53797(19) 0.0367(10)
R merge 0.036 C42C 0.3700(3) −0.1570(2) 0.5562(2) 0.0384(11)
Unique reflections [I > 2σ (I )] 21114 C52C 0.3065(3) −0.1188(3) 0.5129(2) 0.0397(11)
R (for observed reflections) 0.072 C62C 0.3020(2) −0.0854(2) 0.4510(2) 0.0308(8)
Rw (all reflections) 0.179 C13C 0.4128(2) 0.0769(2) 0.43001(18) 0.0237(7)
P1: GVH/HGI P2: HDT
Journal of Chemical Crystallography (JOCC) PP466-372615 May 23, 2002 15:42 Style file version Nov. 07, 2000

An unusual crystal structure with Z 0 = 8 413

Table 2. (Continued) Table 2. (Continued)

x/a y/b z/c Uiso x/a y/b z/c Uiso

C23C 0.3385(2) 0.1164(2) 0.4097(2) 0.0283(8) C62F 0.1952(3) −0.3557(3) 1.0977(2) 0.0440(11)
C16C 0.36800(19) −0.1451(2) 0.20301(18) 0.0226(7) C52F 0.1843(3) −0.3911(3) 1.1536(3) 0.0566(15)
C26C 0.3902(2) −0.2193(2) 0.2254(2) 0.0286(8) C42F 0.1123(4) −0.4212(3) 1.1398(3) 0.0661(19)
C36C 0.3964(2) −0.2747(2) 0.1783(2) 0.0371(9) C32F 0.0568(3) −0.4169(2) 1.0748(3) 0.0509(13)
C46C 0.3806(2) −0.2542(2) 0.1092(2) 0.0348(9) C22F 0.0684(3) −0.3822(2) 1.0205(3) 0.0421(11)
C56C 0.3572(3) −0.1810(3) 0.0876(2) 0.0414(11) C13F 0.0929(3) −0.1848(3) 0.9884(3) 0.0516(14)
C66C 0.3516(3) −0.1253(2) 0.1333(2) 0.0373(10) C23F 0.1641(3) −0.1480(3) 1.0282(2) 0.0500(13)
O4D 0.40064(18) 0.27019(16) 0.33034(15) 0.0351(7) C16F 0.1613(2) −0.4082(2) 0.81079(19) 0.0262(8)
N4D 0.40184(18) 0.28897(18) 0.26417(16) 0.0275(7) C26F 0.1313(2) −0.4811(2) 0.8092(2) 0.0288(8)
N1D 0.37284(19) 0.51719(18) 0.21621(16) 0.0279(7) C36F 0.1337(2) −0.5367(2) 0.7617(2) 0.0370(10)
C2D 0.3594(2) 0.4598(2) 0.15961(18) 0.0265(8) C46F 0.1641(2) −0.5202(2) 0.7146(2) 0.0372(10)
C3D 0.4128(2) 0.3903(2) 0.18918(18) 0.0272(8) C56F 0.1945(3) −0.4476(2) 0.7157(2) 0.0401(11)
C4D 0.4087(2) 0.3610(2) 0.25594(19) 0.0247(8) C66F 0.1947(3) −0.3929(2) 0.7649(2) 0.0361(9)
C5D 0.4148(3) 0.4227(2) 0.30995(19) 0.0331(9) O4G 0.40602(17) 0.76419(16) 0.72558(14) 0.0318(6)
C6D 0.3579(2) 0.4877(2) 0.27489(19) 0.0296(8) N4G 0.40346(19) 0.78444(18) 0.79101(16) 0.0281(7)
C12D 0.3684(2) 0.5003(2) 0.0988(2) 0.0307(9) N1G 0.36676(18) 1.01358(17) 0.81417(15) 0.0227(6)
C22D 0.4342(3) 0.5403(2) 0.1117(2) 0.0357(10) C2G 0.3533(2) 0.9532(2) 0.85892(19) 0.0252(8)
C32D 0.4446(3) 0.5764(2) 0.0566(3) 0.0453(12) C3G 0.4076(2) 0.8873(2) 0.87118(19) 0.0262(8)
C42D 0.3878(3) 0.5718(3) −0.0124(2) 0.0528(15) C4G 0.4045(2) 0.8575(2) 0.80138(19) 0.0261(8)
C52D 0.3245(3) 0.5339(3) −0.0238(2) 0.0531(14) C5G 0.4076(3) 0.9195(2) 0.7508(2) 0.0325(9)
C62D 0.3141(3) 0.4973(3) 0.0310(2) 0.0397(11) C6G 0.3539(2) 0.9850(2) 0.74358(19) 0.0266(8)
C13D 0.3986(2) 0.3273(2) 0.13199(18) 0.0285(8) C12G 0.3599(2) 0.9921(2) 0.92633(18) 0.0258(8)
C23D 0.4660(2) 0.2745(2) 0.1451(2) 0.0273(8) C22G 0.4250(2) 1.0262(2) 0.9716(2) 0.0303(9)
C16D 0.3646(2) 0.5484(2) 0.3287(2) 0.0323(9) C32G 0.4306(3) 1.0632(2) 1.0331(2) 0.0366(10)
C26D 0.4155(3) 0.6088(2) 0.3445(2) 0.0403(10) C42G 0.3695(3) 1.0668(2) 1.0488(2) 0.0447(12)
C36D 0.4198(3) 0.6619(3) 0.3965(2) 0.0456(11) C52G 0.3030(3) 1.0338(3) 1.0041(2) 0.0447(11)
C46D 0.3755(3) 0.6550(3) 0.4326(2) 0.0479(12) C62G 0.2982(2) 0.9964(2) 0.9428(2) 0.0330(9)
C56D 0.3258(3) 0.5947(3) 0.4183(2) 0.0429(11) C13G 0.4014(2) 0.8237(2) 0.9201(2) 0.0313(9)
C66D 0.3192(2) 0.5431(3) 0.3654(2) 0.0374(10) C23G 0.3306(3) 0.7847(3) 0.8990(3) 0.0606(15)
O4E 0.10348(17) 0.00546(15) 0.90732(13) 0.0307(6) C16G 0.3644(2) 1.0499(2) 0.6994(2) 0.0292(9)
N4E 0.10756(19) 0.02564(17) 0.84248(16) 0.0265(7) C26G 0.4207(2) 1.1044(2) 0.7277(2) 0.0348(9)
N1E 0.15115(18) 0.25153(17) 0.82463(15) 0.0231(6) C36G 0.4304(3) 1.1627(2) 0.6848(3) 0.0416(10)
C2E 0.1647(2) 0.1931(2) 0.77954(18) 0.0253(8) C46G 0.3841(3) 1.1657(3) 0.6147(2) 0.0446(12)
C3E 0.1061(2) 0.1269(2) 0.76363(19) 0.0268(8) C56G 0.3276(3) 1.1111(3) 0.5855(3) 0.0579(15)
C4E 0.1053(2) 0.0989(2) 0.83206(18) 0.0223(7) C66G 0.3182(3) 1.0540(3) 0.6284(2) 0.0478(12)
C5E 0.0996(2) 0.1599(2) 0.8804(2) 0.0256(8) O4H 0.4104(2) 0.62901(16) 0.83607(14) 0.0398(7)
C6E 0.1615(2) 0.22109(19) 0.89340(18) 0.0222(7) N4H 0.4160(2) 0.60874(18) 0.77209(17) 0.0384(9)
C12E 0.1588(2) 0.2321(2) 0.71158(19) 0.0264(8) N1H 0.38138(18) 0.38131(17) 0.72038(16) 0.0235(6)
C22E 0.0942(2) 0.2737(2) 0.66989(19) 0.0294(8) C2H 0.3691(3) 0.4415(2) 0.6663(2) 0.0318(9)
C32E 0.0874(3) 0.3090(2) 0.6080(2) 0.0371(10) C3H 0.4282(3) 0.5060(2) 0.6985(2) 0.0381(10)
C42E 0.1438(3) 0.3041(2) 0.5862(2) 0.0418(11) C4H 0.4226(3) 0.5354(2) 0.7650(2) 0.0367(10)
C52E 0.2088(3) 0.2637(2) 0.6266(2) 0.0414(11) C5H 0.4246(2) 0.4738(2) 0.8174(2) 0.0322(9)
C62E 0.2159(2) 0.2280(2) 0.6892(2) 0.0341(9) C6H 0.3661(2) 0.4119(2) 0.77878(19) 0.0253(8)
C13E 0.1205(4) 0.0615(3) 0.7181(2) 0.0580(17) C12H 0.3711(3) 0.4048(2) 0.6006(2) 0.0382(11)
C23E 0.0550(3) 0.0150(3) 0.6755(2) 0.0468(12) C22H 0.4365(4) 0.3777(2) 0.6011(3) 0.0566(15)
C16E 0.1530(2) 0.2847(2) 0.94053(19) 0.0230(7) C32H 0.4356(5) 0.3459(3) 0.5374(4) 0.082(2)
C26E 0.1055(2) 0.3478(2) 0.9143(2) 0.0347(9) C42H 0.3699(5) 0.3377(3) 0.4783(3) 0.085(3)
C36E 0.0970(3) 0.4022(3) 0.9593(3) 0.0441(11) C52H 0.3071(5) 0.3635(3) 0.4797(3) 0.084(2)
C46E 0.1356(3) 0.3935(2) 1.0322(2) 0.0401(10) C62H 0.3053(3) 0.3959(3) 0.5399(2) 0.0494(12)
C56E 0.1820(3) 0.3307(2) 1.0588(2) 0.0397(10) C13H 0.4301(3) 0.5702(3) 0.6473(3) 0.0469(12)
C66E 0.1913(2) 0.2767(2) 1.01352(19) 0.0291(8) C23H 0.3557(3) 0.6045(3) 0.6079(3) 0.0535(13)
O4F 0.1192(2) −0.12708(17) 0.80288(15) 0.0434(8) C16H 0.3654(2) 0.3485(2) 0.82935(18) 0.0228(7)
N4F 0.1097(2) −0.14702(19) 0.86556(18) 0.0358(8) C26H 0.3954(2) 0.2751(2) 0.8307(2) 0.0269(8)
N1F 0.14118(18) −0.37410(17) 0.91739(16) 0.0228(6) C36H 0.3938(2) 0.2195(2) 0.8779(2) 0.0319(9)
C2F 0.1499(2) −0.3141(2) 0.97113(19) 0.0276(8) C46H 0.3637(2) 0.2367(2) 0.9257(2) 0.0334(9)
C3F 0.0929(2) −0.2485(2) 0.9369(2) 0.0316(9) C56H 0.3341(2) 0.3094(3) 0.9256(2) 0.0372(10)
C4F 0.1035(2) −0.2199(2) 0.8721(2) 0.0302(9) C66H 0.3353(2) 0.3645(2) 0.8778(2) 0.0302(8)
C5F 0.1057(3) −0.2815(2) 0.8219(2) 0.0323(9)
C6F 0.1613(2) −0.3449(2) 0.86121(19) 0.0261(8) aU(eq) is defined as one third of the orthogonalized Ui j
C12F 0.1379(2) −0.3517(2) 1.0310(2) 0.0292(9) tensor.
P1: GVH/HGI P2: HDT
Journal of Chemical Crystallography (JOCC) PP466-372615 May 23, 2002 15:42 Style file version Nov. 07, 2000

414 Kumar, Subramanian, Schreurs, Kroon, and Steiner

Fig. 1. Molecular structure of (1), shown for all eight symmetry-independent molecules (displacement ellipsoids drawn at the
50% probability level). The four symmetry-independent molecular dimers, composed of molecules A and B, C and D, E and
F, G and H are shown in projections roughly on the dimer plane in plates (a)–(d), respectively. Note that within each pair, the
molecules have the same chirality (A, B, C, D have opposite chiralities as E, F, G, H). Note also that the conformation of the
ethyl group hurts the internal pseudo-twofold axis of dimers A–B, C–D, and E–F, but not of G–H.

Results and discussion ring is in a chair conformation with all substituents


in equatorial position, and the oxime O atom is ori-
The molecular structure of 1 does not ented trans with respect to C3. The amino H atom
show unexpected features, Fig. 1. For all eight (located in difference Fourier calculations and re-
symmetry-independent molecules, the piperidine fined isotropically) is in the expected equatorial

Table 3. Torsion Angles Defining the Side Chain Orientations (in Degrees)

Molecule N1 C2 C12 C22 N1 C6 C16 C26 C2 C3 C13 C23

A 67.9(5) −0.8(7) −56.1(6)


B 63.9(4) −34.0(4) 154.2(3)
C 57.9(4) −8.7(5) −54.2(4)
D 57.9(4) −33.2(5) 156.2(3)
E −54.7(4) 31.8(5) −155.3(3)
F −65.1(5) 12.3(5) 55.0(5)
G −61.7(4) 39.6(5) 58.9(5)
H −70.1(5) 16.4(5) 51.8(5)
P1: GVH/HGI P2: HDT
Journal of Chemical Crystallography (JOCC) PP466-372615 May 23, 2002 15:42 Style file version Nov. 07, 2000

An unusual crystal structure with Z 0 = 8 415

position too. Although the overall conformation is Table 4. Hydrogen Bond Geometry (in Å and Degrees)
similar for all eight molecules, there are substan-
Bond O H H···N O···N O H···N
tial variations in the orientation of the phenyl rings
and the ethyl group. For example, the torsion an- O4A H · · · N4B 1.07(7) 1.84(7) 2.812(4) 149(6)
gle N1 C6 C16 C26 varies between −0.8(7) O4B H · · · N4A 1.03(7) 1.91(7) 2.780(4) 140(5)
and −34.0(4)◦ , and 12.3(5) and 39.6(5)◦ for the O4C H · · · N4D 0.79(4) 2.11(4) 2.813(4) 149(4)
O4D H · · · N4C 0.93(5) 1.93(5) 2.799(4) 155(4)
two isomers, respectively (Table 3). O4E H · · · N4F 0.98(5) 1.83(5) 2.790(4) 165(4)
In the crystal lattice, pairs of symmetry- O4F H · · · N4E 0.84(4) 1.99(4) 2.799(4) 161(3)
independent molecules of the same chirality form O4G H · · · N4H 0.80(5) 2.08(5) 2.832(4) 156(4)
O4H H · · · N4G 0.87(4) 2.01(4) 2.827(4) 155(4)
hydrogen-bonded dimers (hydrogen bond geome-
tries given in Table 4). Formation of cyclic dimers
is typical for oximes7,8 (for an early example, see
Ref. 9), but normally these dimers are centrosym- try is hurt by the orientation of the ethyl groups
metric whereas in the present structure they are (one oriented “up” and one “down” with respect
not. Each of the molecular pairs in 1 possesses to the projection plane). Surprisingly, the ethyl
rough internal pseudo-twofold symmetry, but in orientation in the fourth pair, G–H, is different
the three pairs, A–B, C–D, and E–F, this symme- and does obey internal pseudo-twofold symmetry

Fig. 2. One of the two symmetry-independent layers (containing dimers


A–B and E–F) parallel to the y–z plane.
P1: GVH/HGI P2: HDT
Journal of Chemical Crystallography (JOCC) PP466-372615 May 23, 2002 15:42 Style file version Nov. 07, 2000

416 Kumar, Subramanian, Schreurs, Kroon, and Steiner

(both “up” with respect to the projection plane). As is usual for crystal structures with high
These features show that the structure cannot con- Z 0 values, no reason for the complicated crystal
tain a center of symmetry that has been overlooked packing is immediately obvious from the structure
in structure solution (due to its ethyl orientations, itself, and we prefer not to speculate here on these
pair G–H cannot be inversion related to either of matters.
the pairs A–B and C–D).
The molecular dimers form layers parallel to
the y–z plane that contain molecules of both chiral- References
ities. There are two symmetry-independent layers,
one containing the pairs A–B and E–F, and other 1. Kumar, S.; Steiner, T.; Subramanian, K. J. Chem. Crystallogr
containing C–D and G–H; it is sufficient to show 2000, 30, 143.
2. Steiner, T. Acta Crystallogr., Sect. B 2000, 56, 673.
only one in Fig. 2. The layers are then stacked with 3. Baliah, V.; Lakshmanan; Pandiarajan, K. Indian J. Chem.,
a lateral offset defined by the monoclinic angle β. Sect. B 1978, 16, 72.
4. Sheldrick, G.M. SHELXS-90, Program for Crystal Structure
It is a strange feature of the packing that for none Refinement; Univerity of Göttingen: Germany, 1990.
of the molecules, the amino N–H group donates 5. Dalhus, B.; Görbitz, C.H. Acta Crystallogr., Sect. B 2000, 56,
a hydrogen bond, not even to a π-acceptor (inter- 715.
6. Sheldrick, G.M. SHELXL-97, Program for Crystal Structure
molecular contacts checked to a maximal distance Refinement; University of Göttingen: Germany, 1997.
of H · · · X = 3.2 Å: for literature on N H · · · π 7. Bertolasi, V.; Gilli, G.; Veronese, A.C. Acta Crystallogr.,
Sect. B 1982, 38, 502.
hydrogen bonds, see Ref. 10). A reason for this 8. Allen, F.H.; Motherwell, W.S.S.; Raithby, P.R.; Shields, G.P.;
lack of N H · · · X hydrogen bonding are possibly Taylor, R. New J. Chem. 1999, 23, 25–34.
9. Oonk, H.A.J.; Kroon, J. Acta Crystallogr., Sect. B 1976, 32, 500.
the two phenyl rings adjacent to N H preventing 10. Desiraju, G.R.; Steiner, T. The Weak Hydrogen Bond in
easy steric approach. In related structures, how- Structural Chemistry and Biology; Oxford University Press:
Oxford, 1999.
ever, we have observed hydrogen bonding in this 11. Kumar, S.; Subramanian, K.; Schreurs, A.M.M.; Kroon, J.;
situation.11 Steiner, T. unpublished.

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