Z. Kristallogr. NCS 229 (2014) xxx-xxx / DOI 10.1515/ncrs-2014-0005
1
© by Oldenbourg Wissenschaftsverlag, München
Crystal structure of N-(2,6-diisopropylphenyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxamide, C22H28N2O Sphelele C. SosiboI, Majid D. FarahaniI, Thavendran GovenderI, Hendrik G. KrugerI and Glenn E. M. Maguire*, II I II
School of Health Sciences, University of KwaZulu-Natal, Durban, 4000, South Africa School of Chemistry and Physics, University of KwaZulu-Natal, Durban, 4000, South Africa
Received May 07, 2013, accepted October 17, 2013, available online November 21, 2013, CCDC no. 969164
duced pressure to afford the crude amide, which was purified by column chromatography using hexane/ethyl acetate and silica gel as the stationary phase (Rf = 0.4). The pure product was an off white solid (0.66 g, yield 93% ). M.p. = 415-417 K [a]D20 = –58.3 (c 0.48, CHCl3). Crystals suitable for x-ray diffraction were obtained by slow evaporation of the title compound in a combination of acetonitrile with ethyl acetate at room temperature. Experimental details All H atoms were positioned geometrically and allowed to ride on their respective parent atoms. The coordinates of the H1a atom were refined isotropically.
Abstract C22H28N2O, monoclinic, P21 (no. 4), a = 6.1771(3) Å, b = 16.3756(7) Å, c = 9.3741(4) Å, b = 93.763(2)°, V = 946.2 Å3, Z = 2, Rgt(F) = 0.0336, wRref(F2) = 0.0823, T = 173 K.
Discussion Chiral catalysts containing a tetrahydroisoquinoline (TIQ) backbone is a topic currently being explored in our research group. TIQ catalysts have shown to be efficient for several asymmetric transformations [1-3]. The absolute configurations of the TIQ derivative is known from the chiral starting amino acid. From the crystal structure it is evident that the N-containing six membered ring assumes a twisted boat conformation [(Q) = 0.6507(14) Å, q = 87.70(13)°, f = 114.53(13)°]. We have reported similar conformations for TIQ derivatives previously [4, 5]. The structure displays intermolecular hydrogen bonding N···O = 3.0132(13) Å. Table 2. Atomic coordinates and displacement parameters (in Å2).
Table 1. Data collection and handling.
Atom
Site
x
y
z
Uiso
Crystal: Wavelength: m: Diffractometer, scan mode: 2qmax: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:
H(1A) H(3) H(4) H(6) H(8) H(9A) H(9B) H(9C) H(10A) H(10B) H(10C) H(11) H(12A) H(12B) H(12C) H(13A) H(13B) H(13C) H(15) H(16A)
2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a
0.139(3) 1.1524 1.2589 1.0891 0.7226 0.9298 0.8496 1.0524 0.4605 0.4879 0.5935 0.7265 1.0839 0.9663 1.1292 0.6759 0.6032 0.8266 0.3756 0.5757
0.231(1) 0.2350 0.3697 0.4612 0.4111 0.5500 0.5394 0.4906 0.4324 0.5123 0.5060 0.1464 0.1065 0.0407 0.1022 0.0828 0.1744 0.1474 0.1492 0.1837
0.576(2) 1.0332 1.0331 0.8747 0.5851 0.7098 0.5487 0.6116 0.7497 0.6607 0.8170 0.8064 0.7781 0.8669 0.9445 1.0247 1.0305 1.1047 0.5180 0.3148
0.028(4) 0.027 0.028 0.024 0.022 0.038 0.038 0.038 0.044 0.044 0.044 0.023 0.049 0.049 0.049 0.041 0.041 0.041 0.021 0.023
colourless blocks, size 0.24´0.30´0.43 mm Mo Ka radiation (0.71073 Å) 0.72 cm-1 Bruker Smart ApexII CCD, j and w 56° 17769, 4404 Iobs > 2 s(Iobs), 4179 234 SADABS [6], OLEX2 [7], SHELX [8], WinGX [9]
Source of material A solution of carbobenzyloxy protected N-(2,6-diisopropylphenyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxamide (1.0 g) in THF (20 mL) was added to a suspension of activated Pd/C (500 mg, 10 wt-%) in methanol. The reaction mixture was connected to a hydrogen gas source at one atm and stirred at room temperature for 3 h. Completion of the reaction was monitored by TLC using hexane/ethyl acetate (7:3). The solution was filtered on a pad of Celite and washed with ethyl acetate (10 mL) followed by dichloromethane (5 mL). The filtrate was concentrated under re_____________
* Correspondence author (e-mail:
[email protected])
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C22H28N2O
2 Table 2. continued.
Table 2. continued.
Atom
Site
x
y
z
Uiso
Atom
Site
x
y
z
Uiso
H(16B) H(18) H(19) H(20)
2a 2a 2a 2a
0.3233 0.7407 0.7683 0.5270
0.1926 0.2981 0.4374 0.5265
0.2844 0.1883 0.1484 0.2440
0.023 0.023 0.029 0.032
H(21) H(23A) H(23B) H(1)
2a 2a 2a 2a
0.2518 0.0795 0.0521 0.5028
0.4767 0.3614 0.2916 0.2959
0.3780 0.4940 0.3794 0.7037
0.030 0.030 0.030 0.018
Table 3. Atomic coordinates and displacement parameters (in Å2). Atom
Site
x
y
z
U11
U22
U33
C(1) C(2) C(3) C(4) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23) N(1) N(2) O(1)
2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a
0.8074(2) 0.9088(2) 1.0808(2) 1.1463(2) 1.0439(2) 0.8746(2) 0.7645(2) 0.9130(2) 0.5572(2) 0.8350(2) 1.0208(3) 0.7249(2) 0.6381(2) 0.4180(2) 0.4489(2) 0.4773(2) 0.6420(2) 0.6591(2) 0.5144(2) 0.3491(2) 0.3302(2) 0.1559(2) 0.6275(2) 0.2486(2) 0.8028(1)
0.30022(7) 0.24376(7) 0.27157(9) 0.35214(9) 0.40700(8) 0.38216(7) 0.44159(7) 0.51202(8) 0.47632(9) 0.15532(7) 0.09564(9) 0.13838(9) 0.22137(7) 0.20578(7) 0.21425(8) 0.30329(7) 0.33370(8) 0.41732(8) 0.47063(8) 0.44075(9) 0.35742(8) 0.31906(9) 0.27500(6) 0.25960(7) 0.18495(5)
0.7839(1) 0.8786(1) 0.9705(1) 0.9698(1) 0.8746(1) 0.7789(1) 0.6725(1) 0.6318(2) 0.7304(2) 0.8859(1) 0.8671(2) 1.0244(2) 0.5826(1) 0.5000(1) 0.3395(1) 0.3054(1) 0.2259(1) 0.2025(2) 0.2593(2) 0.3398(2) 0.3625(1) 0.4451(2) 0.6901(1) 0.5510(1) 0.5514(1)
0.0125(5) 0.0183(5) 0.0212(6) 0.0205(6) 0.0202(6) 0.0154(5) 0.0181(5) 0.0234(6) 0.0211(6) 0.0236(6) 0.0351(8) 0.0341(7) 0.0164(5) 0.0167(5) 0.0218(6) 0.0176(5) 0.0188(5) 0.0230(6) 0.0339(7) 0.0273(6) 0.0170(5) 0.0156(5) 0.0124(4) 0.0132(4) 0.0181(4)
0.0193(5) 0.0174(5) 0.0294(7) 0.0327(7) 0.0210(6) 0.0181(5) 0.0144(5) 0.0182(6) 0.0248(6) 0.0164(6) 0.0247(7) 0.0220(6) 0.0158(5) 0.0181(6) 0.0206(6) 0.0203(6) 0.0241(6) 0.0282(7) 0.0192(6) 0.0256(6) 0.0273(6) 0.0332(7) 0.0172(4) 0.0291(6) 0.0241(4)
0.0120(5) 0.0143(6) 0.0154(6) 0.0167(6) 0.0191(7) 0.0149(6) 0.0229(6) 0.0334(8) 0.0416(9) 0.0182(6) 0.0395(9) 0.0268(8) 0.0134(6) 0.0167(6) 0.0153(6) 0.0127(6) 0.0150(6) 0.0216(7) 0.0260(7) 0.0225(7) 0.0165(6) 0.0260(7) 0.0158(5) 0.0186(5) 0.0197(5)
Acknowledgments. The authors wish to thank Dr Bernard Owaga from the University of KwaZulu-Natal for assistance with the data collection and refinement.
References 1. Chakka, S. K.; Andersson, P. G.; Maguire, G. E. M.; Kruger, H. G.; Govender, T.: Synthesis and Screening of Novel C1 Substituted Tetrahydroisoquinoline Derivatives for Asymmetric Transfer Hydrogenation Reactions. Eur. J. Org. Chem. (2010) 972-980. 2. Kawthekar, R. B.; Chakka, S. K.; Francis, V.; Andersson, P. G.; Kruger, H. G.; Mag uire, G. E. M.; Gov end er, T.: Syn the sis o f tetrahydroisoquinoline(TIQ)-oxazoline ligands and their application in enantioselective Henry reactions. Tetrahedron: Asymmetry. 21 (2010) 846-852. 3. Naicker, T.; Petzold, K.; Singh, T.; Arvidsson, P. I.; Kruger, H. G.; Maguire, G. E. M.; Govender, T.: Novel tetrahydroisoquinoline based organocatalysts for asymmetric Diels-Alder reactions: insight into the catalytic mode using ROESY NMR and DFT studies. Tetrahedron Asymmetry. 21 (2010) 2859-2867.
U12 -0.0004(4) 0.0005(4) 0.0012(5) -0.0051(5) -0.0051(5) 0.0006(4) 0.0024(4) 0.0001(5) 0.0072(5) 0.0014(5) 0.0071(6) -0.0004(5) -0.0034(4) -0.0051(4) -0.0041(5) -0.0022(4) -0.0013(4) -0.0062(5) -0.0018(5) 0.0070(5) 0.0017(5) 0.0030(5) 0.0006(3) -0.0012(4) 0.0008(3)
U13 0.0008(4) 0.0024(4) -0.0034(5) -0.0039(5) 0.0011(5) 0.0020(4) 0.0001(5) 0.0009(5) 0.0053(6) 0.0004(5) 0.0092(7) 0.0083(6) 0.0001(4) -0.0006(4) -0.0020(5) -0.0042(4) -0.0003(4) -0.0003(5) -0.0029(6) 0.0001(5) -0.0016(4) 0.0017(5) -0.0005(4) 0.0007(4) 0.0017(3)
U23 -0.0014(5) 0.0010(4) 0.0030(5) -0.0015(5) -0.0041(5) -0.0021(5) 0.0010(5) 0.0057(5) 0.0005(6) 0.0021(5) 0.0024(6) 0.0049(6) 0.0028(4) 0.0000(5) -0.0020(5) 0.0008(5) -0.0006(5) 0.0050(6) 0.0034(5) 0.0018(5) 0.0018(5) 0.0061(6) -0.0007(4) 0.0040(5) -0.0030(4)
4. Naicker, T.; Govender, T.; Kruger, H. G.; Maguire, G. E. M.: (S)-NBenzyl-2-methyl-1,2,3,4-tetrahydroisoquinoline-3-carboxamide. Acta Crystallogr. E67 (2011) o67. 5. Naicker, T., Govender, T., Kruger, H. G.; Maguire, G. E. M.: (S)-2Benzyl-N-(2,6-diisopropylphenyl)-1,2,3,4-tetrahydro-isoquinoline-3carboxamide. Acta Crystallogr. E67 (2011) o1106. 6. APEX2, SAINT and SADABS, Bruker AXS Inc., (2006) Madison, Wisconsin, USA. 7. Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K; Puschmann, H.: OLEX2: A complete structure solution, refinement & analysis program. J. Appl. Crystallogr. 42 (2009) 339-341. 8. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112-122. 9. L.J. Farrugia.: WinGX suite for small-molecule single-crystal crystallography. J. Appl. Crystallogr. 32 (1999) 837-838.
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