5,6,7,8-Tetra­hydro­quinoline 1-oxide hemihydrate

Karczmarzyk, Z.; Lipińska, T.M.; Wysocki, W.; Urbańczyk-Lipkowska, Z.; Kalicki, P.

doi:10.1107/S1600536810008779

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages o806-o807

doi:10.1107/S1600536810008779

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5,6,7,8-Tetrahydroquinoline 1-oxide hemihydrate

Zbigniew Karczmarzyk,^a ^* Teodozja M. Lipińska,^a Waldemar Wysocki,^a Zofia Urbańczyk-Lipkowska ^b and Przemysław Kalicki ^b

^aDepartment of Chemistry, University of Podlasie, ul. 3 Maja 54, 08-110 Siedlce, Poland, and ^bInstitute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw 42, POB 58, Poland
^*Correspondence e-mail: kar@ap.siedlce.pl

(Received 3 March 2010; accepted 8 March 2010; online 13 March 2010)

In the title compound, C₉H₁₁NO·0.5H₂O, the asymmetric unit contains two similar molecules of 5,6,7,8-tetrahydroquinoline 1-oxide and one water molecule. The water molecule links the two O atoms of both independent N-oxides into dimers via O—H⋯O hydrogen bonds, forming a three-dimensional network along [101], which is additionally stabilized by weak C—H⋯O intermolecular interactions. In each molecule, the saturated six-membered rings exist in a conformation intermediate between a half-chair and sofa.

Related literature

For background to the chemistry of the title compound and its applications, see: Coperet et al. (1998 ); Li (2005 ); Kaiser et al. (2006 ); Kaczorowski et al. (2009 ). For the synthesis, see: Jacobs et al. (2000 ); Barbay et al. (2008 ). For the biological activity of 5,6,7,8-tetrahydroquinoline derivatives, see: Calhoun et al. (1995 ); Abd El-Salam et al. (2009 ). For a related structure, see: HXTHQO (CSD, November 2009 release). For structure interpretation tools, see: Duax & Norton (1975 ); Allen et al. (1987 ); Allen (2002 ); Bruno et al. (2002 ).

Experimental

Crystal data

C₉H₁₁NO·0.5H₂O
M_r = 158.20
Orthorhombic, P b c a
a = 14.725 (4) Å
b = 14.464 (4) Å
c = 15.474 (3) Å
V = 3295.7 (14) Å³
Z = 16
Cu Kα radiation
μ = 0.70 mm⁻¹
T = 293 K
0.28 × 0.26 × 0.21 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.832, T_max = 0.873
11258 measured reflections
2727 independent reflections
1989 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.205
S = 1.39
2727 reflections
215 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H21⋯O1A	0.96 (3)	1.87 (3)	2.825 (3)	170 (3)
O2—H22⋯O1B	0.95 (4)	1.86 (3)	2.799 (3)	170 (3)
C2B—H2B⋯O1A	0.93	2.53	3.454 (3)	171
C3A—H3A⋯O2ⁱ	0.93	2.50	3.392 (3)	160
C3B—H3B⋯O2ⁱⁱ	0.93	2.56	3.342 (4)	142
C5A—H52A⋯O1Bⁱⁱⁱ	0.97	2.49	3.383 (4)	153
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008779/jj2025sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810008779/jj2025Isup2.hkl

checkCIF report

Comment top

5,6,7,8-Tetrahydroquinoline 1-oxide, (I), is an important intermediate for the synthesis of quinoline derivatives via Boekelheide rearrangement (Li, 2002; Kaiser et al., 2006; Coperet et al., 1998). The 5,6,7,8-tetrahydroquinoline moiety is found as a subunit in numerous medicinally interesting compounds (Calhoun et al., 1995; Abd El-Salam et al., 2009). Compound (I) can be obtained by the reaction of 5,6,7,8-tetrahydroquinoline with hydrogen peroxide or with MCPBA (Jacobs et al., 2000; Barbay et al., 2008). A search of the Cambridge Structural Database (November 2009 Release; Allen, 2002; Bruno et al., 2002) showed 26 organic compounds with the 5,6,7,8-tetrahydroquinoline moiety. Due to our interest in the preparartion of new nanomaterials based on organometallic complexes similar to those obtained from Cinchona alkaloids (Kaczorowski et al., 2009), a new method of synthesis for (I), by the oxidation of 5,6,7,8-tetrahydroquinoline with the catalytic system of oxone/TlOAc/PhI in a water-acetonitrile solution at room temperature has been developed and its crystal and molecular structure reported.

The asymmetric unit contains two similar molecules of 5,6,7,8-tetrahydroquinoline 1-oxide and one water molecule (Fig. 1). The water molecule links the two O atoms of both independent N-oxides by O—H···O hydrogen bonds into dimmers, which form a three-dimensional network along the [101] (Fig. 2). Additional weak C—H···O intermolecular interactions help stabilize the crystal packing (Table 1). The water molecule is observed in the ¹H NMR spectrum as a broad signal at 2.4 ppm and in the IR spectrum as two absorption maxima for two different O—H bonds at 3368 and 3312 cm^-1, respectively. The bond distances and angles in (I) are in normal ranges (Allen et al., 1987) and are comparable to the corresponding values observed in related structure of 5-hydroxy-5,6,7,8-tetrahydroquinoline 1-oxide (HXTHQO; CSD, November 2009 Release). In (I) the 6-membered fused-ring systems of the molecules A and B, are observed in an intermediate conformation between a half-chair and sofa with asymmetry parameters ΔC_s(C6A) = 13.4 (3)°, ΔC₂(C6A,C7A) = 11.2 (4)°, ΔC_s(C6B) = 11.1 (2)° and ΔC₂(C6B, C7B) =14.8 (3)° (Duax & Norton, 1975).

Related literature top

For background information, see: Coperet et al. (1998); Li (2005); Kaiser et al. (2006); Kaczorowski et al. (2009). For the synthesis, see: Jacobs et al. (2000); Barbay et al. (2008). For the biological activity of 5,6,7,8-tetrahydroquinoline derivatives, see: Calhoun et al. (1995); Abd El-Salam et al. (2009). For a related structure, see: HXTHQO (CSD, November 2009 release). For structure interpretation tools, see: Duax & Norton (1975); Allen et al. (1987); Allen (2002); Bruno et al. (2002).

Experimental top

The title compound, C₉H₁₁NO.0.5H₂O, was synthesized by the oxidation process of the 5,6,7,8-tetrahydroquinoline with an oxone/TlOAc/PhI in water-acetonitrile solution, catalytic system at room temperature. To a solution of 5,6,7,8-tetrahydroquinoline (333 mg, 0.325 ml, 2.5 mmol,), in acetonitrile (7.5 ml) and water (7.5 ml), PhI (1.25 ml of a 0.1M solution in MeCN, 0.124 mmol) and thallous acetate (50 µl of 0.16M solution in water, 0.008 mmol) were added. Next, oxone (6.98 g, 11.5 mmol) was added in five portions over 6 h under stirring at room temperature. Substrate disappearing and new product forming was observed by TLC (R_f = 0.75 and R_f = 015, respectively, in ethyl acetate/methanol 50:1). The next day (after 20 h), 10% sodium hydroxide (10 ml), dichloromethane (30 ml) and water (30 ml) were added and the mixture was stirred for 5 min. The organic solution was separated and the aqueous phase was extracted with CH₂Cl₂ (2 x 15 ml). The combined organic phase was dried (anhydrous Na₂SO₄) and concentrated. Pure products 350 mg (95.0%) were obtained in oily form. After purification on column chromatography with silica gel and using ethyl acetate, the trace of the substrate was first removed. The product was eluted with a mixture of ethyl acetate/methanol (50:1) and colourless crystals were obtained. Yield: 310 mg (83%) and m.p. 344 K. Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of a dichloromethane/hexane (1:10) solution.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms. Dashed lines indicate O—H ··· O hydrogen bonds.
	Fig. 2. A view of the molecular packing in (I) (black - molecules A, red - molecules B, green - H₂O). Dashed lines indicate O—H ··· O hydrogen bonds and weak C—H···O intermolecular interactions.

5,6,7,8-Tetrahydroquinoline 1-oxide hemihydrate top

Crystal data top

C₉H₁₁NO·0.5H₂O	F(000) = 1360
M_r = 158.20	D_x = 1.275 Mg m⁻³
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 3676 reflections
a = 14.725 (4) Å	θ = 5.7–66.9°
b = 14.464 (4) Å	µ = 0.70 mm⁻¹
c = 15.474 (3) Å	T = 293 K
V = 3295.7 (14) Å³	Block, colourless
Z = 16	0.28 × 0.26 × 0.21 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2727 independent reflections
Radiation source: fine-focus sealed tube	1989 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 65.4°, θ_min = 5.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −17→16
T_min = 0.832, T_max = 0.873	k = −16→17
11258 measured reflections	l = −18→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.205	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
S = 1.39	(Δ/σ)_max < 0.001
2727 reflections	Δρ_max = 0.44 e Å⁻³
215 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (4)

Crystal data top

C₉H₁₁NO·0.5H₂O	V = 3295.7 (14) Å³
M_r = 158.20	Z = 16
Orthorhombic, Pbca	Cu Kα radiation
a = 14.725 (4) Å	µ = 0.70 mm⁻¹
b = 14.464 (4) Å	T = 293 K
c = 15.474 (3) Å	0.28 × 0.26 × 0.21 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	2727 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1989 reflections with I > 2σ(I)
T_min = 0.832, T_max = 0.873	R_int = 0.053
11258 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.205	H atoms treated by a mixture of independent and constrained refinement
S = 1.39	Δρ_max = 0.44 e Å⁻³
2727 reflections	Δρ_min = −0.24 e Å⁻³
215 parameters

Special details top

Experimental. ¹H MNR (400 MHz, CDCl₃) δ: 8.13 (d, 1H, J = 6.0 Hz), 7.04–6.99 (m, 2H), 2.93 (t, 2H, J = 6.4 Hz), 2.75 (t, 2H, J = 6.4 Hz), 2.40 (br s, 1H), 1.92–1.85 (m, 2H), 1,78–1.72 (m, 2H); ¹³C MNR (100 MHz, CDCl₃) δ: 148.8, 136.9, 136.4, 126.6, 121.9, 28.6, 24.6, 21.8, 21.6; IR (KBr, ν, cm^-1): 3368 (s, OH), 3312 (s, OH), 3076 (m), 3050 (m), 3009 (m), 2935 (s), 2871 (m), 2837 (m), 2498 (w), 2410 (w), 2151 (w), 1970 (w), 1686 (m, NO), 1596 (m), 1482 (m), 1449 (s), 1334 (m), 1253 (s), 1232 (s), 1211 (s), 1194 (s), 1155 (m), 1089 (m), 1074 (s), 1041 (m), 971 (s), 897 (m), 865 (w), 830 (m), 797 (s), 701 (m), 676 (m).

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1A	0.11925 (15)	0.33158 (10)	0.13008 (9)	0.0703 (6)
N1A	0.13994 (15)	0.41708 (12)	0.11018 (11)	0.0502 (6)
C2A	0.16947 (18)	0.47498 (16)	0.17206 (15)	0.0581 (7)
H2A	0.1737	0.4547	0.2290	0.087*
C3A	0.1930 (2)	0.56261 (17)	0.15166 (17)	0.0666 (8)
H3A	0.2143	0.6025	0.1942	0.100*
C4A	0.1853 (2)	0.59244 (16)	0.06758 (18)	0.0669 (8)
H4A	0.2018	0.6527	0.0536	0.100*
C5A	0.1449 (2)	0.56465 (16)	−0.08980 (17)	0.0686 (8)
H51A	0.0900	0.6010	−0.0964	0.103*
H52A	0.1961	0.6041	−0.1041	0.103*
C6A	0.1422 (2)	0.4849 (2)	−0.15194 (16)	0.0774 (9)
H61A	0.1268	0.5075	−0.2091	0.116*
H62A	0.2018	0.4566	−0.1551	0.116*
C7A	0.0749 (2)	0.41457 (18)	−0.12508 (14)	0.0673 (8)
H71A	0.0741	0.3649	−0.1672	0.101*
H72A	0.0149	0.4424	−0.1242	0.101*
C8A	0.09560 (19)	0.37485 (14)	−0.03650 (13)	0.0534 (7)
H81A	0.0408	0.3472	−0.0132	0.080*
H82A	0.1405	0.3262	−0.0426	0.080*
C9A	0.13012 (16)	0.44502 (14)	0.02589 (12)	0.0455 (6)
C10A	0.15331 (17)	0.53397 (15)	0.00343 (15)	0.0520 (6)
O1B	0.13846 (14)	0.36329 (13)	0.38241 (10)	0.0701 (6)
N1B	0.05059 (15)	0.35441 (11)	0.39183 (10)	0.0489 (6)
C2B	−0.0012 (2)	0.33685 (15)	0.32153 (14)	0.0571 (7)
H2B	0.0258	0.3314	0.2674	0.086*
C3B	−0.0921 (2)	0.32725 (16)	0.32982 (17)	0.0647 (8)
H3B	−0.1277	0.3148	0.2815	0.097*
C4B	−0.1320 (2)	0.33585 (16)	0.40978 (19)	0.0658 (7)
H4B	−0.1946	0.3297	0.4153	0.099*
C5B	−0.1198 (3)	0.3615 (2)	0.57197 (19)	0.0843 (11)
H51B	−0.1695	0.3179	0.5776	0.126*
H52B	−0.1441	0.4232	0.5800	0.126*
C6B	−0.0486 (3)	0.3418 (2)	0.64194 (17)	0.0941 (12)
H61B	−0.0747	0.3538	0.6984	0.141*
H62B	−0.0315	0.2771	0.6397	0.141*
C7B	0.0323 (3)	0.3992 (2)	0.63022 (15)	0.0853 (11)
H71B	0.0747	0.3870	0.6768	0.128*
H72B	0.0151	0.4638	0.6331	0.128*
C8B	0.0784 (2)	0.38036 (16)	0.54433 (14)	0.0591 (7)
H81B	0.1162	0.4329	0.5295	0.089*
H82B	0.1177	0.3270	0.5505	0.089*
C9B	0.01368 (19)	0.36319 (13)	0.47254 (13)	0.0475 (6)
C10B	−0.0792 (2)	0.35369 (15)	0.48235 (15)	0.0569 (7)
O2	0.21964 (17)	0.24427 (13)	0.26255 (13)	0.0781 (7)
H21	0.188 (2)	0.269 (2)	0.213 (2)	0.117*
H22	0.195 (2)	0.280 (2)	0.308 (2)	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1A	0.1126 (19)	0.0511 (9)	0.0473 (9)	−0.0176 (9)	−0.0026 (9)	0.0080 (7)
N1A	0.0606 (16)	0.0485 (10)	0.0415 (9)	−0.0037 (8)	0.0024 (8)	−0.0043 (8)
C2A	0.0615 (18)	0.0618 (14)	0.0510 (11)	−0.0026 (12)	−0.0041 (11)	−0.0143 (11)
C3A	0.067 (2)	0.0616 (14)	0.0708 (15)	−0.0049 (12)	−0.0088 (14)	−0.0202 (12)
C4A	0.070 (2)	0.0476 (12)	0.0833 (17)	−0.0082 (12)	0.0021 (15)	−0.0046 (12)
C5A	0.079 (2)	0.0593 (14)	0.0676 (14)	−0.0017 (13)	0.0070 (14)	0.0177 (12)
C6A	0.099 (3)	0.0823 (18)	0.0509 (12)	0.0069 (16)	0.0040 (14)	0.0130 (13)
C7A	0.086 (3)	0.0698 (16)	0.0463 (12)	0.0007 (14)	−0.0053 (12)	−0.0003 (11)
C8A	0.069 (2)	0.0491 (12)	0.0426 (11)	−0.0037 (10)	0.0005 (11)	−0.0051 (9)
C9A	0.0486 (16)	0.0471 (11)	0.0408 (10)	0.0002 (9)	0.0054 (10)	−0.0019 (9)
C10A	0.0497 (17)	0.0473 (12)	0.0590 (12)	−0.0006 (9)	0.0060 (11)	0.0004 (11)
O1B	0.0602 (16)	0.0916 (13)	0.0584 (10)	−0.0088 (10)	0.0101 (9)	−0.0125 (9)
N1B	0.0553 (16)	0.0495 (10)	0.0418 (9)	−0.0027 (8)	0.0034 (9)	−0.0025 (8)
C2B	0.071 (2)	0.0567 (13)	0.0439 (11)	−0.0008 (12)	−0.0046 (12)	−0.0036 (10)
C3B	0.074 (2)	0.0562 (14)	0.0638 (15)	−0.0020 (12)	−0.0162 (14)	0.0025 (11)
C4B	0.0531 (19)	0.0587 (14)	0.0855 (18)	0.0083 (12)	0.0009 (15)	0.0121 (13)
C5B	0.089 (3)	0.0870 (19)	0.0769 (18)	0.0294 (17)	0.0379 (18)	0.0192 (15)
C6B	0.142 (4)	0.086 (2)	0.0537 (15)	0.026 (2)	0.0270 (18)	0.0116 (14)
C7B	0.136 (4)	0.0739 (17)	0.0454 (13)	0.0120 (19)	0.0020 (16)	−0.0034 (13)
C8B	0.081 (2)	0.0520 (12)	0.0446 (11)	0.0045 (11)	−0.0058 (12)	−0.0046 (10)
C9B	0.0632 (19)	0.0377 (10)	0.0416 (11)	0.0064 (9)	0.0042 (10)	0.0016 (8)
C10B	0.065 (2)	0.0469 (12)	0.0583 (13)	0.0125 (11)	0.0090 (12)	0.0092 (10)
O2	0.0836 (19)	0.0752 (12)	0.0755 (11)	0.0184 (10)	0.0147 (11)	0.0021 (9)

Geometric parameters (Å, º) top

O1A—N1A	1.310 (2)	N1B—C2B	1.353 (3)
N1A—C2A	1.344 (3)	N1B—C9B	1.368 (3)
N1A—C9A	1.373 (3)	C2B—C3B	1.352 (4)
C2A—C3A	1.351 (3)	C2B—H2B	0.9300
C2A—H2A	0.9300	C3B—C4B	1.375 (4)
C3A—C4A	1.375 (4)	C3B—H3B	0.9300
C3A—H3A	0.9300	C4B—C10B	1.390 (4)
C4A—C10A	1.387 (4)	C4B—H4B	0.9300
C4A—H4A	0.9300	C5B—C10B	1.514 (4)
C5A—C6A	1.503 (4)	C5B—C6B	1.534 (5)
C5A—C10A	1.514 (3)	C5B—H51B	0.9700
C5A—H51A	0.9700	C5B—H52B	0.9700
C5A—H52A	0.9700	C6B—C7B	1.462 (5)
C6A—C7A	1.480 (4)	C6B—H61B	0.9700
C6A—H61A	0.9700	C6B—H62B	0.9700
C6A—H62A	0.9700	C7B—C8B	1.517 (4)
C7A—C8A	1.517 (3)	C7B—H71B	0.9700
C7A—H71A	0.9700	C7B—H72B	0.9700
C7A—H72A	0.9700	C8B—C9B	1.484 (3)
C8A—C9A	1.490 (3)	C8B—H81B	0.9700
C8A—H81A	0.9700	C8B—H82B	0.9700
C8A—H82A	0.9700	C9B—C10B	1.383 (4)
C9A—C10A	1.376 (3)	O2—H21	0.96 (3)
O1B—N1B	1.308 (3)	O2—H22	0.95 (4)

O1A—N1A—C2A	119.72 (18)	O1B—N1B—C9B	119.0 (2)
O1A—N1A—C9A	118.46 (17)	C2B—N1B—C9B	121.9 (2)
C2A—N1A—C9A	121.83 (19)	N1B—C2B—C3B	120.1 (2)
N1A—C2A—C3A	120.0 (2)	N1B—C2B—H2B	120.0
N1A—C2A—H2A	120.0	C3B—C2B—H2B	120.0
C3A—C2A—H2A	120.0	C2B—C3B—C4B	119.9 (3)
C2A—C3A—C4A	119.6 (2)	C2B—C3B—H3B	120.0
C2A—C3A—H3A	120.2	C4B—C3B—H3B	120.0
C4A—C3A—H3A	120.2	C3B—C4B—C10B	120.3 (3)
C3A—C4A—C10A	120.9 (2)	C3B—C4B—H4B	119.8
C3A—C4A—H4A	119.5	C10B—C4B—H4B	119.8
C10A—C4A—H4A	119.5	C10B—C5B—C6B	111.2 (3)
C6A—C5A—C10A	112.75 (19)	C10B—C5B—H51B	109.4
C6A—C5A—H51A	109.0	C6B—C5B—H51B	109.4
C10A—C5A—H51A	109.0	C10B—C5B—H52B	109.4
C6A—C5A—H52A	109.0	C6B—C5B—H52B	109.4
C10A—C5A—H52A	109.0	H51B—C5B—H52B	108.0
H51A—C5A—H52A	107.8	C7B—C6B—C5B	111.3 (3)
C7A—C6A—C5A	111.5 (2)	C7B—C6B—H61B	109.4
C7A—C6A—H61A	109.3	C5B—C6B—H61B	109.4
C5A—C6A—H61A	109.3	C7B—C6B—H62B	109.4
C7A—C6A—H62A	109.3	C5B—C6B—H62B	109.4
C5A—C6A—H62A	109.3	H61B—C6B—H62B	108.0
H61A—C6A—H62A	108.0	C6B—C7B—C8B	111.8 (2)
C6A—C7A—C8A	112.3 (2)	C6B—C7B—H71B	109.3
C6A—C7A—H71A	109.1	C8B—C7B—H71B	109.3
C8A—C7A—H71A	109.1	C6B—C7B—H72B	109.3
C6A—C7A—H72A	109.1	C8B—C7B—H72B	109.3
C8A—C7A—H72A	109.1	H71B—C7B—H72B	107.9
H71A—C7A—H72A	107.9	C9B—C8B—C7B	113.5 (3)
C9A—C8A—C7A	113.33 (19)	C9B—C8B—H81B	108.9
C9A—C8A—H81A	108.9	C7B—C8B—H81B	108.9
C7A—C8A—H81A	108.9	C9B—C8B—H82B	108.9
C9A—C8A—H82A	108.9	C7B—C8B—H82B	108.9
C7A—C8A—H82A	108.9	H81B—C8B—H82B	107.7
H81A—C8A—H82A	107.7	N1B—C9B—C10B	118.9 (2)
N1A—C9A—C10A	119.28 (19)	N1B—C9B—C8B	116.3 (2)
N1A—C9A—C8A	116.81 (18)	C10B—C9B—C8B	124.7 (2)
C10A—C9A—C8A	123.91 (19)	C9B—C10B—C4B	118.9 (2)
C9A—C10A—C4A	118.3 (2)	C9B—C10B—C5B	118.9 (3)
C9A—C10A—C5A	119.6 (2)	C4B—C10B—C5B	122.2 (3)
C4A—C10A—C5A	122.1 (2)	H21—O2—H22	102 (3)
O1B—N1B—C2B	119.10 (19)

O1A—N1A—C2A—C3A	178.4 (2)	O1B—N1B—C2B—C3B	179.9 (2)
C9A—N1A—C2A—C3A	−2.0 (4)	C9B—N1B—C2B—C3B	−0.2 (3)
N1A—C2A—C3A—C4A	0.9 (4)	N1B—C2B—C3B—C4B	0.4 (4)
C2A—C3A—C4A—C10A	0.3 (4)	C2B—C3B—C4B—C10B	−0.5 (4)
C10A—C5A—C6A—C7A	49.6 (3)	C10B—C5B—C6B—C7B	52.8 (3)
C5A—C6A—C7A—C8A	−59.9 (3)	C5B—C6B—C7B—C8B	−61.4 (3)
C6A—C7A—C8A—C9A	38.5 (3)	C6B—C7B—C8B—C9B	37.8 (3)
O1A—N1A—C9A—C10A	−178.6 (2)	O1B—N1B—C9B—C10B	−179.94 (19)
C2A—N1A—C9A—C10A	1.7 (4)	C2B—N1B—C9B—C10B	0.1 (3)
O1A—N1A—C9A—C8A	0.5 (3)	O1B—N1B—C9B—C8B	−1.3 (3)
C2A—N1A—C9A—C8A	−179.2 (2)	C2B—N1B—C9B—C8B	178.68 (18)
C7A—C8A—C9A—N1A	172.3 (2)	C7B—C8B—C9B—N1B	174.06 (19)
C7A—C8A—C9A—C10A	−8.7 (4)	C7B—C8B—C9B—C10B	−7.4 (3)
N1A—C9A—C10A—C4A	−0.5 (4)	N1B—C9B—C10B—C4B	−0.2 (3)
C8A—C9A—C10A—C4A	−179.5 (2)	C8B—C9B—C10B—C4B	−178.7 (2)
N1A—C9A—C10A—C5A	178.5 (2)	N1B—C9B—C10B—C5B	178.77 (19)
C8A—C9A—C10A—C5A	−0.6 (4)	C8B—C9B—C10B—C5B	0.3 (3)
C3A—C4A—C10A—C9A	−0.5 (4)	C3B—C4B—C10B—C9B	0.4 (3)
C3A—C4A—C10A—C5A	−179.4 (3)	C3B—C4B—C10B—C5B	−178.5 (2)
C6A—C5A—C10A—C9A	−19.7 (4)	C6B—C5B—C10B—C9B	−22.2 (3)
C6A—C5A—C10A—C4A	159.2 (3)	C6B—C5B—C10B—C4B	156.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H21···O1A	0.96 (3)	1.87 (3)	2.825 (3)	170 (3)
O2—H22···O1B	0.95 (4)	1.86 (3)	2.799 (3)	170 (3)
C2B—H2B···O1A	0.93	2.53	3.454 (3)	171
C3A—H3A···O2ⁱ	0.93	2.50	3.392 (3)	160
C3B—H3B···O2ⁱⁱ	0.93	2.56	3.342 (4)	142
C5A—H52A···O1Bⁱⁱⁱ	0.97	2.49	3.383 (4)	153

Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x−1/2, y, −z+1/2; (iii) −x+1/2, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₉H₁₁NO·0.5H₂O
M_r	158.20
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	14.725 (4), 14.464 (4), 15.474 (3)
V (Å³)	3295.7 (14)
Z	16
Radiation type	Cu Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.28 × 0.26 × 0.21

Data collection
Diffractometer	Bruker SMART APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.832, 0.873
No. of measured, independent and observed [I > 2σ(I)] reflections	11258, 2727, 1989
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.590

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.205, 1.39
No. of reflections	2727
No. of parameters	215
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.24

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H21···O1A	0.96 (3)	1.87 (3)	2.825 (3)	170 (3)
O2—H22···O1B	0.95 (4)	1.86 (3)	2.799 (3)	170 (3)
C2B—H2B···O1A	0.93	2.53	3.454 (3)	171
C3A—H3A···O2ⁱ	0.93	2.50	3.392 (3)	160
C3B—H3B···O2ⁱⁱ	0.93	2.56	3.342 (4)	142
C5A—H52A···O1Bⁱⁱⁱ	0.97	2.49	3.383 (4)	153

Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x−1/2, y, −z+1/2; (iii) −x+1/2, −y+1, z−1/2.

References

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Volume 66| Part 4| April 2010| Pages o806-o807

doi:10.1107/S1600536810008779

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