Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
In the crystal structure of the title compound, C9H9NO3, there are strong intra­molecular O—H...N and inter­molecular O—H...O hydrogen bonds which, together with weak inter­molecular C—H...O hydrogen bonds, lead to the formation of infinite chains of mol­ecules. The calculated inter­molecular hydrogen-bond energies are −11.3 and −2.7 kJ mol−1, respectively, showing the dominant role of the O—H...O hydrogen bonding. A natural bond orbital analysis revealed the electron contribution of the lone pairs of the oxazoline N and O atoms, and of the two hydr­oxy O atoms, to the order of the relevant bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107004131/dn2121sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107004131/dn2121Isup2.hkl
Contains datablock I

CCDC reference: 641814

Comment top

The present study of the title compound, (I), is a continuation of our previous studies of bifunctional monophenols (Langer et al., 2005, 2006), which are monomers of the AB type that provide linear poly(etheramide)s in a thermally initiated polymerization (Lustoň et al., 2006). According to Flory (1952), analogous compounds containing two phenolic groups, hence compounds of the AB2 type, provide hyperbranched polymers during thermal treatment (Lustoň & Kronek, 2007; Huber et al., 1999). Therefore, it was of interest to study also the crystal structure of these monomers, compounds with two phenolic groups and a 2-oxazoline ring. In this paper, we present the results for (I), one of the six possible isomers.

The atom-numbering scheme, together with the corresponding atomic displacement ellipsoid plot for (I), are shown in Fig. 1. Selected geometric parameters for (I) are listed in Table 1. The C1—C4 bond in (I) is significantly shorter than the usual single C—C bond (Table 1; Standard reference?), indicating weak conjugation between the 2-oxazoline ring substituted at the C-2 position (C1) and the benzene ring. The acute angle between the planes of the oxazoline and benzene rings is 2.76 (15)°. The 2-oxazoline ring in (I) is almost planar [χ2 = 63.5, maximum deviation 0.012 (2) Å], as it is, for example, for 2-(2-hydroxyphenyl)-2-oxazoline and 2-(4-hydroxyphenyl)-2-oxazoline (Langer et al., 2005).

A natural bond orbital (NBO) analysis (Foster & Weinhold, 1980) reveals that the electrons of the lone pairs of atoms N1, O1, O5 and O8 participate in the electron density within the N1C1, O1—C1, O5—C5 and O8—C8 bonds. The Wiberg indices illustrated in Fig. 2 show bond orders in the molecule of (I).

There are strong hydrogen bonds in the structure of (I), of the O—H···N (intramolecular) and O—H···O (intermolecular) types, as well as weak hydrogen bonds of the C—H···O type (intermolecular) (Fig.3. and Table 2). Calculations using the GAUSSIAN98 program package (Frisch et al., 1998) confirmed the experimental data, with more realistic H···A distances and D—H···A angles (Table 2).

The hydrogen-bonding pattern can be described using graph theory (Bernstein et al., 1995; Grell et al., 1999). On the first-level graph set, S(6) intramolecular strings formed by hydrogen bonds a, C(7) chains formed by hydrogen bonds b and C(6) chains formed by hydrogen bonds c were identified (see Fig. 3 for definitions of hydrogen bonds). On the second-level graph set, chains C22(11) and rings R44(22), formed by hydrogen bonds b and c, could be recognized.

The energy of the intermolecular hydrogen bonds was calculated and corrected to BSSE [Please define] using a standard procedure (Boys & Bernardi, 1970). The energy of hydrogen bond b was estimated to be approximately -11.3 kJ mol-1, and that of hydrogen bond c - 2.7 kJ mol-1. Hydrogen bond b plays a dominant role in the intermolecular interactions in the structure of (I) (Fig. 3).

Related literature top

For related literature, see: Becke (1993); Bernstein et al. (1995); Boys & Bernardi (1970); Flory (1952); Foster & Weinhold (1980); Frisch (1998); Glendening et al. (1993); Grell et al. (1999); Huber et al. (1999); Langer et al. (2005, 2006); Lustoň & Kronek (2007); Lustoň et al. (2006).

Experimental top

The relevant data for the synthetic and analytical methods, as well as a description of the instruments and materials used for the preparation and characterization of 2-(2,5-dihydroxyfenyl)-2-oxazoline, have been reported previously (Lustoň & Kronek, 2007). After recrystallization from toluene, well developed yellow needles of the (I) were obtained (m.p. 388–389 K).

Refinement top

H atoms were constrained to ideal geometry using an appropriate riding model and refined isotropically. For the hydroxyl groups, the O—H distances (0.84 Å) and C—O—H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine, with the starting positions based on the circular Fourier synthesis.

In the absence of significant anomalous scattering, the absolute configuration could not be reliably determined. Therefore, Friedel pairs were merged and any references to the Flack parameter have been removed.

The theoretical investigation of the hydrogen bonds was performed using the GAUSSIAN98 program package (Frisch et al., 1998) at the B3LYP/6–31G** level of theory (Becke, 1993). A cluster (66 atoms) consisted of three neighbouring molecules of (I), which represented hydrogen bonds existing in this compound. Only partial optimization of the positions of the H atoms participating in the hydrogen bonds was carried out. Natural bond orbital (NBO) calculations were carried out by means of the NBO program (Glendening et al., 1993) included in the GAUSSIAN98 package.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Wiberg bond orders calculated for an isolated molecule of (I) using NBO formalism. Arrows indicate predicted transfers of electron density from lone pairs.
[Figure 3] Fig. 3. The hydrogen-bonding pattern in the crystal structure of (I). See Table 2 for symbols and symmetry codes.
2-(2-Oxazolin-2-yl)benzene-1,4-diol top
Crystal data top
C9H9NO3Dx = 1.383 Mg m3
Mr = 179.17Melting point: 389 K
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 3265 reflections
a = 24.4297 (3) Åθ = 2.6–26.4°
b = 31.7167 (7) ŵ = 0.11 mm1
c = 4.4409 (1) ÅT = 173 K
V = 3440.94 (12) Å3Needle, yellow
Z = 161.00 × 0.06 × 0.04 mm
F(000) = 1504
Data collection top
Bruker SMART CCD area-detector
diffractometer
1010 independent reflections
Radiation source: fine-focus sealed tube840 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.073
ω scansθmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 3030
Tmin = 0.513, Tmax = 0.996k = 3938
9919 measured reflectionsl = 55
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.055P)2 + 2.545P]
where P = (Fo2 + 2Fc2)/3
1010 reflections(Δ/σ)max < 0.001
129 parametersΔρmax = 0.20 e Å3
1 restraintΔρmin = 0.18 e Å3
Crystal data top
C9H9NO3V = 3440.94 (12) Å3
Mr = 179.17Z = 16
Orthorhombic, Fdd2Mo Kα radiation
a = 24.4297 (3) ŵ = 0.11 mm1
b = 31.7167 (7) ÅT = 173 K
c = 4.4409 (1) Å1.00 × 0.06 × 0.04 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1010 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
840 reflections with I > 2σ(I)
Tmin = 0.513, Tmax = 0.996Rint = 0.073
9919 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0371 restraint
wR(F2) = 0.096H-atom parameters constrained
S = 1.03Δρmax = 0.20 e Å3
1010 reflectionsΔρmin = 0.18 e Å3
129 parameters
Special details top

Experimental. Data were collected at 173 K using a Siemens SMART CCD diffractometer equipped with an LT-2a low-temperature device. An almost-full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 30 s per frame. The preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003). The collected frames were integrated using the preliminary orientation matrix, which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 3265 reflections with I>10σ(I), after integration of all the frames data using SAINT (Bruker, 2003).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
xyzUiso*/Ueq
O10.13506 (6)0.06136 (5)0.5991 (5)0.0329 (5)
O50.02876 (7)0.06893 (6)0.3460 (5)0.0382 (5)
H50.01340.05320.47270.065 (12)*
O80.11289 (7)0.19201 (6)0.0585 (6)0.0433 (6)
H80.14540.18750.00500.056 (11)*
N10.04979 (8)0.03503 (6)0.6357 (6)0.0330 (6)
C10.08141 (9)0.06343 (7)0.5294 (6)0.0250 (6)
C20.08311 (11)0.00695 (8)0.8252 (7)0.0342 (7)
H2A0.07070.00791.03740.045 (9)*
H2B0.08120.02250.75230.034 (7)*
C30.14114 (11)0.02448 (8)0.7942 (8)0.0385 (7)
H3A0.16580.00340.70150.060 (10)*
H3B0.15610.03270.99310.050 (10)*
C40.06306 (10)0.09721 (7)0.3334 (6)0.0248 (6)
C50.00738 (9)0.09864 (7)0.2496 (7)0.0287 (6)
C60.01071 (10)0.13077 (7)0.0664 (7)0.0340 (7)
H60.04820.13180.00960.028 (7)*
C70.02479 (10)0.16149 (8)0.0358 (8)0.0345 (7)
H70.01180.18340.16310.031 (7)*
C80.07983 (10)0.16025 (7)0.0484 (7)0.0304 (6)
C90.09858 (10)0.12836 (7)0.2298 (7)0.0275 (6)
H90.13610.12750.28530.025 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0230 (9)0.0299 (9)0.0459 (12)0.0017 (7)0.0112 (9)0.0110 (10)
O50.0211 (9)0.0378 (10)0.0557 (14)0.0069 (8)0.0053 (9)0.0138 (11)
O80.0261 (10)0.0389 (10)0.0650 (17)0.0037 (8)0.0027 (10)0.0225 (11)
N10.0292 (11)0.0287 (11)0.0411 (15)0.0045 (9)0.0029 (11)0.0086 (11)
C10.0204 (11)0.0264 (12)0.0283 (15)0.0003 (9)0.0045 (11)0.0032 (12)
C20.0375 (15)0.0275 (12)0.0376 (17)0.0008 (11)0.0080 (14)0.0043 (14)
C30.0376 (15)0.0319 (14)0.0460 (19)0.0023 (12)0.0113 (14)0.0124 (15)
C40.0208 (11)0.0243 (11)0.0293 (14)0.0003 (9)0.0039 (10)0.0026 (12)
C50.0198 (12)0.0284 (13)0.0380 (17)0.0008 (10)0.0015 (12)0.0014 (13)
C60.0189 (11)0.0380 (14)0.0450 (18)0.0011 (11)0.0049 (13)0.0070 (15)
C70.0286 (13)0.0333 (13)0.0414 (17)0.0053 (11)0.0042 (13)0.0105 (13)
C80.0234 (12)0.0293 (12)0.0385 (17)0.0000 (10)0.0016 (12)0.0052 (13)
C90.0193 (11)0.0291 (12)0.0342 (16)0.0011 (10)0.0018 (11)0.0005 (12)
Geometric parameters (Å, º) top
O1—C11.348 (3)C3—H3A0.9900
N1—C11.277 (3)C3—H3B0.9900
C1—C41.451 (3)C4—C91.393 (3)
O1—C31.463 (3)C4—C51.411 (3)
O5—C51.361 (3)C5—C61.377 (3)
O5—H50.8400C6—C71.381 (4)
O8—C81.375 (3)C6—H60.9500
O8—H80.8400C7—C81.396 (3)
N1—C21.471 (3)C7—H70.9500
C2—C31.529 (4)C8—C91.372 (4)
C2—H2A0.9900C9—H90.9500
C2—H2B0.9900
C1—O1—C3105.88 (18)C9—C4—C5119.4 (2)
C5—O5—H5109.5C9—C4—C1121.9 (2)
C8—O8—H8109.5C5—C4—C1118.7 (2)
C1—N1—C2107.7 (2)O5—C5—C6119.4 (2)
N1—C1—O1117.9 (2)O5—C5—C4121.4 (2)
N1—C1—C4123.7 (2)C6—C5—C4119.3 (2)
O1—C1—C4118.3 (2)C5—C6—C7121.0 (2)
N1—C2—C3104.0 (2)C5—C6—H6119.5
N1—C2—H2A111.0C7—C6—H6119.5
C3—C2—H2A111.0C8—C7—C6119.8 (2)
N1—C2—H2B111.0C8—C7—H7120.1
C3—C2—H2B111.0C6—C7—H7120.1
H2A—C2—H2B109.0C9—C8—O8123.1 (2)
O1—C3—C2104.5 (2)C9—C8—C7120.0 (2)
O1—C3—H3A110.9O8—C8—C7116.9 (2)
C2—C3—H3A110.9C8—C9—C4120.6 (2)
O1—C3—H3B110.9C8—C9—H9119.7
C2—C3—H3B110.9C4—C9—H9119.7
H3A—C3—H3B108.9
C2—N1—C1—O11.9 (4)C1—C4—C5—O50.7 (4)
C2—N1—C1—C4179.4 (2)C9—C4—C5—C60.1 (4)
C3—O1—C1—N10.7 (3)C1—C4—C5—C6179.3 (2)
C3—O1—C1—C4179.5 (2)O5—C5—C6—C7180.0 (3)
C1—N1—C2—C32.2 (3)C4—C5—C6—C70.0 (4)
C1—O1—C3—C20.7 (3)C5—C6—C7—C80.4 (4)
N1—C2—C3—O11.7 (3)C6—C7—C8—C90.6 (4)
N1—C1—C4—C9178.0 (3)C6—C7—C8—O8179.3 (3)
O1—C1—C4—C93.4 (4)O8—C8—C9—C4179.5 (3)
N1—C1—C4—C51.2 (4)C7—C8—C9—C40.5 (4)
O1—C1—C4—C5177.5 (3)C5—C4—C9—C80.1 (4)
C9—C4—C5—O5179.9 (2)C1—C4—C9—C8179.0 (3)

Experimental details

Crystal data
Chemical formulaC9H9NO3
Mr179.17
Crystal system, space groupOrthorhombic, Fdd2
Temperature (K)173
a, b, c (Å)24.4297 (3), 31.7167 (7), 4.4409 (1)
V3)3440.94 (12)
Z16
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)1.00 × 0.06 × 0.04
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.513, 0.996
No. of measured, independent and
observed [I > 2σ(I)] reflections
9919, 1010, 840
Rint0.073
(sin θ/λ)max1)0.626
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.096, 1.03
No. of reflections1010
No. of parameters129
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.18

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT and SADABS (Sheldrick, 2003), SHELXTL (Bruker, 2003), SHELXTL, DIAMOND (Brandenburg, 2006).

Selected geometric parameters (Å, º) top
O1—C11.348 (3)O5—C51.361 (3)
N1—C11.277 (3)O8—C81.375 (3)
C1—C41.451 (3)
C2—N1—C1—O11.9 (4)N1—C1—C4—C9178.0 (3)
C3—O1—C1—N10.7 (3)O1—C1—C4—C93.4 (4)
C1—N1—C2—C32.2 (3)N1—C1—C4—C51.2 (4)
C1—O1—C3—C20.7 (3)O1—C1—C4—C5177.5 (3)
N1—C2—C3—O11.7 (3)
Comparison of experimental and calculated hydrogen-bonding geometry (Å, °) for compound (I) top
NotationD—H···AD—HH···AD···AD—H···A
aO5—H5···N10.841.802.548 (3)147
calc1.0061.6422.549147.7
bO8—H8···O5i0.841.922.756 (3)175
calc0.9751.7812.755176.0
cC6—H6···O1ii0.952.533.284 (3)136
calc1.0842.4423.282133.3
Symmetry codes: (i) -1/4 + x, 1/4 - y, -1/4 + z; (ii) 1/4 + x, 1/4 - y, -3/4 + z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds