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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages 231-234

Crystal structure of 2-pentyl­oxybenzamide

aInstitute of Inorganic Chemistry, University of Hamburg, Hamburg, Germany, bDepartment of Chemical Engineering, United Arab Emirates University, AL Ain, Abu Dhabi, United Arab Emirates, and cDepartment of Chemistry, United Arab Emirates University, AL Ain, Abu Dhabi, United Arab Emirates
*Correspondence e-mail: thies@uaeu.ac.ae

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 31 August 2014; accepted 14 September 2014; online 20 September 2014)

In the title mol­ecule, C12H17NO2, the amide NH2 group is oriented toward the pent­yloxy substituent and an intra­molecular N—H⋯O hydrogen bond is formed with the pent­yloxy O atom. The benzene ring forms dihedral angles of 2.93 (2) and 5.60 (2)° with the amide group and the pent­yloxy group mean planes, respectively. In the crystal, mol­ecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with their mol­ecular planes parallel, but at an offset of 0.45 (1) Å to each other. These dimers are ordered into two types of symmetry-related columns extended along the a axis, with the mean plane of one set of dimers in a column approximately parallel to (121) and the other in a column approximately parallel to (1-21). The two planes form a dihedral angle of 85.31 (2)°, and are linked via C—H⋯O hydrogen bonds and C—H⋯π inter­actions, forming a three-dimensional framework structure.

1. Chemical context

2-Alk­oxy­benzamide moieties can be found as structural units in medicinally active compounds, such in dopamine (DA) receptor antagonists (van de Waterbeemd & Testa, 1983[Waterbeemd, H. van de & Testa, B. (1983). J. Med. Chem. 26, 203-207.]). Typically such components are Sulpiride®, Metoclopramide® and Tiapride®. Other substituted 2-alk­oxy­benzamides have been found to be antagonists of chemotherapy-induced nausea (Monkovic et al., 1988[Monkovic, I., Willner, D., Adam, M. A., Brown, M., Crenshaw, R. R., Fuller, C. E., Juby, P. F., Luke, G. M., Matiskella, J. A. & Montzka, T. A. (1988). J. Med. Chem. 31, 1548-1566.]). Also, 2-alk­oxy­benzamides have been proposed as agonists of the α7 nicotinic receptor (Bodnar et al., 2005[Bodnar, A. L., Cortes-Burgos, L. A., Cook, K. K., Dinh, D. M., Groppi, V. E., Hajos, M., Higdon, N. R., Hoffmann, W. E., Hurst, R. S., Myers, J. K., Rogers, N. B., Wall, T. M., Wolfe, M. L. & Wong, E. (2005). J. Med. Chem. 48, 905-908.]) and as neuroleptic compounds (Florvall & Oegren, 1982[Florvall, L. & Oegren, S.-O. (1982). J. Med. Chem. 1982, 25, 1280-1286.]). 2-Eth­oxy­benzamide, under the name ethenzamide, is a commonly used analgesicum (Darias et al., 1992[Darias, V., Bravo, L., Abdallah, S. S., Sánchez Mateo, C. C., Expósito-Orta, M. A., Lissavetsky, J. & Manzanares, J. (1992). Arch. Pharm. 325, 83-87.]).

[Scheme 1]

In our efforts to use 2-alk­oxy­benzamides as components in co-crystal formation (Aitipamula et al., 2012[Aitipamula, S., Wong, A. B. H., Chow, P. S. & &Tan, R. B. H. (2012). CrystEngComm, 14, 8515-8524.]), we prepared the title compound, 2-pentyl­oxybenzamide, and report herein on its crystal structure. 2-Pentyl­oxybenzamide was first studied for its anti­pyretic and analgesic properties (Bavin et al., 1952[Bavin, E. M., Macrae, F. J., Seymour, D. E. & Waterhouse, P. D. (1952). J. Pharm. Pharmacol. 4, 872-878.]; Macrae & Seymour, 1956[Macrae, F. J. & Seymour, D. E. (1956). GB 726786 (May 1955) [Herts Pharmaceuticals Ltd.], Chem. Abstr. 50, 28262.]). Afterwards, it was found to have anti­fungal activity and to be useful in the treatment of dermatomycosis (Simmonite & Tattersall, 1962[Simmonite, D. & Tattersall, K. (1962). GB 872891 (July 1961) [Smith, T. J. & Nephew Ltd.], Chem. Abstr. 56, 18626.]; Coates et al., 1957[Coates, L. V., Drain, D. J., Kerridge, K. A., Macrae, F. J. & Tattersall, K. (1957). J. Pharm. Pharmacol. 9, 855-862.]). Under the name penta­lamide, it is still used as an ingredient in anti­fungal agents for topical use.

2. Structural commentary

In the title mol­ecule, Fig. 1[link], the benzene ring is nearly coplanar with the amide group [C6—C1—C7—O1 = −2.48 (18)°] and the pent­yloxy group [C3—C2—O2—C8 = 0.37 (18)°]. The amide NH2 group is oriented towards the ether group allowing for an intra­molecular hydrogen bond (N1—H1B⋯O2; Fig. 1[link] and Table 1[link]). The latter is also present in analogous compounds, such as 3-hy­droxy-2-meth­oxy­benzamide (Wilbrand et al., 2012[Wilbrand, S., Neis, C. & Hegetschweiler, K. (2012). Acta Cryst. E68, o3494.]), 2-propoxybenzamide (Al Jasem et al., 2012[Al Jasem, Y., Hindawi, B. al, Thiemann, T. & White, F. (2012). Acta Cryst. E68, o2639-o2640.]) and 2-(prop-2-en­yloxy)benzamide (Bugenhagen et al., 2012[Bugenhagen, B., Al Jasem, Y., Barkhad, F., Hindawi, B. al & Thiemann, T. (2012). Acta Cryst. E68, o3169-o3170.]). 2-Eth­oxy­benzamide is the only studied 2-alk­oxy­benzamide that does not exhibit an intra­molecular hydrogen bond in the single component crystal (Pagola & Stephens, 2009[Pagola, S. & Stephens, P. W. (2009). Acta Cryst. C65, o583-o586.]). However, it shows a similar conformation to the other 2-alk­oxy­benzamides in the co-crystal form with thio­urea (Moribe et al., 2004[Moribe, K., Tsuchiya, M., Tosuka, Y., Yamaguchi, K., Oguchi, T. & Yamamoto, K. (2004). Chem. Pharm. Bull. 52, 524—529.]), and with salicylic acid (Back et al., 2012[Back, K. R., Davey, R. J., Grecu, T., Hunter, C. A. & Taylor, L. S. (2012). Cryst. Growth Des. 12, 6110-6117.]).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 benzene ring.

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1B⋯O2 0.915 (17) 1.921 (18) 2.6510 (15) 135.4 (15)
N1—H1A⋯O1i 0.919 (19) 1.964 (19) 2.8824 (15) 177.8 (17)
C3—H3⋯O1ii 0.93 2.62 3.546 (2) 178
C4—H4⋯O1iii 0.93 2.53 3.306 (2) 141
C11—H11ACg1iv 0.97 2.90 3.7283 (16) 141
Symmetry codes: (i) -x, -y+1, -z; (ii) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (iii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (iv) x-1, y, z.
[Figure 1]
Figure 1
A view of the mol­ecular structure of the title mol­ecule, with atom labelling. Displacement ellipsoids are shown at the 50% probability level. The intra­molecular N—H⋯O hydrogen bond is shown as a green dashed line (see Table 1[link] for details).

3. Supra­molecular features

In the crystal, mol­ecules are linked by pairs of N-H⋯O (N1—H1A⋯O1) hydrogen bonds forming inversion dimers (Fig. 2[link] and Table 1[link]). These dimers form a nested network of mol­ecules, made of two layers, (121) and (1[\overline{2}]1), which form an angle of 85.31 (2)° between their planes (Fig. 3[link]). The dimers in the layers are linked by C—H⋯O (C4—H4⋯O1) hydrogen bonds and C—H⋯π inter­actions, forming a three-dimensional framework (Fig. 3[link] and Table 1[link]). Within two parallel layers, pairs of mol­ecules lie with an offset to each other without any noticeable, direct inter­action between them; the parallel layers are at a distance of 3.81 (3) Å from each other. Along the a axis the pairs are ordered in two symmetry-related columns. The plane of the benzene ring (C1–C6) of the 2-pentyl­oxybenzamide forms an angle of 25.29 (2)° with the column axis.

[Figure 2]
Figure 2
A partial view of the crystal packing of the title compound. The hydrogen bonds are shown as green dashed lines [see Table 1[link] for details; symmetry codes: (i) −x + 1, y + [{1\over 2}], −z + [{1\over 2}]; (ii) x, y, z; (iii) x, −y + [{1\over 2}], z + [{1\over 2}]; (iv) −x, y − [{1\over 2}], −z + [{1\over 2}]]
[Figure 3]
Figure 3
A view of the crystal network formed by the layers of inversion dimers in the planes (121) in red, and (1[\overline{2}]1) in blue. The hydrogen bonds are shown as green dashed lines (see Table 1[link] for details; H atoms have been omitted for clarity).

4. Database survey

From a database survey (Cambridge Structural Database, Version 5.35, last update May 2014; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]), the following were picked as relevant comparable structures: 3-hy­droxy-2-meth­oxy­benzamide (Wilbrand et al., 2012[Wilbrand, S., Neis, C. & Hegetschweiler, K. (2012). Acta Cryst. E68, o3494.]), 2-meth­oxy­benzamide (Moribe et al., 2006[Moribe, K., Tsuchiya, M., Tozuka, Y., Yamaguchi, K., Oguchi, T. & Yamamoto, K. (2006). J. Inclusion Phenom. Macrocycl. Chem. 54, 9-16.]), 2-eth­oxy­benzamide (Pagola & Stephens, 2009[Pagola, S. & Stephens, P. W. (2009). Acta Cryst. C65, o583-o586.]; Back et al., 2012[Back, K. R., Davey, R. J., Grecu, T., Hunter, C. A. & Taylor, L. S. (2012). Cryst. Growth Des. 12, 6110-6117.]), 2-propoxybenzamide (Al Jasem et al., 2012[Al Jasem, Y., Hindawi, B. al, Thiemann, T. & White, F. (2012). Acta Cryst. E68, o2639-o2640.]) and 2-(prop-2-en­yloxy)benzamide (Bugen­hagen et al., 2012[Bugenhagen, B., Al Jasem, Y., Barkhad, F., Hindawi, B. al & Thiemann, T. (2012). Acta Cryst. E68, o3169-o3170.]). For 2-propoxybenzamide, a homologue of the title compound, a similar formation of inversion-related mol­ecular pairs in the crystal was reported, hence the two compounds exhibit a similar packing. The noticeable difference between the two compounds is the larger dihedral angle between the carboxamide group and the benzene ring in 2-propoxybenzamide, 12.41 (2)° compared to 3.30 (15)° in the title compound, 2-pentyl­oxybenzamide. Also, the parallel layers of mol­ecules in the title compound are further apart [separated by 3.81 (3) Å] than is found for a similar packing of 2-propoxybenzamide [3.69 (2) Å]. Similarly, inversion-related pairs of mol­ecules are formed by inter­molecular (amide–amide) hydrogen bonding in 2-eth­oxy­benzamide and 3-hy­droxy-2-meth­oxy­benzamide. As 2-eth­oxy­benzamide exhibits no intra­molecular hydrogen bonding, the freed acceptor–donor sites are used for additional inter­molecular hydrogen bonding with the adjacent mol­ecule.

In contrast, in 2-meth­oxy­benzamide and in 2-(prop-2-en­yloxy)benzamide the inter­molecular N—H⋯O hydrogen bonds involving the amide groups do not lead to pair formation but generate C(4) and R32(7) motifs.

5. Synthesis and crystallization

The preparation of the title compound follows a Williamson ether synthesis using DMSO as solvent, analogous to a general procedure (Johnstone & Rose, 1979[Johnstone, R. A. W. & Rose, M. E. (1979). Tetrahedron, 35, 2169-2173.]): To powdered KOH (1.12 g, 20.0 mmol) in DMSO (18 ml) was added salicyl­amide (1.37 g, 10.0 mmol), and the resulting mixture was stirred for 10 min. at rt. Then, n-amyl iodide (4.2 g, mmol, 21.2 mmol) was added dropwise. The solution was stirred for 12 h at rt. It was then poured into water (200 ml) and extracted with chloro­form (3 × 75 ml). The organic phase was dried over anhydrous MgSO4, concentrated in vacuo, and the residue was subjected to column chromatography on silica gel (CHCl3/MtBE/hexane v/v/v 1:1:1) to give the title compound (1.55 g, 75%) as colourless crystals (m.p. 362 K). IR (KBr, cm−1) νmax 3434, 3168, 2948, 2868, 1664, 1593, 1387, 1232, 1164, 1018, 832, 788, 765, 575; 1H NMR (400 MHz, CDCl3, δH) 0.93 (3H, t, 3J = 7.2 Hz, CH3), 1.38–1.48 (4H, m), 1.84–1.89 (2H, m), 4.11 (2H, d, 3J = 6.4 Hz); 6.03 (1H, bs, NH), 6.96 (1H, d, 3J = 8.4 Hz), 7.03–7.07 (1H, m), 7.42–7.46 (1H, m), 7.85 (1H, bs, NH), 8.20 (1H, dd, 3J = 7.6 Hz, 4J = 2.0 Hz), 13C NMR (100.5 MHz, CDCl3, δC) 14.0 (CH3), 22.4 (CH2), 28.2 (CH2), 28.9 (CH2), 69.1 (OCH2), 112.2 (CH), 120.7 (Cquat), 121.0 (CH), 132.5 (CH), 133.3 (Cquat), 157.4 (Cquat), 167.2 (Cquat, CO).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. All C-bound H atoms were placed in calculated positions and refined as riding atoms: C—H distances of 0.95 − 1.00 Å with Uiso(H) = xUeq(C), where x = 1.5 for methyl and = 1.2 for other H-atoms. The N-bound H atoms were located in a difference electron-density map and freely refined.

Table 2
Experimental details

Crystal data
Chemical formula C12H17NO2
Mr 207.27
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 8.1830 (2), 11.2706 (2), 14.5386 (4)
β (°) 119.696 (2)
V3) 1164.76 (5)
Z 4
Radiation type Cu Kα
μ (mm−1) 0.64
Crystal size (mm) 0.25 × 0.19 × 0.10
 
Data collection
Diffractometer SuperNova, Dual, Cu at zero, Atlas
Absorption correction Multi-scan (CrysAlis PRO; Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.])
Tmin, Tmax 0.854, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections 6112, 2268, 1900
Rint 0.022
(sin θ/λ)max−1) 0.621
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.115, 1.03
No. of reflections 2268
No. of parameters 145
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.19, −0.22
Computer programs: CrysAlis PRO (Agilent, 2012[Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, England.]), SHELXS97 and SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) within OLEX2 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]).

Supporting information


Chemical context top

2-Alk­oxy­benzamide moieties can be found as structural units in medicinally active compounds, such in dopamine (DA) receptor antagonists (van de Waterbeemd & Testa, 1983). Typical such components are Sulpiride®, Metoclopramide® and Tiapride®. Other substituted 2-alk­oxy­benzamides have been found to be antagonists of chemotherapy-induced nausea (Monkovic et al., 1988). Also, 2-alk­oxy­benzamides have been proposed as agonists of the α7 nicotinic receptor (Bodnar et al., 2005) and as neuroleptic compounds (Florvall & Oegren, 1982). 2-Eth­oxy­benzamide, under the name ethenzamide, is a commonly used analgesicum (Darias et al., 1992). In our efforts to use 2-alk­oxy­benzamides as components in co-crystal formation (Aitipamula et al., 2012), we prepared the title compound, 2-pentyl­oxybenzamide, and report herein on its crystal structure. 2-Pentyl­oxybenzamide was first studied for its anti­pyretic and analgesic properties (Bavin et al., 1952; Macrae & Seymour, 1956). Afterwards, it was found to have anti­fungal activity and to be useful in the treatment of dermatomycosis (Simmonite & Tattersall, 1962; Coates et al., 1957). Under the name penta­lamide, it is still used as an ingredient in anti­fungal agents for topical use.

Structural commentary top

In the title molecule, Fig. 1, the benzene ring is nearly coplanar with the amide group [C6—C1—C7—O1 = -2.48 (18)°] and the pentyl­oxy group [C3—C2—O2—C8 = 0.37 (18)°]. The amide NH2 group is oriented towards the ether group allowing for an intra­molecular hydrogen bond (N1—H1B···O2; Fig. 1 and Table 1). The latter is also present in analogous compounds, such as 3-hy­droxy-2-meth­oxy­benzamide (Wilbrand et al., 2012), 2-propoxybenzamide (Al Jasem et al., 2012) and 2-(prop-2-enyl­oxy)benzamide (Bugenhagen et al., 2012). 2-Eth­oxy­benzamide is the only studied 2-alk­oxy­benzamide that does not exhibit an intra­molecular hydrogen bond in the single component crystal (Pagola & Stephens, 2009). However, it shows a similar conformation to the other 2-alk­oxy­benzamides in the co-crystal form with thio­urea (Moribe et al., 2004), and with salicylic acid (Back et al., 2012).

Supra­molecular features top

In the crystal, molecules are linked by pairs of N—H···O (N1—H1A···O1) hydrogen bonds forming inversion dimers (Fig. 2 and Table 1). These dimers form a nested network of molecules, made of two layers, (121) and (121), which form an angle of 85.31 (2)° between their planes (Fig. 3). The dimers in the layers are linked by C—H···O (C4—H4···O1) hydrogen bonds and C—H···π inter­actions, forming a three-dimensional framework (Fig. 3 and Table 1). Within two parallel layers, pairs of molecules lie with an offset to each other without any noticeable, direct inter­action between them; the parallel layers are at a distance of 3.81 (3) Å from each other. Along the a axis the pairs are ordered in two symmetry-related columns. The plane of the benzene ring (C1–C6) of the 2-pentyl­oxybenzamide forms an angle of 25.29 (2)° with the column axis.

Database survey top

From a database survey (Cambridge Structural Database, Version 5.35, last update May 2014; Allen, 2002), the following were picked as relevant comparable structures: 3-hy­droxy-2-meth­oxy­benzamide (Wilbrand et al., 2012), 2-meth­oxy­benzamide (Moribe et al., 2006), 2-eth­oxy­benzamide (Pagola & Stephens, 2009; Back et al., 2012), 2-propoxybenzamide (Al Jasem et al., 2012) and 2-(prop-2-enyl­oxy)benzamide (Bugenhagen et al., 2012). For 2-propoxybenzamide, a homologue of the title compound, a similar formation of inversion-related molecular pairs in the crystal was reported, hence the two compounds exhibit a similar packing. The noticeable difference between the two compounds is the larger dihedral angle between the carboxamide group and the benzene ring in 2-propoxybenzamide, 12.41 (2)° compared to 3.30 (15)° in the title compound, 2-pentyl­oxybenzamide. Also, the parallel layers of molecules in the title compound are further apart [separated by 3.81 (3) Å] than is found for a similar packing of 2-propoxybenzamide [3.69 (2) Å]. Similarly, inversion-related pairs of molecules are formed by inter­molecular (amide–amide) hydrogen bonding in 2-eth­oxy­benzamide and 3-hy­droxy-2-meth­oxy­benzamide. As 2-eth­oxy­benzamide exhibits no intra­molecular hydrogen bonding, the freed acceptor–donor sites are used for additional inter­molecular hydrogen bonding with the adjacent molecule.

In contrast, in 2-meth­oxy­benzamide and in 2-(prop-2-enyl­oxy)benzamide the inter­molecular N—H···O hydrogen bonds involving the amide groups do not lead to pair formation but generate C(4) and R23(7) motifs.

Synthesis and crystallization top

The preparation of the title compound follows a Williamson ether synthesis using DMSO as solvent, analogous to a general procedure (Johnstone & Rose, 1979): To powdered KOH (1.12 g, 20.0 mmol) in DMSO (18 ml) was added salicyl­amide (1.37 g, 10.0 mmol), and the resulting mixture was stirred for 10 min. at rt. Then, n-amyl iodide (4.2 g, mmol, 21.2 mmol) was added dropwise. The solution was stirred for 12 h at rt. It was then poured into water (200 ml) and extracted with chloro­form (3 × 75 ml). The organic phase was dried over anhydrous MgSO4, concentrated in vacuo, and the residue was subjected to column chromatography on silica gel (CHCl3/MtBE/hexane v/v/v 1:1:1) to give the title compound (1.55 g, 75%) as colourless crystals (m.p. 362 K). IR (KBr, cm-1) νmax 3434, 3168, 2948, 2868, 1664, 1593, 1387, 1232, 1164, 1018, 832, 788, 765, 575; 1H NMR (400 MHz, CDCl3, δH ) 0.93 (3H, t, 3J = 7.2 Hz, CH3), 1.38–1.48 (4H, m), 1.84–1.89 (2H, m), 4.11 (2H, d, 3J = 6.4 Hz); 6.03 (1H, bs, NH), 6.96 (1H, d, 3J = 8.4 Hz), 7.03–7.07 (1H, m), 7.42–7.46 (1H, m), 7.85 (1H, bs, NH), 8.20 (1H, dd, 3J = 7.6 Hz, 4J = 2.0 Hz), 13C NMR (100.5 MHz, CDCl3, δC) 14.0 (CH3), 22.4 (CH2), 28.2 (CH2), 28.9 (CH2), 69.1 (OCH2), 112.2 (CH), 120.7 (Cquat), 121.0 (CH), 132.5 (CH), 133.3 (Cquat), 157.4 (Cquat), 167.2 (Cquat, CO).

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All C-bound H atoms were placed in calculated positions and refined as riding atoms: C—H distances of 0.95 - 1.00 Å with Uiso(H) = xUeq(C), where x = 1.5 for methyl and = 1.2 for other H-atoms. The N-bound H atoms were located in a difference electron-density map and freely refined.

Related literature top

For related literature, see: Aitipamula et al. (2012); Al Jasem, al Hindawi, Thiemann & White (2012); Back et al. (2012); Bavin et al. (1952); Bodnar et al. (2005); Bugenhagen et al. (2012); Coates et al. (1957); Darias et al. (1992); Florvall & Oegren (1982); Johnstone & Rose (1979); Monkovic et al. (1988); Moribe et al. (2004, 2006); Pagola & Stephens (2009); Waterbeemd & Testa (1983); Wilbrand et al. (2012).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) within OLEX2 (Dolomanov et al., 2009); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are shown at the 50% probability level. The intramolecular N—H···O hydrogen bond is shown as a green dashed line (see Table 1 for details).
[Figure 2] Fig. 2. A partial view of the crystal packing of the title compound. The hydrogen bonds are shown as green dashed lines [see Table 1 for details; symmetry codes: (i) -x+1, y+1/2, -z+1/2; (ii) x, y, z; (iii) x, -y+1/2, z+1/2; (iv) -x, y-1/2, -z+1/2]
[Figure 3] Fig. 3. A view of the crystal network formed by the layers of inversion dimers in the planes (121) in red, and (121) in blue. The hydrogen bonds are shown as green dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).
2-pentyloxybenzamide top
Crystal data top
C12H17NO2F(000) = 448
Mr = 207.27Dx = 1.182 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.5418 Å
a = 8.1830 (2) ÅCell parameters from 2743 reflections
b = 11.2706 (2) Åθ = 3.9–73.1°
c = 14.5386 (4) ŵ = 0.64 mm1
β = 119.696 (2)°T = 100 K
V = 1164.76 (5) Å3Block, colourless
Z = 40.25 × 0.19 × 0.10 mm
Data collection top
SuperNova, Dual, Cu at zero, Atlas
diffractometer
2268 independent reflections
Radiation source: SuperNova (Cu) X-ray Source1900 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.022
Detector resolution: 10.4127 pixels mm-1θmax = 73.3°, θmin = 5.3°
ω scansh = 105
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 1314
Tmin = 0.854, Tmax = 1.000l = 1618
6112 measured reflections
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0645P)2 + 0.2593P]
where P = (Fo2 + 2Fc2)/3
2268 reflections(Δ/σ)max < 0.001
145 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C12H17NO2V = 1164.76 (5) Å3
Mr = 207.27Z = 4
Monoclinic, P21/cCu Kα radiation
a = 8.1830 (2) ŵ = 0.64 mm1
b = 11.2706 (2) ÅT = 100 K
c = 14.5386 (4) Å0.25 × 0.19 × 0.10 mm
β = 119.696 (2)°
Data collection top
SuperNova, Dual, Cu at zero, Atlas
diffractometer
2268 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
1900 reflections with I > 2σ(I)
Tmin = 0.854, Tmax = 1.000Rint = 0.022
6112 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.115H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.19 e Å3
2268 reflectionsΔρmin = 0.22 e Å3
145 parameters
Special details top

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
C10.25614 (18)0.29076 (11)0.20599 (10)0.0233 (3)
C100.14119 (19)0.33945 (13)0.46481 (11)0.0269 (3)
C110.29380 (19)0.41079 (13)0.47067 (11)0.0294 (3)
C120.3051 (2)0.37915 (16)0.56955 (12)0.0389 (4)
C20.21475 (18)0.25854 (12)0.28594 (10)0.0240 (3)
C30.31443 (19)0.16670 (12)0.35597 (11)0.0279 (3)
C40.45350 (19)0.10654 (13)0.34698 (11)0.0303 (3)
C50.49609 (19)0.13709 (13)0.26885 (11)0.0301 (3)
C60.39777 (18)0.22849 (12)0.19968 (10)0.0266 (3)
C70.15680 (18)0.38484 (11)0.12366 (10)0.0232 (3)
C80.03619 (19)0.28821 (12)0.37434 (10)0.0263 (3)
C90.11424 (18)0.36885 (12)0.37063 (10)0.0256 (3)
H10A0.17140.25580.46180.032*
H10B0.02290.35260.52950.032*
H11A0.41420.39500.40820.035*
H11B0.26720.49480.47170.035*
H12A0.33290.29620.56830.058*
H12B0.40270.42500.57100.058*
H12C0.18690.39630.63150.058*
H1A0.056 (2)0.4934 (17)0.0658 (14)0.042 (5)*
H1B0.021 (2)0.4242 (16)0.1713 (14)0.041 (5)*
H30.28730.14580.40890.033*
H40.51880.04520.39370.036*
H50.58960.09670.26300.036*
H60.42700.24900.14750.032*
H8A0.14950.29500.44270.032*
H8B0.00620.20650.36500.032*
H9A0.23130.35700.30490.031*
H9B0.07670.45110.37420.031*
N10.01348 (16)0.44361 (11)0.12198 (9)0.0282 (3)
O10.20767 (12)0.40558 (9)0.05777 (7)0.0264 (2)
O20.07616 (13)0.32058 (8)0.29182 (7)0.0271 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0293 (5)0.0312 (5)0.0239 (5)0.0023 (4)0.0171 (4)0.0000 (4)
O20.0312 (5)0.0313 (5)0.0271 (5)0.0063 (4)0.0207 (4)0.0059 (4)
N10.0343 (6)0.0299 (6)0.0271 (6)0.0063 (5)0.0204 (5)0.0060 (5)
C10.0233 (6)0.0263 (6)0.0213 (6)0.0034 (5)0.0116 (5)0.0028 (5)
C20.0227 (6)0.0269 (7)0.0250 (6)0.0002 (5)0.0139 (5)0.0021 (5)
C30.0293 (7)0.0316 (7)0.0266 (7)0.0015 (5)0.0168 (6)0.0028 (5)
C40.0302 (7)0.0313 (7)0.0300 (7)0.0060 (6)0.0153 (6)0.0045 (6)
C50.0279 (7)0.0347 (8)0.0309 (7)0.0044 (6)0.0169 (6)0.0018 (6)
C60.0259 (7)0.0331 (7)0.0244 (6)0.0013 (5)0.0153 (6)0.0028 (5)
C70.0252 (7)0.0244 (6)0.0224 (6)0.0053 (5)0.0135 (5)0.0046 (5)
C80.0303 (7)0.0300 (7)0.0250 (6)0.0035 (5)0.0186 (6)0.0055 (5)
C90.0260 (7)0.0296 (7)0.0247 (6)0.0022 (5)0.0152 (5)0.0034 (5)
C100.0281 (7)0.0318 (7)0.0259 (7)0.0031 (6)0.0173 (6)0.0039 (5)
C110.0290 (7)0.0357 (7)0.0284 (7)0.0037 (6)0.0180 (6)0.0032 (6)
C120.0405 (9)0.0513 (10)0.0375 (8)0.0100 (7)0.0288 (7)0.0064 (7)
Geometric parameters (Å, º) top
O1—C71.2412 (15)C6—H60.9300
O2—C21.3706 (15)C8—H8A0.9700
O2—C81.4381 (14)C8—H8B0.9700
N1—C71.3366 (17)C8—C91.5095 (18)
N1—H1A0.919 (19)C9—H9A0.9700
N1—H1B0.915 (17)C9—H9B0.9700
C1—C21.4099 (17)C9—C101.5272 (17)
C1—C61.3962 (18)C10—H10A0.9700
C1—C71.5013 (18)C10—H10B0.9700
C2—C31.3966 (19)C10—C111.5227 (18)
C3—H30.9300C11—H11A0.9700
C3—C41.3853 (19)C11—H11B0.9700
C4—H40.9300C11—C121.5278 (18)
C4—C51.3866 (19)C12—H12A0.9600
C5—H50.9300C12—H12B0.9600
C5—C61.385 (2)C12—H12C0.9600
C1—C6—H6119.0C6—C1—C7116.23 (11)
C10—C11—C12111.28 (12)C6—C1—C2118.09 (12)
C10—C11—H11B109.4C7—N1—H1B118.2 (11)
C10—C11—H11A109.4C7—N1—H1A118.0 (10)
C10—C9—H9B110.0C8—C9—C10108.35 (11)
C10—C9—H9A110.0C8—C9—H9B110.0
C11—C12—H12C109.5C8—C9—H9A110.0
C11—C12—H12B109.5C9—C10—H10B108.5
C11—C12—H12A109.5C9—C10—H10A108.5
C11—C10—H10B108.5C9—C8—H8B109.7
C11—C10—H10A108.5C9—C8—H8A109.7
C11—C10—C9114.98 (11)H10A—C10—H10B107.5
C12—C11—H11B109.4H11A—C11—H11B108.0
C12—C11—H11A109.4H12A—C12—H12C109.5
C2—C3—H3119.9H12A—C12—H12B109.5
C2—C1—C7125.65 (12)H12B—C12—H12C109.5
C2—O2—C8117.38 (10)H1A—N1—H1B123.2 (14)
C3—C4—C5120.48 (13)H8A—C8—H8B108.2
C3—C4—H4119.8H9A—C9—H9B108.4
C3—C2—C1119.99 (12)N1—C7—C1119.22 (11)
C4—C5—H5120.4O1—C7—C1119.48 (11)
C4—C3—H3119.9O1—C7—N1121.29 (12)
C4—C3—C2120.29 (12)O2—C8—C9109.63 (10)
C5—C6—H6119.0O2—C8—H8B109.7
C5—C6—C1121.92 (12)O2—C8—H8A109.7
C5—C4—H4119.8O2—C2—C3122.35 (11)
C6—C5—H5120.4O2—C2—C1117.66 (11)
C6—C5—C4119.22 (12)
C1—C2—C3—C40.3 (2)C6—C1—C2—O2179.67 (11)
C2—C3—C4—C50.3 (2)C7—C1—C6—C5177.98 (12)
C2—C1—C7—N11.4 (2)C7—C1—C2—C3178.07 (12)
C2—C1—C7—O1179.44 (12)C7—C1—C2—O22.27 (19)
C2—C1—C6—C50.3 (2)C8—C9—C10—C11178.10 (12)
C2—O2—C8—C9177.89 (11)C8—O2—C2—C30.37 (18)
C3—C4—C5—C60.1 (2)C8—O2—C2—C1179.28 (11)
C4—C5—C6—C10.2 (2)C9—C10—C11—C12177.64 (12)
C6—C1—C7—N1176.66 (12)O2—C8—C9—C10175.11 (10)
C6—C1—C7—O12.48 (18)O2—C2—C3—C4179.95 (12)
C6—C1—C2—C30.02 (19)
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1–C6 benzene ring.
D—H···AD—HH···AD···AD—H···A
N1—H1B···O20.915 (17)1.921 (18)2.6510 (15)135.4 (15)
N1—H1A···O1i0.919 (19)1.964 (19)2.8824 (15)177.8 (17)
C3—H3···O1ii0.932.623.546 (2)178
C4—H4···O1iii0.932.533.306 (2)141
C11—H11A···Cg1iv0.972.903.7283 (16)141
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x1, y, z.
Hydrogen-bond geometry (Å, º) top
Cg1 is the centroid of the C1–C6 benzene ring.
D—H···AD—HH···AD···AD—H···A
N1—H1B···O20.915 (17)1.921 (18)2.6510 (15)135.4 (15)
N1—H1A···O1i0.919 (19)1.964 (19)2.8824 (15)177.8 (17)
C3—H3···O1ii0.932.6163.546 (2)178
C4—H4···O1iii0.932.5343.306 (2)141
C11—H11A···Cg1iv0.972.903.7283 (16)141
Symmetry codes: (i) x, y+1, z; (ii) x, y+1/2, z+1/2; (iii) x+1, y1/2, z+1/2; (iv) x1, y, z.

Experimental details

Crystal data
Chemical formulaC12H17NO2
Mr207.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)8.1830 (2), 11.2706 (2), 14.5386 (4)
β (°) 119.696 (2)
V3)1164.76 (5)
Z4
Radiation typeCu Kα
µ (mm1)0.64
Crystal size (mm)0.25 × 0.19 × 0.10
Data collection
DiffractometerSuperNova, Dual, Cu at zero, Atlas
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.854, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
6112, 2268, 1900
Rint0.022
(sin θ/λ)max1)0.621
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.115, 1.03
No. of reflections2268
No. of parameters145
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.22

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

 

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Volume 70| Part 10| October 2014| Pages 231-234
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