organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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CHEMISTRY
ISSN: 2053-2296

Weak C—H⋯O hydrogen bonds in anisaldehyde, salicyl­aldehyde and cinnamaldehyde

aFaculty of Chemistry, University Duisburg–Essen, Universitätsstrasse 7, D-45117 Essen, Germany, and bSolid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India
*Correspondence e-mail: roland.boese@uni-due.de

(Received 13 June 2011; accepted 2 September 2011; online 16 September 2011)

In situ cryocrystallization has been employed to grow single crystals of 4-meth­oxy­benzaldehyde (anisaldehyde), C8H8O2, 2-hy­droxy­benzaldehyde (salicyl­aldehyde), C7H6O2, and (2E)-3-phenyl­prop-2-enal (cinnamaldehyde), C9H8O, all of which are liquids at room temperature. Several weak C—H⋯O inter­actions of the types Caryl—H⋯O, Cformyl—H⋯O and Csp3—H⋯O are present in these related crystal structures.

Comment

Experimental sophistication and developments in theoretical methodologies have improved the reliability of studies of weaker and lesser known inter­molecular inter­actions (Desiraju & Steiner, 1999[Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology. New York: Oxford University Press Inc.]). As a result, weakly bound complexes such as those involving C—H⋯O inter­actions are being extensively studied, and the nature and strength of these inter­actions are being assessed. The formyl C—H⋯O hydrogen bond in small-mol­ecule aldehydes is one such example. Many simple aldehydes are liquids, so not many structural reports are available for these compounds. Even if solid, there are not many crystal structure determinations for aldehydes. [There are 37 simple aromatic aldehydes in the Cambridge Structural Database (CSD, Version 5.32, November 2010 update; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) with refcodes ANTHAL, AYOHAL, BARFOT, DEWLOH, DPEDAL, FATVUS, FAXXEI, FEDSAJ, FIXHIE, FIXHOK, FIYQOT, FOMZUD, FORBZA, HEQXOR, HODMAP, IHEMAJ, IHEMIR, IZALAW, JULZAR, KATKIA, KERKOI, LOSGOQ, MASBUD, NARZUC, OKUHEH, PHBALD10, RAJKOC, RAFJOC, SAZQIT, SOCHAT, SUNDUA, TEBBOR, WASLOS, XAMVUJ, XAMVEN, XAYCIJ and XIGWAM; four α,β-unsaturated aldehydes with refcodes JAZLAX, SIPKEH, WOBJOM and WOBJUS; and nine salicyl­aldehyde derivatives with refcodes KOYTOH, MAYWEO, NEJJOB, OVANIL, RAPLAW, XEVRUL, YIQYIH, YOMXOO and YOMXUU.] Therefore, we chose to investigate the nature and type of inter­molecular inter­actions in the crystal structures of some very simple aldehydes.

[Scheme 1]

Anisaldehyde (4-meth­oxy­benzaldehyde), (I)[link], salicyl­alde­hyde (2-hy­droxy­benzaldehyde), (II)[link], and cinnamaldehyde [(2E)-3-phenyl­prop-2-enal], (III)[link], are liquids with melting points of 272, 266 and 265.5 K, respectively. These compounds are widely used in the chemical industry as inter­mediates in the preparation of perfumes, flavouring agents, dyes, pharma­ceuticals and agrochemicals. The inter­esting feature of these compounds is that they do not possess any strong hydrogen-bonding functionalities. In salicyl­aldehyde, the OH group is bound intra­molecularly to the aldehyde C=O group. The possible inter­molecular inter­actions in these three compounds are of the types Car­yl—H⋯O, Cform­yl—H⋯O, Csp2—H⋯O, Csp3—H⋯O, C—H⋯π and ππ. The formyl C—H⋯O inter­action is known to be very weak, owing to the poor electropositive character of the formyl H atom (Breneman & Wiberg, 1990[Breneman, C. M. & Wiberg, K. B. (1990). J. Comput. Chem. 11, 361-373.]; Williams, 1988[Williams, D. E. (1988). J. Comput. Chem. 9, 745-763.]). Despite this, short Cformyl—H⋯O contacts are frequently observed in the crystal structures of aliphatic aldehydes (Thakur et al., 2011[Thakur, T. S., Kirchner, M. T., Bläser, D., Boese, R. & Desiraju, G. R. (2011). Phys. Chem. Chem. Phys. 13, 14076-14091.]). The stabilizing nature of these Cformyl—H⋯O contacts has also been confirmed by computations on formaldehyde clusters; these calculations show a gradual increase in the electro­positive nature of the formyl H atom on going from an isolated gas-phase environment to the crystal. X-ray crystallographic studies of aromatic aldehydes by Moorthy and Venugopalan also established that formyl C—H⋯O inter­actions are relevant to crystal packing (Moorthy et al., 2003[Moorthy, J. N., Natarajan, R., Mal, P., Dixit, S. & Venugopalan, P. (2003). Cryst. Growth Des. 3, 581-585.], 2004[Moorthy, J. N., Natarajan, R., Mal, P. & Venugopalan, P. (2004). New J. Chem. 28, 1416-1419.], 2005[Moorthy, J. N., Natarajan, R. & Venugopalan, P. (2005). J. Mol. Struct. 741, 107-114.]; Lo Presti et al., 2006[Lo Presti, L., Soave, R. & Destro, R. (2006). J. Phys. Chem. B, 110, 6405-6414.]). However, in the case of aromatic aldehydes, the Cformyl—H⋯O inter­actions have to compete with Caryl—H⋯O inter­actions involving a relatively more acidic H atom. With our ongoing inter­est in the study of C—H⋯O hydrogen bonds in aldehydes, we report here the crystal structures of (I)[link], (II)[link] and (III)[link] (Fig. 1[link]). Crystals were obtained in each case by means of in situ cryocrystallization.

Compound (I)[link] crystallizes in the space group P212121 with Z′ = 1. The formyl and meth­oxy groups lie slightly out of the plane of the benzene ring by 4.3 (4) and −2.9 (3)°, respectively (torsion angles O1—C7—C1—C6 and C3—C4—O2—C8). The Caryl—Cformyl bond [1.455 (3) Å] is slightly shorter than a normal C—C single-bond distance (Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). This is possibly a result of extended conjugation between the aldehyde group and the aromatic ring. There are several weak C—H⋯O hydrogen bonds (Table 1[link]). Mol­ecules are arranged in zigzag chains along the c axis and are held together by weak Csp3—H⋯O hydrogen bonds between atom H8A of the meth­oxy group and the carbonyl O atom of a neighbouring mol­ecule. The chains are stacked along the a axis via weak Csp3—H⋯π inter­actions (Fig. 2[link]a). Mol­ecules in adjacent chains (along the b axis) are held together by weak Caryl—H⋯O inter­actions, viz. C3—H3⋯O2i and C5—H5⋯O1ii (Fig. 2[link]b; symmetry codes as in Table 1[link]). The formyl H atom is not engaged in a directed inter­molecular inter­action (Ribeiro-Claro et al., 2002[Ribeiro-Claro, P. J. A., Drewbm, M. G. B. & Félixa, V. (2002). Chem. Phys. Lett. 356, 318-324.]).

Compound (II)[link] crystallizes in the space group P21/c with Z′ = 1. The hy­droxy group is intra­molecularly hydrogen bonded to the formyl O atom (O2—H2⋯O1), as expected. A shorter Caryl—Cformyl bond [1.449 (2) Å] and a slightly elongated C=O bond [1.230 (2) Å] are observed. Mol­ecules in (II)[link] are linked by weak Car­yl—H⋯O hydrogen bonds (Table 2[link]): C3—H3 and C6—H6 inter­act with the carbonyl O atom (O1) and hy­droxy O atom (O6), respectively, of different neighbouring mol­ecules (Fig. 3[link]a). Additionally, a weak Cformyl—H⋯O inter­action is also observed [C7—H7⋯O1(−x, −y + 1, −z + 1); Fig. 3[link]b].

Compound (III)[link] crystallizes in the space group P21/c with Z′ = 1. The propenal fragment lies out of the plane of the benzene ring by −9.36 (18)° (torsion angle C2—C3—C11—C12), with a Caryl—Csp2 bond length of 1.4656 (16) Å. This indicates poor resonance between the propenal fragment and the aromatic ring. The mol­ecules are arranged in linear chains arranged in a head-to-tail fashion via C14—H14⋯O1(x + 1, y, z + 1) hydrogen bonds (Table 3[link] and Fig. 4[link]). The carbonyl O atom has weak C—H⋯O inter­actions with one Car­yl—H group (C13—H13 or C16—H16) from each of two adjacent chains. Despite the high acidity of the Csp2—H group relative to the Caryl—H groups, no Csp2—H⋯O hydrogen bonds (between the carbonyl O atom and aliphatic fragment) are observed. However, such inter­actions have been observed frequently in the crystal structures of some substituted cinnamaldehydes (CSD refcodes CUBNUJ, LUJTEQ, CUBJUJ and QODVAH).

[Figure 1]
Figure 1
The asymmetric units of the crystal structures of (I)[link], (II)[link] and (III)[link]. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2]
Figure 2
The crystal packing in (I)[link], with inter­molecular inter­actions shown as thin lines. [Symmetry codes: (i) x + [{1\over 2}], −y + [{1\over 2}], −z + 1; (ii) −x + [{1\over 2}], −y + 1, z + [{1\over 2}]; (iii) −x + [{3\over 2}], −y, z − [{1\over 2}]; (iv) −x + [{1\over 2}], −y, z − [{1\over 2}]; (v) −x + 2, y + [{1\over 2}], −z + [{3\over 2}].]
[Figure 3]
Figure 3
(a) The crystal packing in (II)[link], viewed down the c axis, showing the layers formed by the Caryl—H⋯O inter­actions. (b) The Cformyl—H⋯O inter­actions between the mol­ecules of adjacent layers. The inter­actions are shown as thin lines. [Symmetry codes: (i) −x + 1, y − [{1\over 2}], −z + [{3\over 2}]; (ii) −x + 2, y − [{1\over 2}], −z + [{3\over 2}]; (iii) −x, −y + 1, −z + 1.]
[Figure 4]
Figure 4
The crystal packing in (III)[link], with inter­molecular inter­actions shown as thin lines. [Symmetry codes: (i) −x, −y + 1, −z; (ii) −x − 1, −y + 1, −z − 1; (iii) −x − 1, y + [{1\over 2}], −z − [{1\over 2}].]

Experimental

Crystallization was performed on the diffractometer using a miniature zone-melting procedure with focused IR laser radiation, according to Boese & Nussbaumer (1994[Boese, R. & Nussbaumer, M. (1994). Organic Crystal Chemistry, edited by D. W. Jones, pp. 20-37. Oxford University Press.]). The temperature of crystallization was 263 K for (I)[link], 253 K for (II)[link] (Fluka) and 248 K for (III)[link] (Fluka, 98%, lot No. 1222882 24005132). The first crystal of (I)[link] obtained was of low quality. Therefore, only a reduced set of frames was collected, but afterwards no better crystals could be obtained. For (I)–(III)[link], the low coverage of the reflection data resulted from the orientation of the cylindrical crystal and the chosen scan mode, both due to the in situ crystal-growing technique. Any other mounting of the crystal or different scan mode would lead to melting of the crystals.

Compound (I)[link]

Crystal data
  • C8H8O2

  • Mr = 136.14

  • Orthorhombic, P 21 21 21

  • a = 4.970 (4) Å

  • b = 9.034 (9) Å

  • c = 15.544 (14) Å

  • V = 697.9 (11) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 203 K

  • 0.30 × 0.30 × 0.30 mm

Data collection
  • Siemens SMART three-axis goniometer with an APEXII area-detector system

  • 2015 measured reflections

  • 885 independent reflections

  • 705 reflections with I > 2σ(I)

  • Rint = 0.069

  • θmax = 24.0°

Refinement
  • R[F2 > 2σ(F2)] = 0.036

  • wR(F2) = 0.071

  • S = 0.94

  • 885 reflections

  • 92 parameters

  • H-atom parameters constrained

  • Δρmax = 0.12 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3⋯O2i 0.96 2.75 3.603 (4) 149
C5—H5⋯O1ii 0.96 2.70 3.447 (4) 135
C8—H8A⋯O1iii 0.97 2.71 3.582 (4) 150
C8—H8B⋯O1iv 0.97 2.75 3.434 (4) 128
Symmetry codes: (i) [-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]; (iii) [-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]; (iv) [-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}].

Compound (II)[link]

Crystal data
  • C7H6O2

  • Mr = 122.12

  • Monoclinic, P 21 /c

  • a = 6.3945 (3) Å

  • b = 13.8939 (9) Å

  • c = 6.9172 (4) Å

  • β = 103.262 (3)°

  • V = 598.17 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 233 K

  • 0.3 × 0.3 × 0.3 mm

Data collection
  • Siemens SMART three-axis goniometer with an APEXII area-detector system

  • 8643 measured reflections

  • 1853 independent reflections

  • 1002 reflections with I > 2σ(I)

  • Rint = 0.056

  • θmax = 36.2°

Refinement
  • R[F2 > 2σ(F2)] = 0.057

  • wR(F2) = 0.185

  • S = 1.00

  • 1853 reflections

  • 82 parameters

  • H-atom parameters constrained

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.18 e Å−3

Table 2
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
O2—H2⋯O1 1.07 1.61 2.6231 (18) 156
C3—H3⋯O1i 0.96 2.76 3.460 (2) 130
C7—H7⋯O1ii 0.96 2.73 3.443 (2) 132
C6—H6⋯O2iii 0.96 2.70 3.513 (2) 143
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) -x, -y+1, -z+1; (iii) x-1, y, z.

Compound (III)[link]

Crystal data
  • C9H8O

  • Mr = 132.15

  • Monoclinic, P 21 /c

  • a = 5.9626 (2) Å

  • b = 12.9977 (3) Å

  • c = 9.2522 (2) Å

  • β = 94.282 (2)°

  • V = 715.04 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 173 K

  • 0.3 × 0.3 × 0.3 mm

Data collection
  • Siemens SMART three-axis goniometer with an APEXII area-detector system

  • 7349 measured reflections

  • 1775 independent reflections

  • 1648 reflections with I > 2σ(I)

  • Rint = 0.023

  • θmax = 31.8°

Refinement
  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.125

  • S = 1.06

  • 1775 reflections

  • 92 parameters

  • H-atom parameters constrained

  • Δρmax = 0.28 e Å−3

  • Δρmin = −0.17 e Å−3

Table 3
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A DA D—H⋯A
C13—H13⋯O1i 0.96 2.81 3.5982 (18) 140
C14—H14⋯O1ii 0.96 2.63 3.304 (2) 128
C16—H16⋯O1iii 0.96 2.73 3.3880 (17) 126
Symmetry codes: (i) -x, -y+1, -z; (ii) x+1, y, z+1; (iii) [x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}].

H atoms of the meth­oxy group were idealized with tetra­hedral angles in a combined rotating and rigid-group refinement, with C—H = 0.97 Å and Uiso(H) = 1.5Ueq(C). All other C-bound H atoms were refined using a riding model starting from idealized geometries, with C—H = 0.96 Å and Uiso(H) = 1.2Ueq(C). The hy­droxy H-atom position in (II)[link] was taken from a Fourier map and also refined as a riding atom, with Uiso(H) = 1.5Ueq(O).

For all compounds, data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2 (Version 2.0-2) and SAINT (Version 7.34A). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2; data reduction: SAINT (Bruker, 2006[Bruker (2006). APEX2 (Version 2.0-2) and SAINT (Version 7.34A). Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: 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.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Experimental sophistication and developments in theoretical methodologies have improved the reliability of studies of weaker and lesser known intermolecular interactions (Desiraju & Steiner, 1999). As a result, weakly bound complexes such as those involving C—H···O interactions are being extensively studied, and the nature and strength of these interactions are being assessed. The formyl C—H···O hydrogen bond in small-molecule aldehydes is one such example. Many simple aldehydes are liquids, so not many structural reports are available for these compounds. Even if solid, there are not many crystal structure determinations for aldehydes. [37 simple aromatic aldehydes in the Cambridge Structural Database (CSD, Version?; Allen, 2002) with refcodes ANTHAL, AYOHAL, BARFOT, DEWLOH, DPEDAL, FATVUS, FAXXEI, FEDSAJ, FIXHIE, FIXHOK, FIYQOT, FOMZUD, FORBZA, HEQXOR, HODMAP, IHEMAJ, IHEMIR, IZALAW, JULZAR, KATKIA, KERKOI, LOSGOQ, MASBUD, NARZUC, OKUHEH, PHBALD10, RAJKOC, RAFJOC, SAZQIT, SOCHAT, SUNDUA, TEBBOR, WASLOS, XAMVUJ, XAMVEN, XAYCIJ and XIGWAM; four α,β-unsaturated aldehydes with refcodes JAZLAX, SIPKEH, WOBJOM and WOBJUS; and nine salicylaldehyde derivatives with refcodes KOYTOH, MAYWEO, NEJJOB, OVANIL, RAPLAW, XEVRUL, YIQYIH, YOMXOO and YOMXUU]. Therefore, we chose to investigate the nature and type of intermolecular interactions in the crystal structures of some very simple aldehydes.

Anisaldehyde (4-methoxybenzaldehyde), (I), salicylaldehyde (2-hydroxybenzaldehyde), (II), and cinnamaldehyde [(2E)-3-phenylprop-2-enal], (III), are liquids with melting points of 272, 266 and 265.5 K, respectively. These compounds are widely used in the chemical industry as intermediates in the preparation of perfumes, flavouring agents, dyes, pharmaceuticals and agrochemicals. The interesting feature of these compounds is that they do not possess any strong hydrogen-bonding functionalities. In salicylaldehyde, the OH group is bound intramolecularly to the aldehyde CO group. The possible intermolecular interactions in these three compounds are of the types Caryl—H···O, Cformyl—H···O, Csp2—H···O, Csp3—H···O, C—H···π and π···π. The formyl C—H···O interaction is known to be very weak, owing to the poor electropositive character of the formyl H atom (Breneman & Wiberg, 1990; Williams, 1988). Despite this, short Cformyl—H···O contacts are frequently observed in the crystal structures of aliphatic aldehydes (Thakur et al., 2011). The stabilizing nature of these Cformyl—H···O contacts has also been confirmed by computations on formaldehyde clusters; these calculations show a gradual increase in the electropositive nature of the formyl H atom on going from an isolated gas-phase environment to the crystal. X-ray crystallographic studies of aromatic aldehydes by Moorthy and Venugopalan also established that formyl C—H···O interactions are relevant to crystal packing (Moorthy et al., 2003, 2004, 2005; Lo Presti et al., 2006). However, in the case of aromatic aldehydes, the Cformyl—H···O interactions have to compete with Caryl—H···O interactions involving a relatively more acidic H atom. With our ongoing interest in the study of C—H···O hydrogen bonds in aldehydes we report here the crystal structures of (I), (II) and (III) (Fig. 1). Crystals were obtained in each case by means of in situ cryocrystallization.

Compound (I) crystallizes in space group P212121 with Z' = 1. The formyl and methoxy groups lie slightly out of the phenyl-ring plane by 4.3 (4) and -2.9 (3)°, respectively (torsion angles O1—C7—C1—C6 and C3—C4—O2—C8). The Caryl—Cformyl bond [1.455 (3) Å] is slightly shorter than a normal C—C single-bond distance (Standard reference?). This is possibly a result of extended conjugation between the aldehyde group and the aromatic ring. However, the non-coplanarity of the aromatic ring and the formyl group shows that this conjugation is not very pronounced. [This sentence is not consistent with the almost perfect coplanarity of the substituents with the ring, as indicated by the very small torsion angles mentioned a few lines above (4.3 deg. is NOT a very significant deviation from the plane). Please reconsider this statement about the conjugation.] There are several weak C—H···O hydrogen bonds (Table 1). Molecules are arranged in zigzag chains along the c axis and are held together by weak Csp3—H···O hydrogen bonds between atom H8A of the methoxy group and the carbonyl O atom of a neighbouring molecule. The chains are stacked along the a axis via weak Csp3—H···π interactions (Fig. 2a). Molecules in adjacent chains (along the b axis) are held together by weak Caryl—H···O interactions, C3—H3···O2i and C5—H5···O1ii (Fig. 2b; symmetry codes as in Table 1). The formyl H atom is not engaged in a directed intermolecular interaction (Ribeiro-Claro et al., 2002).

Compound (II) crystallizes in space group P21/c with Z' = 1. The hydroxy group is intramolecularly hydrogen-bonded to the formyl O atom (O2—H2···O1), as expected. A shorter Caryl—Cformyl bond [1.449 (2) Å] and a slightly elongated CO bond [1.230 (2) Å] are observed. Molecules in (II) are linked by weak Caryl—H···O hydrogen bonds (Table 2): C3—H3 and C6—H6 interact with the carbonyl O atom, O1, and hydroxy O atom, O6, respectively, of different neighbouring molecules (Fig. 3a). Additionally, a weak Cformyl—H···O interaction is also observed [C7—H7···O1(-x, 1-y, 1-z), Fig. 3b].

Compound (III) crystallizes in space group P21/c with Z' = 1. The propenal fragment lies out of the phenyl-ring plane by -9.36 (18)° (torsion angle C2—C3—C11—C12), with a Caryl—Csp2 bond length of 1.4656 (16) Å. This indicates poor resonance between the propenal fragment and the aromatic ring. The molecules are arranged in linear chains arranged in a head-to-tail fashion via C14—H14···O1(x + 1, y, z + 1) hydrogen bonds (Table 3, Fig. 4). The carbonyl O atom has weak C—H···O interactions with one Caryl—H group (C13—H13 or C16—H16) from each of two adjacent chains. Despite the high acidity of the Csp2—H group relative to the Caryl—H groups, no Csp2—H···O hydrogen bonds (between the carbonyl O atom and aliphatic fragment) are observed. However, such interactions have been observed frequently in the crystal structures of some substituted cinnamaldehydes (CSD refcodes CUBNUJ, LUJTEQ, CUBJUJ and QODVAH).

Related literature top

For related literature, see: Allen (2002); Boese & Nussbaumer (1994); Breneman & Wiberg (1990); Desiraju & Steiner (1999); Lo Presti, Soave & Destro (2006); Moorthy et al. (2003, 2004, 2005); Ribeiro-Claro, Drewbm & Félixa (2002); Thakur et al. (2011); Williams (1988).

Experimental top

Crystallization was performed on the diffractometer with a miniature zone-melting procedure using focused infrared laser radiation, according to Boese & Nussbaumer (1994). The respective temperatures of crystallization were 263 K for (I), 253 K for (II) (Fluka) and 248 K for (III) (Fluka, 98%, lot No. 1222882 24005132). The low coverage of the reflection data resulted from the orientation of the cylindrical crystal and the chosen scan mode, both due to the in situ crystal-growing technique. Any other mounting of the crystal or different scan mode would lead to melting of the crystals.

Refinement top

H atoms of the methoxy group were idealized with tetrahedral angles in a combined rotating and rigid-group refinement, with C—H = 0.97 Å and with Uiso(H) = 1.5Ueq(C). All other C-bound H atoms were refined using a riding model starting from idealized geometries, with C—H = 0.96 Å and with Uiso(H) = 1.2Ueq(C). [Please check added C–H distances] The hydroxy H-atom position in (II) was taken from a Fourier map and also refined as a riding atom, with Uiso(H) = 1.5Ueq(O).

Computing details top

For all compounds, data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 [or SAINT?] (Bruker, 2006); program(s) used to solve structure: APEX2 (Bruker, 2006); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The asymmetric units of the crystal structures of (I), (II) and (III). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The crystal packing in (I), with intermolecular interactions shown as thin lines. [Symmetry codes: (i) 1/2 + x, 1/2 - y, 1 - z; (ii) 1/2 + x, 1/2 - y, 1 - z [Please check - should be -x + 1/2, 1 - y, z + 1/2 ?]; (iii) 3/2 - x, -y, z - 1/2; (iv) 1/2 - x, -y, z - 1/2; (v) 2 - x, 1/2 + y, 3/2 - z.]
[Figure 3] Fig. 3. The crystal packing in (II). (a) View, down the c axis, showing the layers fromed by the Caryl—H···O interactions. (b) The Cformyl—H···O interactions between the molecules of adjacent layers. The interactions are shown as thin lines. [Symmetry codes: (i) 1 - x, y - 1/2, 3/2 - z; (ii) 2 - x, y - 1/2, 3/2 - z; (iii) -x, 1 - y, 1 - z.]
[Figure 4] Fig. 4. The crystal packing in (III), with intermolecular interactions shown as thin lines. [Symmetry codes: (i) -x, 1 - y , -z; (ii) -x - 1, 1 -y, -z - 1; (iii) -1 - x, 1/2 + y, -1/2 - z.]
(I) 4-methoxybenzaldehyde top
Crystal data top
C8H8O2F(000) = 288
Mr = 136.14Dx = 1.296 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 637 reflections
a = 4.970 (4) Åθ = 2.6–22.8°
b = 9.034 (9) ŵ = 0.09 mm1
c = 15.544 (14) ÅT = 203 K
V = 697.9 (11) Å3Cylinder, colourless
Z = 40.30 × 0.30 × 0.30 mm
Data collection top
Siemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
705 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.069
Graphite monochromatorθmax = 24.0°, θmin = 2.6°
Detector resolution: 512 pixels mm-1h = 33
Data collection strategy APEX 2/COSMO with chi = 0 scansk = 103
2015 measured reflectionsl = 1717
885 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.071 w = 1/[σ2(Fo2) + (0.0204P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max < 0.001
885 reflectionsΔρmax = 0.12 e Å3
92 parametersΔρmin = 0.13 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.012 (3)
Crystal data top
C8H8O2V = 697.9 (11) Å3
Mr = 136.14Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 4.970 (4) ŵ = 0.09 mm1
b = 9.034 (9) ÅT = 203 K
c = 15.544 (14) Å0.30 × 0.30 × 0.30 mm
Data collection top
Siemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
705 reflections with I > 2σ(I)
2015 measured reflectionsRint = 0.069
885 independent reflectionsθmax = 24.0°
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.071H-atom parameters constrained
S = 0.94Δρmax = 0.12 e Å3
885 reflectionsΔρmin = 0.13 e Å3
92 parameters
Special details top

Experimental. The crystallization was performed on the diffractometer at a temperature of 263 K with a miniature zone melting procedure using focused infrared-laser- radiation according to (Boese, 1994).

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. Treatment of hydrogen atoms Riding model on idealized geometrics with the 1.2 fold isotropic displacement parameters of the equivalent Uij of the corresponding carbon atom. The methyl groups are idealized with tetrahedral angles in a combined rotating and rigid group refinement with the 1.5 fold isotropic displacement parameters of the equivalent Uij of the corresponding carbon atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O11.0019 (4)0.0164 (2)0.53640 (11)0.0593 (6)
C70.8823 (5)0.0842 (3)0.48084 (15)0.0464 (8)
H70.92830.18670.47390.056*
C10.6769 (5)0.0255 (3)0.42348 (13)0.0369 (7)
C20.5485 (6)0.1195 (3)0.36659 (14)0.0422 (7)
H20.59880.22200.36640.051*
C30.3539 (6)0.0705 (2)0.30975 (14)0.0391 (8)
H30.26920.13830.27070.047*
C40.2870 (5)0.0793 (3)0.31038 (14)0.0347 (7)
C50.4129 (6)0.1759 (3)0.36761 (14)0.0414 (7)
H50.36310.27860.36850.050*
C60.6059 (6)0.1246 (3)0.42320 (13)0.0419 (7)
H60.69690.19150.46140.050*
O20.1022 (3)0.14176 (18)0.25731 (9)0.0455 (6)
C80.0230 (6)0.0499 (3)0.19443 (14)0.0498 (8)
H8A0.11290.00150.15960.075*
H8B0.13710.11020.15790.075*
H8C0.13150.02440.22320.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0564 (15)0.0673 (13)0.0530 (9)0.0061 (12)0.0073 (10)0.0009 (10)
C70.047 (2)0.0471 (17)0.0448 (14)0.0043 (15)0.0084 (13)0.0037 (13)
C10.0349 (19)0.0400 (14)0.0357 (12)0.0009 (13)0.0065 (12)0.0024 (12)
C20.048 (2)0.0338 (15)0.0450 (13)0.0046 (13)0.0095 (14)0.0012 (12)
C30.044 (2)0.0339 (14)0.0395 (13)0.0029 (14)0.0022 (13)0.0050 (11)
C40.032 (2)0.0390 (14)0.0336 (12)0.0008 (12)0.0030 (12)0.0072 (12)
C50.047 (2)0.0304 (14)0.0466 (14)0.0018 (13)0.0008 (14)0.0006 (12)
C60.048 (2)0.0380 (15)0.0392 (13)0.0052 (14)0.0028 (14)0.0024 (12)
O20.0449 (15)0.0435 (11)0.0481 (10)0.0000 (10)0.0052 (10)0.0025 (8)
C80.045 (2)0.0576 (16)0.0472 (13)0.0070 (15)0.0094 (12)0.0003 (14)
Geometric parameters (Å, º) top
O1—C71.214 (3)C4—O21.357 (3)
C7—C11.455 (3)C4—C51.394 (3)
C7—H70.9601C5—C61.372 (3)
C1—C21.382 (3)C5—H50.9600
C1—C61.402 (4)C6—H60.9600
C2—C31.383 (3)O2—C81.425 (3)
C2—H20.9600C8—H8A0.9700
C3—C41.394 (3)C8—H8B0.9700
C3—H30.9601C8—H8C0.9699
O1—C7—C1126.6 (3)C5—C4—C3120.3 (3)
O1—C7—H7116.8C6—C5—C4120.3 (2)
C1—C7—H7116.7C6—C5—H5119.8
C2—C1—C6118.4 (2)C4—C5—H5119.9
C2—C1—C7119.5 (2)C5—C6—C1120.3 (2)
C6—C1—C7122.1 (2)C5—C6—H6120.4
C3—C2—C1122.4 (2)C1—C6—H6119.2
C3—C2—H2119.3C4—O2—C8118.04 (19)
C1—C2—H2118.3O2—C8—H8A110.0
C2—C3—C4118.2 (2)O2—C8—H8B109.2
C2—C3—H3120.5H8A—C8—H8B109.5
C4—C3—H3121.3O2—C8—H8C109.2
O2—C4—C5115.5 (2)H8A—C8—H8C109.5
O2—C4—C3124.1 (2)H8B—C8—H8C109.5
O1—C7—C1—C2176.4 (2)O2—C4—C5—C6179.0 (2)
O1—C7—C1—C64.3 (4)C3—C4—C5—C60.7 (4)
C6—C1—C2—C30.1 (4)C4—C5—C6—C10.5 (4)
C7—C1—C2—C3179.3 (2)C2—C1—C6—C50.1 (4)
C1—C2—C3—C40.1 (4)C7—C1—C6—C5179.4 (2)
C2—C3—C4—O2179.19 (19)C5—C4—O2—C8176.8 (2)
C2—C3—C4—C50.5 (4)C3—C4—O2—C82.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O2i0.962.753.603 (4)149
C5—H5···O1ii0.962.703.447 (4)135
C8—H8A···O1iii0.972.713.582 (4)150
C8—H8B···O1iv0.972.753.434 (4)128
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x1/2, y+1/2, z+1; (iii) x+3/2, y, z1/2; (iv) x+1/2, y, z1/2.
(II) 2-hydroxybenzaldehyde top
Crystal data top
C7H6O2F(000) = 256
Mr = 122.12Dx = 1.356 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1182 reflections
a = 6.3945 (3) Åθ = 2.9–24.4°
b = 13.8939 (9) ŵ = 0.10 mm1
c = 6.9172 (4) ÅT = 233 K
β = 103.262 (3)°Cylinder, colourless
V = 598.17 (6) Å30.3 × 0.3 × 0.3 mm
Z = 4
Data collection top
Siemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
1002 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
Graphite monochromatorθmax = 36.2°, θmin = 2.9°
Detector resolution: 512 pixels mm-1h = 1010
Data collection strategy APEX2/COSMO with chi = 0 scansk = 1523
8643 measured reflectionsl = 55
1853 independent 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)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.185H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.1022P)2]
where P = (Fo2 + 2Fc2)/3
1853 reflections(Δ/σ)max < 0.001
82 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C7H6O2V = 598.17 (6) Å3
Mr = 122.12Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.3945 (3) ŵ = 0.10 mm1
b = 13.8939 (9) ÅT = 233 K
c = 6.9172 (4) Å0.3 × 0.3 × 0.3 mm
β = 103.262 (3)°
Data collection top
Siemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
1002 reflections with I > 2σ(I)
8643 measured reflectionsRint = 0.056
1853 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.185H-atom parameters constrained
S = 1.00Δρmax = 0.32 e Å3
1853 reflectionsΔρmin = 0.18 e Å3
82 parameters
Special details top

Experimental. The crystallization was performed on the diffractometer at a temperature of 253 K with a miniature zone melting procedure using focused infrared-laser- radiation according to (Boese, 1994).

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. Treatment of hydrogen atom: Riding model on idealized geometries with the 1.2 fold isotropic displacement parameters of the equivalent Uij of the corresponding carbon atom. Hydroxy hydrogen atom position taken from a Fourier-map and also refined as riding group with the 1.5 fold isotropic displacement parameters of the equivalent Uij of the corresponding hydroxy atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.2556 (2)0.54061 (8)0.6616 (2)0.0596 (5)
O20.55260 (18)0.67452 (9)0.7310 (2)0.0587 (5)
H20.46550.60800.70590.088*
C10.1738 (2)0.70760 (10)0.6451 (3)0.0341 (5)
C20.3892 (2)0.73841 (11)0.6956 (3)0.0389 (5)
C30.4344 (3)0.83638 (12)0.7087 (3)0.0490 (5)
H30.58110.85810.74320.059*
C40.2677 (3)0.90140 (12)0.6715 (3)0.0519 (6)
H40.29930.96920.68370.062*
C50.0553 (3)0.87229 (12)0.6211 (3)0.0491 (5)
H50.05890.91900.59330.059*
C60.0090 (2)0.77528 (12)0.6079 (3)0.0409 (5)
H60.13770.75350.57420.049*
C70.1222 (3)0.60588 (11)0.6320 (3)0.0452 (5)
H70.02710.58800.60260.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0661 (8)0.0368 (6)0.0743 (13)0.0031 (6)0.0129 (7)0.0033 (6)
O20.0340 (5)0.0593 (8)0.0783 (13)0.0071 (5)0.0041 (6)0.0058 (7)
C10.0350 (6)0.0342 (7)0.0327 (13)0.0043 (5)0.0068 (6)0.0015 (6)
C20.0334 (6)0.0428 (7)0.0394 (13)0.0023 (6)0.0060 (6)0.0009 (7)
C30.0465 (8)0.0491 (9)0.0501 (15)0.0159 (7)0.0084 (8)0.0032 (8)
C40.0702 (12)0.0345 (7)0.0515 (16)0.0090 (7)0.0154 (10)0.0020 (8)
C50.0559 (10)0.0405 (8)0.0514 (16)0.0080 (7)0.0134 (8)0.0015 (8)
C60.0349 (7)0.0446 (8)0.0418 (14)0.0011 (6)0.0062 (6)0.0008 (7)
C70.0488 (9)0.0392 (8)0.0474 (16)0.0069 (6)0.0109 (8)0.0003 (7)
Geometric parameters (Å, º) top
O1—C71.230 (2)C3—H30.9621
O2—C21.3499 (19)C4—C51.383 (3)
O2—H21.0726C4—H40.9637
C1—C61.392 (2)C5—C61.378 (2)
C1—C21.4075 (19)C5—H50.9628
C1—C71.449 (2)C6—H60.9620
C2—C31.390 (2)C7—H70.9618
C3—C41.375 (3)
C2—O2—H2100.7C3—C4—H4119.2
C6—C1—C2119.78 (13)C5—C4—H4118.8
C6—C1—C7119.68 (13)C6—C5—C4119.08 (16)
C2—C1—C7120.53 (14)C6—C5—H5120.3
O2—C2—C3119.43 (14)C4—C5—H5120.6
O2—C2—C1121.18 (14)C5—C6—C1120.43 (14)
C3—C2—C1119.40 (14)C5—C6—H6120.4
C4—C3—C2119.36 (15)C1—C6—H6119.2
C4—C3—H3120.6O1—C7—C1124.69 (15)
C2—C3—H3120.0O1—C7—H7117.5
C3—C4—C5121.94 (15)C1—C7—H7117.8
C6—C1—C2—O2179.50 (17)C3—C4—C5—C60.1 (3)
C7—C1—C2—O20.6 (3)C4—C5—C6—C10.1 (3)
C6—C1—C2—C30.4 (3)C2—C1—C6—C50.3 (3)
C7—C1—C2—C3179.50 (19)C7—C1—C6—C5179.58 (18)
O2—C2—C3—C4179.66 (19)C6—C1—C7—O1179.85 (19)
C1—C2—C3—C40.2 (3)C2—C1—C7—O10.3 (3)
C2—C3—C4—C50.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O11.071.612.6231 (18)156
C3—H3···O1i0.962.763.460 (2)130
C7—H7···O1ii0.962.733.443 (2)132
C6—H6···O2iii0.962.703.513 (2)143
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y+1, z+1; (iii) x1, y, z.
(III) (2E)-3-phenylprop-2-enal top
Crystal data top
C9H8OF(000) = 280
Mr = 132.15Dx = 1.228 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3800 reflections
a = 5.9626 (2) Åθ = 2.2–31.2°
b = 12.9977 (3) ŵ = 0.08 mm1
c = 9.2522 (2) ÅT = 173 K
β = 94.282 (2)°Cylinder, colourless
V = 715.04 (3) Å30.3 × 0.3 × 0.3 mm
Z = 4
Data collection top
Siemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
1648 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
Graphite monochromatorθmax = 31.8°, θmin = 2.7°
Detector resolution: 512 pixels mm-1h = 66
Data collection strategy APEX2/COSMO with chi = 0 scansk = 1518
7349 measured reflectionsl = 1313
1775 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.125 w = 1/[σ2(Fo2) + (0.0531P)2 + 0.1822P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1775 reflectionsΔρmax = 0.28 e Å3
92 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.014 (9)
Crystal data top
C9H8OV = 715.04 (3) Å3
Mr = 132.15Z = 4
Monoclinic, P21/cMo Kα radiation
a = 5.9626 (2) ŵ = 0.08 mm1
b = 12.9977 (3) ÅT = 173 K
c = 9.2522 (2) Å0.3 × 0.3 × 0.3 mm
β = 94.282 (2)°
Data collection top
Siemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
1648 reflections with I > 2σ(I)
7349 measured reflectionsRint = 0.023
1775 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.125H-atom parameters constrained
S = 1.06Δρmax = 0.28 e Å3
1775 reflectionsΔρmin = 0.17 e Å3
92 parameters
Special details top

Experimental. The crystallization was performed on the diffractometer at a temperature of 248 K with a miniature zone melting procedure using focused infrared-laser- radiation according to (Boese, 1994).

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. Treatment of hydrogen atoms Riding model on idealized geometrics with the 1.2 fold isotropic displacement parameters of the equivalent Uij of the corresponding carbon atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.0048 (2)0.36499 (9)0.40008 (12)0.0603 (4)
C10.1694 (3)0.35814 (9)0.32532 (14)0.0415 (4)
H10.30330.34240.37260.050*
C20.1944 (2)0.37243 (9)0.16888 (13)0.0375 (3)
H20.06540.38990.11770.045*
C30.3937 (2)0.36146 (8)0.09649 (12)0.0331 (3)
H30.51540.34300.15360.040*
C110.4498 (2)0.37396 (8)0.05945 (12)0.0315 (3)
C120.2969 (2)0.41471 (9)0.15176 (13)0.0362 (3)
H120.14990.43510.11280.043*
C130.3560 (3)0.42581 (10)0.29890 (14)0.0413 (4)
H130.24960.45370.36130.050*
C140.5676 (3)0.39691 (10)0.35563 (14)0.0404 (4)
H140.60600.40440.45770.048*
C150.7210 (2)0.35616 (10)0.26582 (14)0.0393 (3)
H150.86900.33700.30450.047*
C160.6614 (2)0.34481 (9)0.11886 (13)0.0355 (3)
H160.76660.31580.05660.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0558 (9)0.0722 (7)0.0496 (6)0.0015 (5)0.0178 (6)0.0016 (5)
C10.0460 (11)0.0380 (6)0.0396 (6)0.0018 (5)0.0021 (6)0.0014 (5)
C20.0351 (10)0.0402 (6)0.0370 (6)0.0001 (5)0.0011 (6)0.0008 (4)
C30.0333 (9)0.0299 (5)0.0360 (6)0.0008 (4)0.0030 (5)0.0009 (4)
C110.0303 (9)0.0282 (5)0.0360 (5)0.0027 (4)0.0024 (5)0.0007 (4)
C120.0303 (9)0.0382 (6)0.0400 (6)0.0008 (5)0.0021 (5)0.0017 (4)
C130.0397 (10)0.0460 (6)0.0389 (6)0.0034 (5)0.0074 (6)0.0053 (5)
C140.0424 (10)0.0433 (6)0.0352 (6)0.0074 (5)0.0005 (6)0.0016 (5)
C150.0324 (9)0.0425 (6)0.0420 (6)0.0029 (5)0.0031 (6)0.0059 (5)
C160.0298 (9)0.0367 (6)0.0402 (6)0.0005 (5)0.0034 (5)0.0017 (4)
Geometric parameters (Å, º) top
O1—C11.2078 (18)C12—C131.3881 (18)
C1—C21.4559 (17)C12—H120.9600
C1—H10.9600C13—C141.382 (2)
C2—C31.3270 (19)C13—H130.9600
C2—H20.9600C14—C151.3858 (19)
C3—C111.4656 (16)C14—H140.9600
C3—H30.9599C15—C161.3872 (17)
C11—C161.3907 (19)C15—H150.9600
C11—C121.3993 (16)C16—H160.9600
O1—C1—C2125.44 (14)C11—C12—H12119.6
O1—C1—H1117.6C14—C13—C12120.13 (12)
C2—C1—H1116.9C14—C13—H13120.0
C3—C2—C1120.62 (12)C12—C13—H13119.9
C3—C2—H2119.8C13—C14—C15120.05 (12)
C1—C2—H2119.6C13—C14—H14119.3
C2—C3—C11127.96 (11)C15—C14—H14120.6
C2—C3—H3115.7C16—C15—C14119.75 (13)
C11—C3—H3116.3C16—C15—H15119.9
C16—C11—C12118.38 (11)C14—C15—H15120.4
C16—C11—C3119.53 (11)C15—C16—C11121.11 (11)
C12—C11—C3122.10 (12)C15—C16—H16120.0
C13—C12—C11120.57 (13)C11—C16—H16118.9
C13—C12—H12119.8
O1—C1—C2—C3178.87 (12)C11—C12—C13—C140.23 (19)
C1—C2—C3—C11179.26 (10)C12—C13—C14—C150.40 (19)
C2—C3—C11—C16170.73 (11)C13—C14—C15—C160.20 (19)
C2—C3—C11—C129.36 (18)C14—C15—C16—C110.18 (18)
C16—C11—C12—C130.14 (17)C12—C11—C16—C150.35 (17)
C3—C11—C12—C13179.77 (11)C3—C11—C16—C15179.57 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O1i0.962.813.5982 (18)140
C14—H14···O1ii0.962.633.304 (2)128
C16—H16···O1iii0.962.733.3880 (17)126
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z+1; (iii) x+1, y+1/2, z+1/2.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC8H8O2C7H6O2C9H8O
Mr136.14122.12132.15
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21/cMonoclinic, P21/c
Temperature (K)203233173
a, b, c (Å)4.970 (4), 9.034 (9), 15.544 (14)6.3945 (3), 13.8939 (9), 6.9172 (4)5.9626 (2), 12.9977 (3), 9.2522 (2)
α, β, γ (°)90, 90, 9090, 103.262 (3), 9090, 94.282 (2), 90
V3)697.9 (11)598.17 (6)715.04 (3)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.090.100.08
Crystal size (mm)0.30 × 0.30 × 0.300.3 × 0.3 × 0.30.3 × 0.3 × 0.3
Data collection
DiffractometerSiemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
Siemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
Siemens SMART three-axis goniometer with APEXII area-detector system
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2015, 885, 705 8643, 1853, 1002 7349, 1775, 1648
Rint0.0690.0560.023
θmax (°)24.036.231.8
(sin θ/λ)max1)0.5720.8320.742
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.071, 0.94 0.057, 0.185, 1.00 0.050, 0.125, 1.06
No. of reflections88518531775
No. of parameters928292
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.12, 0.130.32, 0.180.28, 0.17

Computer programs: APEX2 (Bruker, 2006), APEX2 [or SAINT?] (Bruker, 2006), SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O2i0.962.753.603 (4)148.9
C5—H5···O1ii0.962.703.447 (4)135.3
C8—H8A···O1iii0.972.713.582 (4)149.8
C8—H8B···O1iv0.972.753.434 (4)127.8
Symmetry codes: (i) x, y1/2, z+1/2; (ii) x1/2, y+1/2, z+1; (iii) x+3/2, y, z1/2; (iv) x+1/2, y, z1/2.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O11.071.612.6231 (18)155.9
C3—H3···O1i0.962.763.460 (2)129.9
C7—H7···O1ii0.962.733.443 (2)131.6
C6—H6···O2iii0.962.703.513 (2)142.6
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y+1, z+1; (iii) x1, y, z.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O1i0.962.813.5982 (18)140.0
C14—H14···O1ii0.962.633.304 (2)127.5
C16—H16···O1iii0.962.733.3880 (17)126.2
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z+1; (iii) x+1, y+1/2, z+1/2.
 

Acknowledgements

TST thanks the Indian Institute of Science for a postdoctoral fellowship. MTK, DB and RB thank the DFG (grant No. FOR-618). GRD thanks the DST for the award of a J. C. Bose fellowship.

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