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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 10| October 2012| Pages o2991-o2992
https://doi.org/10.1107/S1600536812039736

2-{3-Cyano-4-[2-(4-di­ethylamino-2-hy­droxyphenyl)ethenyl]-5,5-di­methyl-2,5-di­hydro­furan-2-yl­idene}malono­nitrile acetone 0.25-solvate

Graeme J. Gainsford,a* Mohamed Ashrafa and Andrew J. Kaya

aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 31 August 2012; accepted 18 September 2012; online 26 September 2012)

In the title compound, C22H22N4O2·0.25C3H6O, the disordered acetone mol­ecule lies with partial occupancy about the 2 axis. The mol­ecule of the malononitrile derivative is essentially planar excluding the methyl groups, with the largest deviation from the mean plane through the non-H atoms being 0.1955 (13) Å. Two rotamers with different orientations of the benzene ring are observed in the ratio of 0.919 (2):0.081 (2), and as a result the OH group is disordered over two sets of sites. In the crystal, the mol­ecules form ribbons along (101) utilizing a strong O—H⋯N(cyano) hydrogen bond. Inter­leaving of the nearly planar ribbons is provided by the twofold disordered acetone molecule through C—H⋯O inter­actions.

Related literature

For organic push–pull conjugated molecules in electro-optical applications, see: Dalton (2004[Dalton, L. R. (2004). Pure Appl. Chem. 76, 1421-1433.]); Ma et al. (2002[Ma, H., Jen, A. K.-Y. & Dalton, L. R. (2002). Adv. Mater. 14, 1339-1365.]); Marder et al. (1997[Marder, S. R., Kippelen, B., Jen, A. K.-Y. & Peyghambarian, N. (1997). Nature (London), 388, 845-851.]); Li et al. (2007[Li, Z., Li, M., Zhou, X. P., Wu, T., Li, D. & Ng, S. W. (2007). Cryst. Growth Des. 7, 1992-1998.]); Avetisyan et al. (2009[Avetisyan, A. A., Alvandzhyan, A. G. & Avetisyan, K. S. (2009). Russ. J. Org. Chem. 45, 1871-1872.]); Gainsford et al. (2008[Gainsford, G. J., Bhuiyan, M. D. H. & Kay, A. J. (2008). Acta Cryst. C64, o616-o619.]). For related structures, see: Li et al. (2009[Li, S., Li, M., Qin, J., Tong, M., Chen, X., Liu, T., Fu, Y. & Su, Z. (2009). CrystEngComm, 11, 589-596.]); Wu et al. (2012[Wu, J., Liu, J., Zhou, T., Bo, S., Qiu, L., Zhen, Z. & Liu, X. (2012). RSC Advances, 2, 1416-1423.]). For the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data

  • 4C22H22N4O2·C3H6O

  • Mr = 1555.82

  • Monoclinic, C 2/c

  • a = 18.6899 (6) Å

  • b = 14.4941 (4) Å

  • c = 16.7485 (5) Å

  • β = 95.266 (2)°

  • V = 4517.9 (2) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 113 K

  • 0.61 × 0.53 × 0.33 mm
Data collection

  • Bruker-Nonius APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.678, Tmax = 0.746

  • 51842 measured reflections

  • 6086 independent reflections

  • 4957 reflections with I > 2σ(I)

  • Rint = 0.033
Refinement

  • R[F2 > 2σ(F2)] = 0.047

  • wR(F2) = 0.138

  • S = 1.04

  • 6089 reflections

  • 289 parameters

  • 5 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.44 e Å−3

  • Δρmin = −0.34 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O2A—H2OA⋯N1i 0.88 (2) 1.96 (2) 2.8095 (16) 162 (2)
C17—H17⋯O3 0.95 2.37 3.213 (13) 148
C17—H17⋯O3ii 0.95 2.51 3.324 (13) 144
Symmetry codes: (i) [x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) [-x+1, y, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT and SADABS (Bruker, 2005[Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) 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.]); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812039736/yk2072sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812039736/yk2072Isup2.hkl

checkCIF report


Comment top

Organic donor–π-acceptor (D–π-A) molecules show much promise due to their potential application in areas such as photonics, optical power limiting and optical data storage (Dalton, 2004; Ma et al., 2002). These molecules are typically push–pull conjugated systems that can be modified by altering either the donor, acceptor or conjugated interconnect moieties. Consequently, there are typically a number of options available to iteratively improve the overall molecular response and stability of such compounds, especially when applied to their use in second-order nonlinear optics. For example, a successful approach to optimizing their second-order nonlinear optical (NLO) response is based on tuning the ground-state polarization - and hence the degree of bond-length alternation - through modification of the end groups and the spacer (Marder et al., 1997). Furthermore, thermal and photochemical stability can be improved through the use of ring-locked spacer units between the donor–acceptor moieties. However, in order to be successfully deployed in devices the chromophores need to be embedded into a polymer and their dipoles aligned in a non-centrosymmetric fashion using a process known as poling. This can be difficult to achieve as NLO chromophores embedded in polymer matrices have a tendency to aggregate due to their large dipole moments. As a result there is often a need to find expedient methods to minimize aggregation in NLO chromophores and these include the use of bulky fluorinated and non-fluorinated pendant groups as well as the use of hydrogen-bonding substituents to control the molecular interactions.

Studies of hydrogen bonds connecting organic and organic–inorganic compounds have long been a topic of intense research in crystal engineering because this allows not only for a rational approach to bottom-up construction but hydrogen bonds also effectively regulate the molecular architecture (Li et al., 2007). With this in mind, and in line with our on-going work on the development of novel organic NLO compounds, we sought a straightforward route to a D–π-A molecule containing a hydroxyl substituent to allow us to study its impact on crystal packing, as well as providing a potentially reactive site for future modifications. Consequently, we prepared the title compound 3 using the method outlined in Fig. 1. This involved the condensation of 5-diethylaminosalicylaldehyde (1) with 2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-malononitrile 2 and provided the title compound in an 80% yield. Compound 2 was prepared by the general procedure reported in the literature (Avetisyan et al., 2009).

Compound REFCODES are from the C.S.D. (Version 5.33, with May 2012 updates; Allen, 2002). The molecule is rotationally disordered about the C12—C13 bond in the ratio of 0.919 (2):0.081 (2) as determined by refining of the O2—H atoms over two positions with restraints (see experimental). Refinement of the remaining rotamer atoms was not practical at the ~8% level. The asymmetric unit contents of the major rotamer of the title compound (I) are shown in Fig. 2.

The 5-membered ring plane of atoms O1,C4–C7 (hereafter `CDFP', [3-cyano-5,5-dimethyl-2,5-dihydrofuran-2-ylidene]propanedinitrile) is planar with maximum out of plane deviation for O1 of 0.003 (1) Å. The dicyano group (N1,C1,C2,C3,N2,C6) is planar but twisted by 5.46 (6)° with respect to the `CDFP' group as been found in previous studies e.g. 5.69 (17)° in compound NOJKUT (Gainsford et al., 2008). The entire `backbone' including the hydroxyl atom O2 and C2 but excluding the ethyl and methyl atoms (C8,C9,C19–C22) and the dicyano groups can be considered essentially planar with average mean plane deviation 0.019 (1) Å and maximum deviation 0.027 (1) Å for C11. This is in marked contrast to the related benzoyloxy structure KARXAE (Wu et al., 2012) ((4-(2(2-Benzoyloxy)-4-(diethylamino)phenyl)vinyl)-3-cyano-5,5 -dimethylfuran-2(5H)-ylidene) malonitrile), where the CDFP and (diethylamino)phenyl groups make interplanar angles of ~10°. The difference probably relates to the different crystal packing arrangements, as noted below, but this twist also alleviates potential close contacts between the methylene group of the benzoyloxy group and the pendant nearest ethyl group. The pendant ethyl groups in KARXAE are also in the opposite configurations, with the nearest ethyl group pointing away from the benzoyloxy moiety. The acetone molecule is disordered around a 2 fold axis, and the final concentration was decided by a thermal parameter comparison with the other atoms and confirmed by a stable final refinement.

One other related structure, without the ortho oxygen substituent at C15, is NUGNUZ (Li et al., 2009). Here the backbone is twisted along its length, with ~7° between CDFP and the polyene atoms, and a further ~ 8° between the latter and the (diethylamino)phenyl group. This twisting is probably driven by the intermolecular hydrogen bonding interactions which involve one of the polyene H atoms (to the terminal alcohol O) and a phenyl C—H···N(cyano) contact.

The crystal packing can be described as interleaved ribbons of molecules, approximately in the 1,0,1 direction, formed by the major almost in-plane hydrogen bonding (entry 1, Table 1 and Figure 3). The alternate ribbon molecule planes make a dihedral angle of ~15°. The interplanar interactions are provided by weak C—H···O(acetone) interactions (entries 2 and 3, Table 1). Given this weak interaction (and the estimated 0.25 concentration of the acetone), it is not surprising that rotational conformers are present. By contrast the packing in related structure KARXAE is a traditional herringbone pattern, with ~39° between the molecular planes; here the single weak C—H···N(cyano) and (methylene)C–H···π are sufficient for the crystal packing stability.

Related literature top

For general background, see: Dalton (2004); Ma et al. (2002); Marder et al. (1997); Li et al. (2007); Avetisyan et al. (2009); Gainsford et al. (2008). For related structures, see: Li et al. (2009); Wu et al. (2012). For the Cambridge Structural Database, see: Allen (2002).

Experimental top

To a stirred solution of 5-diethylaminosalicyladehyde 1 (0.97 g, 5 mmol) in methanol was added compound 2 (0.99 g, 5 mmol) (Fig. 1). Two drops of triethylamine were then added and the mixture was then refluxed for 6 h, by which time its colour had changed to deep violet. The solid formed was filtered and purified by recrystallization from ethanol to give the titled compound 3 as a violet solid (1.49 g, 80% yield). X-ray quality crystals were grown by slow evaporation from acetone. m.p. 223.8°C. 1H NMR (500 MHz, DMSO): δ 10.80 (s, 1H), 8.21 (d, 1H, J 15 Hz), 7.69 (d, 1H, J 10 Hz), 6.94 (d, 1H, J 15 Hz), 6.45 (d, 1H, J 10 Hz), 6.17 (s, 1H), 3.45 (q, 4H), 1.70 (s, 6H), 1.16 (t, 6H). 13C NMR (75 MHz, CDCl3): δ 177.50, 175.32, 162.21, 154.08, 145.02, 114.03, 113.16, 112.79, 111.99, 107.02, 106.77, 97.18, 96.50, 48.80, 44.54, 25.93, 12.65. LCMS Found: MNa+ 397.1643; C22H22N4O2Na requires MNa+ 397.1640; Δ = 0.8 p.p.m.

Refinement top

The molecule is rotationally disordered about the C12—C13 bond in the ratio of 0.919 (2):0.081 (2) as determined by refining the O2—H atoms over two positions with identical thermal parameters (EADP). Four further restraints were applied to the minor rotamer atoms with C18—O2B and O2B—H2B fixed at 1.340 (5) and 0.84 (1) Å respectively, and two antibumping restraints tied to the equivalent major rotamer distances (using SADI). The final residual difference density is consistent with this ~8% presence for the remaining atoms in the rotated group; their refinement is impractical and would add nothing to the final conclusions.

Four reflections affected by the backstop and 16 others, which were clearly outlier data (mostly at low angle) with Δ(F2)/e.s.d. > 5.0, were omitted from the refinements (using OMIT). The methyl and other H atoms were refined with Uiso 1.5 and 1.2 times respectively that of the Ueq of their parent atom. The hydroxyl hydrogen on major rotamer O2A was located on a difference Fourier map and its position refined. The hydroxyl hydrogen bound to the (8%) O2B atom was located via an HFIX 147 tetrahedral position refinement and refined as noted above. All H atoms bound to carbon were constrained to their expected geometries (C—H 0.95, 0.98 and 0.99 Å).

Structure description top

Organic donor–π-acceptor (D–π-A) molecules show much promise due to their potential application in areas such as photonics, optical power limiting and optical data storage (Dalton, 2004; Ma et al., 2002). These molecules are typically push–pull conjugated systems that can be modified by altering either the donor, acceptor or conjugated interconnect moieties. Consequently, there are typically a number of options available to iteratively improve the overall molecular response and stability of such compounds, especially when applied to their use in second-order nonlinear optics. For example, a successful approach to optimizing their second-order nonlinear optical (NLO) response is based on tuning the ground-state polarization - and hence the degree of bond-length alternation - through modification of the end groups and the spacer (Marder et al., 1997). Furthermore, thermal and photochemical stability can be improved through the use of ring-locked spacer units between the donor–acceptor moieties. However, in order to be successfully deployed in devices the chromophores need to be embedded into a polymer and their dipoles aligned in a non-centrosymmetric fashion using a process known as poling. This can be difficult to achieve as NLO chromophores embedded in polymer matrices have a tendency to aggregate due to their large dipole moments. As a result there is often a need to find expedient methods to minimize aggregation in NLO chromophores and these include the use of bulky fluorinated and non-fluorinated pendant groups as well as the use of hydrogen-bonding substituents to control the molecular interactions.

Studies of hydrogen bonds connecting organic and organic–inorganic compounds have long been a topic of intense research in crystal engineering because this allows not only for a rational approach to bottom-up construction but hydrogen bonds also effectively regulate the molecular architecture (Li et al., 2007). With this in mind, and in line with our on-going work on the development of novel organic NLO compounds, we sought a straightforward route to a D–π-A molecule containing a hydroxyl substituent to allow us to study its impact on crystal packing, as well as providing a potentially reactive site for future modifications. Consequently, we prepared the title compound 3 using the method outlined in Fig. 1. This involved the condensation of 5-diethylaminosalicylaldehyde (1) with 2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-malononitrile 2 and provided the title compound in an 80% yield. Compound 2 was prepared by the general procedure reported in the literature (Avetisyan et al., 2009).

Compound REFCODES are from the C.S.D. (Version 5.33, with May 2012 updates; Allen, 2002). The molecule is rotationally disordered about the C12—C13 bond in the ratio of 0.919 (2):0.081 (2) as determined by refining of the O2—H atoms over two positions with restraints (see experimental). Refinement of the remaining rotamer atoms was not practical at the ~8% level. The asymmetric unit contents of the major rotamer of the title compound (I) are shown in Fig. 2.

The 5-membered ring plane of atoms O1,C4–C7 (hereafter `CDFP', [3-cyano-5,5-dimethyl-2,5-dihydrofuran-2-ylidene]propanedinitrile) is planar with maximum out of plane deviation for O1 of 0.003 (1) Å. The dicyano group (N1,C1,C2,C3,N2,C6) is planar but twisted by 5.46 (6)° with respect to the `CDFP' group as been found in previous studies e.g. 5.69 (17)° in compound NOJKUT (Gainsford et al., 2008). The entire `backbone' including the hydroxyl atom O2 and C2 but excluding the ethyl and methyl atoms (C8,C9,C19–C22) and the dicyano groups can be considered essentially planar with average mean plane deviation 0.019 (1) Å and maximum deviation 0.027 (1) Å for C11. This is in marked contrast to the related benzoyloxy structure KARXAE (Wu et al., 2012) ((4-(2(2-Benzoyloxy)-4-(diethylamino)phenyl)vinyl)-3-cyano-5,5 -dimethylfuran-2(5H)-ylidene) malonitrile), where the CDFP and (diethylamino)phenyl groups make interplanar angles of ~10°. The difference probably relates to the different crystal packing arrangements, as noted below, but this twist also alleviates potential close contacts between the methylene group of the benzoyloxy group and the pendant nearest ethyl group. The pendant ethyl groups in KARXAE are also in the opposite configurations, with the nearest ethyl group pointing away from the benzoyloxy moiety. The acetone molecule is disordered around a 2 fold axis, and the final concentration was decided by a thermal parameter comparison with the other atoms and confirmed by a stable final refinement.

One other related structure, without the ortho oxygen substituent at C15, is NUGNUZ (Li et al., 2009). Here the backbone is twisted along its length, with ~7° between CDFP and the polyene atoms, and a further ~ 8° between the latter and the (diethylamino)phenyl group. This twisting is probably driven by the intermolecular hydrogen bonding interactions which involve one of the polyene H atoms (to the terminal alcohol O) and a phenyl C—H···N(cyano) contact.

The crystal packing can be described as interleaved ribbons of molecules, approximately in the 1,0,1 direction, formed by the major almost in-plane hydrogen bonding (entry 1, Table 1 and Figure 3). The alternate ribbon molecule planes make a dihedral angle of ~15°. The interplanar interactions are provided by weak C—H···O(acetone) interactions (entries 2 and 3, Table 1). Given this weak interaction (and the estimated 0.25 concentration of the acetone), it is not surprising that rotational conformers are present. By contrast the packing in related structure KARXAE is a traditional herringbone pattern, with ~39° between the molecular planes; here the single weak C—H···N(cyano) and (methylene)C–H···π are sufficient for the crystal packing stability.

For general background, see: Dalton (2004); Ma et al. (2002); Marder et al. (1997); Li et al. (2007); Avetisyan et al. (2009); Gainsford et al. (2008). For related structures, see: Li et al. (2009); Wu et al. (2012). For the Cambridge Structural Database, see: Allen (2002).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT and SADABS (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) 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. Chemical synthesis of the title compound 3.
[Figure 2] Fig. 2. Structure of the asymmetric unit (Farrugia, 1997) showing the atom labelling scheme and displacement ellipsoids drawn at the 30% probability level. Only the major rotamer atom (O2A) is shown (see text).
[Figure 3] Fig. 3. Packing diagram (Macrae et al., 2008) of the unit cell. H atoms excluded for clarity. Disordered acetone and H bonding atoms shown as balls. Close contacts indicated by dotted lines identify the key H bond (see text). Symmetry (i) -1/2 + x, -1/2 - y, -1/2 + z (ii) 1/2 + x, -1/2 - y, 1/2 + z.
2-{3-Cyano-4-[2-(4-diethylamino-2-hydroxyphenyl)ethenyl]-5,5-dimethyl- 2,5-dihydrofuran-2-ylidene}malononitrile acetone 0.25-solvate top
Crystal data top
4C22H22N4O2·C3H6OF(000) = 1648
Mr = 1555.82Dx = 1.144 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 9270 reflections
a = 18.6899 (6) Åθ = 2.2–29.2°
b = 14.4941 (4) ŵ = 0.08 mm−1
c = 16.7485 (5) ÅT = 113 K
β = 95.266 (2)°Block, violet
V = 4517.9 (2) Å30.61 × 0.53 × 0.33 mm
Z = 2
Data collection top
Bruker-Nonius APEXII CCD
diffractometer		6086 independent reflections
Radiation source: fine-focus sealed tube4957 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 8.333 pixels mm-1θmax = 29.3°, θmin = 2.4°
φ and ω scansh = −25→25
Absorption correction: multi-scan
(SADABS; Blessing, 1995)		k = −19→19
Tmin = 0.678, Tmax = 0.746l = −22→23
51842 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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0684P)2 + 3.4092P]
where P = (Fo2 + 2Fc2)/3
6089 reflections(Δ/σ)max < 0.001
289 parametersΔρmax = 0.44 e Å−3
5 restraintsΔρmin = −0.34 e Å−3
Crystal data top
4C22H22N4O2·C3H6OV = 4517.9 (2) Å3
Mr = 1555.82Z = 2
Monoclinic, C2/cMo Kα radiation
a = 18.6899 (6) ŵ = 0.08 mm−1
b = 14.4941 (4) ÅT = 113 K
c = 16.7485 (5) Å0.61 × 0.53 × 0.33 mm
β = 95.266 (2)°
Data collection top
Bruker-Nonius APEXII CCD
diffractometer		6086 independent reflections
Absorption correction: multi-scan
(SADABS; Blessing, 1995)		4957 reflections with I > 2σ(I)
Tmin = 0.678, Tmax = 0.746Rint = 0.033
51842 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0475 restraints
wR(F2) = 0.138H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.44 e Å−3
6089 reflectionsΔρmin = −0.34 e Å−3
289 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*/UeqOcc. (<1)
O10.61544 (5)−0.22668 (6)0.49734 (5)0.02549 (19)
N10.74054 (7)−0.33495 (9)0.63481 (7)0.0354 (3)
N20.81037 (8)−0.05230 (10)0.62647 (10)0.0519 (4)
N40.28556 (6)0.21599 (9)0.17128 (7)0.0337 (3)
N30.67592 (6)0.09283 (8)0.51591 (7)0.0342 (3)
C10.72855 (6)−0.26329 (9)0.60753 (7)0.0263 (2)
C20.71622 (6)−0.17294 (9)0.57628 (7)0.0238 (2)
C30.76699 (7)−0.10418 (10)0.60298 (8)0.0318 (3)
C40.56689 (6)−0.09065 (8)0.43879 (6)0.0200 (2)
C50.62913 (6)−0.07176 (8)0.48837 (6)0.0204 (2)
C60.65688 (6)−0.15572 (8)0.52307 (6)0.0211 (2)
C70.55438 (6)−0.19392 (8)0.44206 (7)0.0216 (2)
C80.56100 (7)−0.24283 (9)0.36256 (7)0.0285 (3)
H8A0.5624−0.30970.37130.043*
H8B0.6053−0.22310.34050.043*
H8C0.5196−0.22720.32480.043*
C90.48701 (7)−0.22100 (9)0.48084 (8)0.0286 (3)
H9A0.4870−0.19050.53310.043*
H9B0.4862−0.28810.48820.043*
H9C0.4445−0.20190.44630.043*
C100.65681 (6)0.01838 (8)0.50443 (7)0.0237 (2)
C110.52475 (6)−0.02424 (8)0.39539 (6)0.0215 (2)
H110.54090.03790.39890.026*
C120.46183 (6)−0.04148 (8)0.34801 (6)0.0206 (2)
H120.4463−0.10380.34410.025*
C130.41816 (6)0.02472 (8)0.30455 (6)0.0198 (2)
C140.35532 (6)−0.00359 (8)0.25653 (7)0.0229 (2)
H140.3431−0.06720.25440.027*0.081 (2)
O2A0.34030 (5)−0.09416 (7)0.25497 (6)0.0295 (3)0.919 (2)
H2A0.3035 (10)−0.1063 (13)0.2199 (11)0.035*0.919 (2)
C150.31146 (6)0.05859 (9)0.21287 (7)0.0273 (3)
H150.26960.03710.18200.033*
C160.32793 (7)0.15364 (9)0.21348 (7)0.0268 (3)
C170.39137 (7)0.18304 (9)0.26073 (7)0.0270 (2)
H170.40440.24640.26200.032*
C180.43327 (6)0.12048 (8)0.30389 (7)0.0230 (2)
H180.47480.14220.33520.028*0.919 (2)
O2B0.4814 (5)0.1629 (7)0.3528 (6)0.0295 (3)0.081 (2)
H2B0.5066 (16)0.203 (3)0.333 (3)0.035*0.081 (2)
C190.22046 (8)0.18697 (11)0.12259 (8)0.0385 (3)
H19A0.22970.12750.09630.046*
H19B0.20850.23330.08000.046*
C200.15686 (8)0.17596 (13)0.17183 (11)0.0464 (4)
H20A0.14590.23540.19580.070*
H20B0.16850.13060.21440.070*
H20C0.11500.15480.13710.070*
C210.30658 (8)0.31313 (10)0.16457 (9)0.0357 (3)
H21A0.32800.33530.21740.043*
H21B0.26340.35080.14900.043*
C220.36029 (10)0.32545 (13)0.10298 (10)0.0483 (4)
H22A0.34070.29920.05170.072*
H22B0.40520.29380.12130.072*
H22C0.36980.39130.09620.072*
O30.4975 (9)0.3578 (3)0.2641 (9)0.086 (2)0.25
C230.50000.5166 (6)0.25000.105 (3)0.50
H23A0.51910.50350.19860.158*0.25
H23B0.53590.55070.28470.158*0.25
H23C0.45620.55370.24080.158*0.25
C240.4839 (5)0.4325 (6)0.2875 (7)0.086 (2)0.25
C250.4474 (5)0.4443 (6)0.3616 (8)0.086 (2)0.25
H25A0.44380.38450.38820.129*0.25
H25B0.39910.46930.34800.129*0.25
H25C0.47510.48710.39770.129*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0254 (4)0.0211 (4)0.0284 (4)0.0027 (3)−0.0068 (3)0.0028 (3)
N10.0359 (6)0.0361 (6)0.0331 (6)0.0097 (5)−0.0033 (5)0.0076 (5)
N20.0411 (7)0.0437 (8)0.0659 (9)−0.0064 (6)−0.0213 (7)0.0056 (7)
N40.0316 (6)0.0376 (6)0.0307 (5)0.0118 (5)−0.0044 (4)0.0062 (5)
N30.0336 (6)0.0286 (6)0.0386 (6)−0.0030 (5)−0.0059 (5)−0.0012 (5)
C10.0230 (5)0.0330 (6)0.0222 (5)0.0067 (5)−0.0020 (4)0.0023 (5)
C20.0210 (5)0.0278 (6)0.0219 (5)0.0045 (4)−0.0020 (4)0.0028 (4)
C30.0266 (6)0.0335 (7)0.0335 (6)0.0049 (5)−0.0076 (5)0.0047 (5)
C40.0189 (5)0.0216 (5)0.0191 (5)0.0020 (4)−0.0009 (4)0.0001 (4)
C50.0185 (5)0.0218 (5)0.0202 (5)0.0024 (4)−0.0021 (4)0.0008 (4)
C60.0201 (5)0.0231 (5)0.0200 (5)0.0033 (4)0.0003 (4)0.0008 (4)
C70.0200 (5)0.0212 (5)0.0226 (5)0.0021 (4)−0.0042 (4)0.0009 (4)
C80.0305 (6)0.0272 (6)0.0270 (6)0.0031 (5)−0.0021 (5)−0.0051 (5)
C90.0260 (6)0.0282 (6)0.0315 (6)−0.0025 (5)0.0020 (5)0.0026 (5)
C100.0203 (5)0.0267 (6)0.0230 (5)0.0024 (4)−0.0033 (4)0.0012 (4)
C110.0210 (5)0.0215 (5)0.0212 (5)0.0022 (4)−0.0020 (4)0.0008 (4)
C120.0204 (5)0.0218 (5)0.0191 (5)0.0021 (4)−0.0010 (4)0.0006 (4)
C130.0179 (5)0.0234 (5)0.0177 (5)0.0030 (4)−0.0011 (4)−0.0005 (4)
C140.0206 (5)0.0259 (6)0.0216 (5)0.0020 (4)−0.0018 (4)−0.0032 (4)
O2A0.0274 (5)0.0231 (5)0.0354 (5)−0.0005 (4)−0.0115 (4)−0.0025 (4)
C150.0207 (5)0.0362 (7)0.0235 (5)0.0049 (5)−0.0051 (4)−0.0025 (5)
C160.0254 (6)0.0329 (6)0.0218 (5)0.0095 (5)−0.0001 (4)0.0028 (4)
C170.0287 (6)0.0252 (6)0.0266 (6)0.0036 (5)0.0005 (5)0.0030 (4)
C180.0225 (5)0.0257 (6)0.0200 (5)0.0005 (4)−0.0021 (4)0.0003 (4)
O2B0.0274 (5)0.0231 (5)0.0354 (5)−0.0005 (4)−0.0115 (4)−0.0025 (4)
C190.0359 (7)0.0457 (8)0.0311 (6)0.0147 (6)−0.0121 (5)0.0016 (6)
C200.0317 (7)0.0537 (10)0.0517 (9)0.0122 (7)−0.0083 (6)−0.0029 (7)
C210.0402 (7)0.0335 (7)0.0332 (6)0.0157 (6)0.0025 (6)0.0065 (5)
C220.0616 (11)0.0467 (9)0.0381 (8)0.0144 (8)0.0131 (7)0.0114 (7)
O30.057 (3)0.0470 (19)0.148 (7)0.013 (2)−0.023 (4)−0.023 (3)
C230.120 (7)0.066 (5)0.131 (8)0.0000.016 (6)0.000
C240.057 (3)0.0470 (19)0.148 (7)0.013 (2)−0.023 (4)−0.023 (3)
C250.057 (3)0.0470 (19)0.148 (7)0.013 (2)−0.023 (4)−0.023 (3)
Geometric parameters (Å, º) top
O1—C61.3351 (14)O2A—H2A0.88 (2)
O1—C71.4802 (13)C15—C161.4116 (19)
N1—C11.1484 (17)C15—H150.9500
N2—C31.1485 (19)C16—C171.4286 (18)
N4—C161.3567 (15)C17—C181.3617 (16)
N4—C191.4630 (18)C17—H170.9500
N4—C211.469 (2)C18—O2B1.313 (5)
N3—C101.1473 (17)C18—H180.9500
C1—C21.4212 (17)O2B—H2B0.840 (10)
C2—C61.3803 (15)C19—C201.516 (2)
C2—C31.4198 (18)C19—H19A0.9900
C4—C51.3929 (15)C19—H19B0.9900
C4—C111.4037 (15)C20—H20A0.9800
C4—C71.5167 (16)C20—H20B0.9800
C5—C101.4218 (16)C20—H20C0.9800
C5—C61.4256 (15)C21—C221.514 (2)
C7—C91.5203 (17)C21—H21A0.9900
C7—C81.5235 (16)C21—H21B0.9900
C8—H8A0.9800C22—H22A0.9800
C8—H8B0.9800C22—H22B0.9800
C8—H8C0.9800C22—H22C0.9800
C9—H9A0.9800O3—C241.187 (11)
C9—H9B0.9800C23—C241.416 (10)
C9—H9C0.9800C23—H23A0.9800
C11—C121.3798 (15)C23—H23B0.9800
C11—H110.9500C23—H23C0.9800
C12—C131.4169 (15)C24—C24i1.44 (2)
C12—H120.9500C24—O3i1.447 (14)
C13—C181.4166 (16)C24—C251.480 (12)
C13—C141.4216 (15)C25—H25A0.9800
C14—C151.3816 (16)C25—H25B0.9800
C14—H140.9500C25—H25C0.9800
C14—O2A1.3422 (15)
C6—O1—C7110.24 (8)C16—C17—H17119.9
C16—N4—C19120.99 (12)O2B—C18—C17110.3 (5)
C16—N4—C21122.06 (12)O2B—C18—C13125.4 (5)
C19—N4—C21116.58 (11)C17—C18—C13123.45 (11)
N1—C1—C2177.39 (14)C17—C18—H18118.3
C6—C2—C3123.41 (11)C13—C18—H18118.3
C6—C2—C1119.87 (11)C18—O2B—H2B117 (3)
C3—C2—C1116.72 (10)N4—C19—C20112.37 (12)
N2—C3—C2176.28 (15)N4—C19—H19A109.1
C5—C4—C11124.90 (11)C20—C19—H19A109.1
C5—C4—C7107.19 (9)N4—C19—H19B109.1
C11—C4—C7127.91 (10)C20—C19—H19B109.1
C4—C5—C10124.25 (10)H19A—C19—H19B107.9
C4—C5—C6109.15 (10)C19—C20—H20A109.5
C10—C5—C6126.50 (10)C19—C20—H20B109.5
O1—C6—C2118.49 (10)H20A—C20—H20B109.5
O1—C6—C5110.33 (9)C19—C20—H20C109.5
C2—C6—C5131.18 (11)H20A—C20—H20C109.5
O1—C7—C4103.09 (8)H20B—C20—H20C109.5
O1—C7—C9105.73 (9)N4—C21—C22111.34 (12)
C4—C7—C9114.00 (10)N4—C21—H21A109.4
O1—C7—C8106.11 (9)C22—C21—H21A109.4
C4—C7—C8113.73 (10)N4—C21—H21B109.4
C9—C7—C8112.97 (10)C22—C21—H21B109.4
N3—C10—C5176.62 (13)H21A—C21—H21B108.0
C12—C11—C4125.57 (11)C21—C22—H22A109.5
C12—C11—H11117.2C21—C22—H22B109.5
C4—C11—H11117.2H22A—C22—H22B109.5
C11—C12—C13126.38 (11)C21—C22—H22C109.5
C11—C12—H12116.8H22A—C22—H22C109.5
C13—C12—H12116.8H22B—C22—H22C109.5
C18—C13—C12124.17 (10)C24—C23—H23A109.5
C18—C13—C14115.68 (10)C24—C23—H23B109.5
C12—C13—C14120.15 (10)H23A—C23—H23B109.5
O2A—C14—C13116.99 (10)C24—C23—H23C109.5
O2A—C14—C15120.99 (11)H23A—C23—H23C109.5
C14—O2A—H2A111.0 (12)H23B—C23—H23C109.5
C15—C14—C13122.04 (11)O3—C24—C23125.3 (11)
C15—C14—H14119.0C23—C24—O3i107.9 (8)
C13—C14—H14119.0O3—C24—C25120.8 (11)
C14—C15—C16120.95 (11)C23—C24—C25113.9 (7)
C14—C15—H15119.5O3i—C24—C25137.9 (8)
C16—C15—H15119.5C24—C25—H25A109.5
N4—C16—C15121.99 (12)C24—C25—H25B109.5
N4—C16—C17120.33 (12)H25A—C25—H25B109.5
C15—C16—C17117.68 (11)C24—C25—H25C109.5
C18—C17—C16120.20 (12)H25A—C25—H25C109.5
C18—C17—H17119.9H25B—C25—H25C109.5
C11—C4—C5—C102.82 (18)C4—C11—C12—C13179.20 (11)
C7—C4—C5—C10−176.69 (11)C11—C12—C13—C18−0.24 (19)
C11—C4—C5—C6179.34 (10)C11—C12—C13—C14178.55 (11)
C7—C4—C5—C6−0.17 (13)C18—C13—C14—C15−0.75 (17)
C7—O1—C6—C2179.11 (10)C12—C13—C14—C15−179.65 (11)
C7—O1—C6—C5−0.50 (13)C13—C14—C15—C160.76 (18)
C3—C2—C6—O1175.13 (11)C19—N4—C16—C15−0.26 (19)
C1—C2—C6—O1−5.26 (17)C21—N4—C16—C15−173.06 (12)
C3—C2—C6—C5−5.4 (2)C19—N4—C16—C17179.96 (12)
C1—C2—C6—C5174.26 (12)C21—N4—C16—C177.15 (19)
C4—C5—C6—O10.42 (13)C14—C15—C16—N4−179.80 (12)
C10—C5—C6—O1176.85 (11)C14—C15—C16—C17−0.02 (18)
C4—C5—C6—C2−179.12 (12)N4—C16—C17—C18179.09 (12)
C10—C5—C6—C2−2.7 (2)C15—C16—C17—C18−0.70 (18)
C6—O1—C7—C40.37 (12)C16—C17—C18—O2B−169.5 (6)
C6—O1—C7—C9−119.59 (10)C16—C17—C18—C130.70 (19)
C6—O1—C7—C8120.19 (10)C12—C13—C18—O2B−12.4 (7)
C5—C4—C7—O1−0.10 (12)C14—C13—C18—O2B168.7 (7)
C11—C4—C7—O1−179.60 (11)C12—C13—C18—C17178.87 (11)
C5—C4—C7—C9113.99 (11)C14—C13—C18—C170.02 (17)
C11—C4—C7—C9−65.50 (15)C16—N4—C19—C2082.75 (17)
C5—C4—C7—C8−114.53 (11)C21—N4—C19—C20−104.06 (15)
C11—C4—C7—C865.98 (15)C16—N4—C21—C2278.93 (17)
C5—C4—C11—C12−177.89 (11)C19—N4—C21—C22−94.18 (15)
C7—C4—C11—C121.52 (19)
Symmetry code: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H2OA···N1ii0.88 (2)1.96 (2)2.8095 (16)162 (2)
C17—H17···O30.952.373.213 (13)148
C17—H17···O3i0.952.513.324 (13)144
Symmetry codes: (i) −x+1, y, −z+1/2; (ii) x−1/2, −y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula4C22H22N4O2·C3H6O
Mr1555.82
Crystal system, space groupMonoclinic, C2/c
Temperature (K)113
a, b, c (Å)18.6899 (6), 14.4941 (4), 16.7485 (5)
β (°) 95.266 (2)
V (Å3)4517.9 (2)
Z2
Radiation typeMo Kα
µ (mm−1)0.08
Crystal size (mm)0.61 × 0.53 × 0.33
Data collection
DiffractometerBruker-Nonius APEXII CCD
Absorption correctionMulti-scan
(SADABS; Blessing, 1995)
Tmin, Tmax0.678, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections		51842, 6086, 4957
Rint0.033
(sin θ/λ)max (Å−1)0.688
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.138, 1.04
No. of reflections6089
No. of parameters289
No. of restraints5
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.44, −0.34

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT and SADABS (Bruker, 2005), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2A—H2OA···N1i0.880 (18)1.958 (19)2.8095 (16)162.4 (18)
C17—H17···O30.952.373.213 (13)148
C17—H17···O3ii0.952.513.324 (13)144
Symmetry codes: (i) x−1/2, −y−1/2, z−1/2; (ii) −x+1, y, −z+1/2.
 

Acknowledgements

The authors thank Drs J. Wikaira and C. Fitchett of the University of Canterbury for the data collection. This work was supported by the NZ Ministry for Science and Innovation (contract No. CO8X0704).

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationAvetisyan, A. A., Alvandzhyan, A. G. & Avetisyan, K. S. (2009). Russ. J. Org. Chem. 45, 1871–1872.  Web of Science CrossRef CAS Google Scholar
 First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationBruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationDalton, L. R. (2004). Pure Appl. Chem. 76, 1421–1433.  Web of Science CrossRef CAS Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationGainsford, G. J., Bhuiyan, M. D. H. & Kay, A. J. (2008). Acta Cryst. C64, o616–o619.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationLi, S., Li, M., Qin, J., Tong, M., Chen, X., Liu, T., Fu, Y. & Su, Z. (2009). CrystEngComm, 11, 589–596.  Web of Science CSD CrossRef CAS Google Scholar
 First citationLi, Z., Li, M., Zhou, X. P., Wu, T., Li, D. & Ng, S. W. (2007). Cryst. Growth Des. 7, 1992–1998.  Web of Science CSD CrossRef CAS Google Scholar
 First citationMa, H., Jen, A. K.-Y. & Dalton, L. R. (2002). Adv. Mater. 14, 1339–1365.  Web of Science CrossRef CAS Google Scholar
 First citationMacrae, 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.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
 First citationMarder, S. R., Kippelen, B., Jen, A. K.-Y. & Peyghambarian, N. (1997). Nature (London), 388, 845–851.  CrossRef CAS Web of Science Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWu, J., Liu, J., Zhou, T., Bo, S., Qiu, L., Zhen, Z. & Liu, X. (2012). RSC Advances, 2, 1416–1423.  Web of Science CSD CrossRef CAS Google Scholar

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Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 68| Part 10| October 2012| Pages o2991-o2992
https://doi.org/10.1107/S1600536812039736
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