Crystal structure of 5-[4-(di­ethyl­amino)­benzyl­idene]-2,2-dimethyl-1,3-dioxane-4,6-dione

Stepina, E.; Stepanovs, D.; Mierina, I.; Jure, M.

doi:10.1107/S2056989015017673

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages 1242-1244

doi:10.1107/S2056989015017673

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Crystal structure of 5-[4-(diethylamino)benzylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione

Egija Stepina,^a Dmitrijs Stepanovs,^a,^b ^* Inese Mierina ^a and Mara Jure ^a ^*

^aFaculty of Materials Science and Applied Chemistry, Riga Technical University, Str. P. Valdena 3/7, Riga, LV 1048, Latvia, and ^bLatvian Institute of Organic Synthesis, Str. Aizkraukles 21, Riga, LV 1006, Latvia
^*Correspondence e-mail: d_stepanovs@osi.lv, mara@ktf.rtu.lv

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 17 September 2015; accepted 21 September 2015; online 26 September 2015)

The title compound, C₁₇H₂₁NO₄, consists of substituted Meldrum's acid with a [4-(diethylamino)phenyl]methylidene fragment attached to the fifth position. The heterocycle assumes a distorted boat conformation. The planar part of heterocycle is almost coplanar with the benzene ring due to the presence of a long conjugated system in the molecule. This leads to the formation of C—H⋯O-type intramolecular contacts. As a result of the absence of hydrogen-bond donors in the structure, the crystal packing is controlled by van der Waals forces and weak C—H⋯O interactions, which associate the molecules into inversion dimers.

Keywords: crystal structure; arylidene Meldrum's acid; 5-arylmethylene-2,2-dimethyl-1,3-dioxan-4,6-dione; organic synthesis; intramolecular hydrogen bonding.

CCDC reference: 1426237

1. Chemical context

Arylidene Meldrum's acids (5-arylmethylidene-2,2-dimethyl-1,3-dioxane-4,6-diones) are attractive building blocks in organic chemistry: these compounds are used for the synthesis of different heterocycles. Recent examples include: pyrazolidinones (Pair et al., 2014 ), lactames (Zhang et al., 2013 ), carbocycles (e.g. Trost & Maruniak, 2013 ) and aliphatic compounds (e.g. Mohite & Bhat, 2013 ). Arylidene Meldrum's acids can be easily converted to arylmethyl Meldrum`s acids [for a description of a typical procedure, see Mierina et al. (2015 )], which serve as starting compounds for the synthesis of various valuable compounds [for a mini-review, see Mierina (2014 )]. Apart from their wide application in syntheses, these derivatives of Meldrum's acid have been studied as platelet aggregation inhibitors (El Maatougui et al., 2012 ), antimalarial agents and anti-oxidants (Sandhu et al., 2010 ) and photostable UV-filters for cosmetic applications (Habeck & Krause, 1999 ).

2. Structural commentary

The title compound, C₁₇H₂₁NO₄, consists of substituted Meldrum's acid with a [4-(diethylamino)phenyl]methylidene fragment attached to fifth position (Fig. 1.). The heterocycle assumes a distorted boat conformation. Atoms C2 and C5 deviate from the least-squares plane [maximum deviations ±0.013 (1) Å] calculated for the other four atoms of the heterocycle by 0.549 (3) and 0.154 (3) Å, respectively. The planar part of heterocycle is nearly coplanar with the benzene ring [dihedral angle = 8.05 (10)°] due to the presence of a long conjugated system in the molecule. This leads to the formation of C—H⋯O-type intramolecular contacts (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O19	0.93	2.13	2.915 (2)	141
C17—H17B⋯O20ⁱ	0.97	2.39	3.268 (3)	151
Symmetry code: (i) -x, -y+1, -z+1.

Figure 1
The molecular structure the title compound, showing 50% probability displacement ellipsoids and the atomic numbering

π–π stacking interactions are also observed between conjugated systems of the molecules. The distance between the corresponding least-square planes is 3.54 (su?) Å.

The crystal structure of the zwitterionic form of 5-[4-(diethylamino)benzyl]-2,2-dimethyl-1,3-dioxane-4,6-dione has been already reported (Mierina et al., 2015). The title compound differs from this by the presence of a double bond between atoms C5 and C7.

3. Supramolecular features

Because of the absence of hydrogen-bond donors in the structure, the crystal packing is controlled by van der Waals forces and weak C—H⋯O interactions, which associate molecules into inversion dimers (Fig. 2, Table 1).

Figure 2
The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1

for details).

4. Database survey

Several 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones (Huck et al., 1995 ; Gould et al., 1998 ; Novoa de Armas et al., 2000 ; O'Leary et al., 2001 ; O'Leary & Wallis 2006 ; Crawford & McNab, 2009 ; Wilsily & Fillion, 2009 ; Zeng, 2010a ,b , 2011a ,b ,c , 2013 ; Jie, 2012 ; García-Álvarez et al., 2013 ; Dey et al., 2015 ) and their spiro-analogues (Sato et al., 1989 ; Zeng, 2011d ,e ,f ; Zeng et al. 2013 ) have been characterized by X-ray analysis. However, information on the crystal structure of 5-arylmethylidene-2,2-dimethyl-1,3-dioxane-4,6-diones containing an amino functionality on the aromatic ring is not available.

5. Synthesis and crystallization

5-[4-(Diethylamino)phenylmethylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione was obtained from Meldrum's acid (1.00 g, 6.9 mmol) and 4-diethylaminobenzaldehyde (1.27 g, 6.9 mmol) by heating in water (50 ml) at 348 K for 2 h, followed by cooling to room temperature and filtration of the formed precipitate and recrystallization from ethanol (1.62 g, 80%) analogously to the method described previously (Mierina et al., 2015). The spectroscopic and physical data correspond to those in the literature (Mierina et al., 2015). X-ray quality single crystals were obtained by slow evaporation from ethanol.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The C-bound H atoms were positioned geometrically and refined as riding on their parent atoms: C—H = 0.93–0.98Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₂₁NO₄
M_r	303.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	7.8662 (2), 11.4601 (3), 18.1517 (6)
β (°)	96.858 (1)
V (Å³)	1624.62 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.19 × 0.09

Data collection
Diffractometer	Nonius KappaCCD
No. of measured, independent and observed [I > 2σ(I)] reflections	6627, 3705, 2183
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.127, 1.00
No. of reflections	3705
No. of parameters	203
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19
Computer programs: KappaCCD Server Software (Nonius, 1997 ), HKL DENZO and SCALEPACK (Otwinovski & Minor, 1997 ), SIR2011 (Burla et al., 2012 ), ORTEP-3 for Windows (Farrugia, 2012 ), SHELXL97 (Sheldrick, 2008 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1426237

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015017673/xu5872sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015017673/xu5872Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015017673/xu5872Isup3.cml

checkCIF report

Chemical context top

Arylidene Meldrum's acids (5-arylmethylidene-2,2-dimethyl-1,3-dioxane-4,6-diones) are attractive building blocks in organic chemistry: these compounds are used for the synthesis of different heterocycles. Recent examples include: pyrazolidinones (Pair et al., 2014), lactames (Zhang et al., 2013), carbocycles (e.g. Trost & Maruniak, 2013) and aliphatic compounds (e.g. Mohite & Bhat, 2013). Arylidene Meldrum's acids can be easily converted to arylmethyl Meldrum`s acids [for a description of a typical procedure, see Mierina et al. (2015)], which serve as starting compounds for the synthesis of various valuable compounds [for a mini-review, see Mierina (2014)]. Apart from their wide application in syntheses, these derivatives of Meldrum's acid have been studied as platelet aggregation inhibitors (El Maatougui et al., 2012), antimalarial agents and anti-oxidants (Sandhu et al., 2010) and photostable UV-filters for cosmetic applications (Habeck & Krause, 1999).

Structural commentary top

\ The title compound, C₁₇H₂₁NO₄, consists of the substituted Meldrum's acid with a [4-(diethylamino)phenyl]methylidene fragment attached to fifth position (Fig. 1.). The heterocycle assumes a distorted boat conformation. Atoms C2 and C5 deviate from the least-squares plane [±0.013 (1) Å] calculated for the other four atoms of the heterocycle by 0.549 (3) and 0.154 (3) Å, respectively. The planar part of heterocycle is nearly coplanar with the benzene ring due to the presence of a long conjugated system in the molecule. This leads to the formation of C—H···O-type intramolecular contacts (Table 1).

π–π stacking interactions have been also observed between conjugated systems of the molecules. The distance between the corresponding least-square planes is 3.54 (su?) Å.

The crystal structure of the zwitterionic form of 5-[4-(diethylamino)benzyl]-2,2-dimethyl-\ 1,3-dioxane-4,6-dione has been already reported (Mierina et al., 2015). The title compound differs from this by the presence of a double bond between atoms C5 and C7.

Supramolecular features top

Because of the absence of hydrogen-bond donors in the structure, the crystal packing is controlled by van der Waals forces and weak C—H···O interactions, which associate molecules into dimers (Fig. 2, Table 1).

Database survey top

Several 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones (Huck et al., 1995; Gould et al., 1998; Novoa de Armas et al., 2000; O'Leary et al., 2001; O'Leary & Wallis 2006; Crawford & McNab, 2009; Wilsily & Fillion, 2009; Zeng, 2010a,b, 2011a,b,c, 2013; Jie, 2012; García-Álvarez et al., 2013; Dey et al., 2015) and their spiro-analogues (Sato et al., 1989; Zeng, 2011d,e,f; Zeng et al. 2013) have been characterized by X-ray analysis; in most of the cases X-ray diffraction was used only to determine the structure. However, information on the crystal structure of 5-arylmethylidene-2,2-dimethyl-1,3-dioxane-4,6-diones containing an amino functionality on the aromatic ring is not available.

Synthesis and crystallization top

5-[4-(Diethylamino)phenylmethylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione was obtained from Meldrum`s acid (1.00 g, 6.9 mmol) and 4-diethylaminobenzaldehyde (1.27 g, 6.9 mmol) by heating in water (50 ml) at 348 K for 2 h, followed by cooling to room temperature and filtration of the formed precipitate and recrystallization from ethanol (1.62 g, 80%) analogously to the method described previously (Mierina et al., 2015). The spectroscopic and physical data correspond to those in the literature (Mierina et al., 2015). X-ray quality single crystals were obtained by slow evaporation from ethanol.

Refinement top

Related literature top

For related literature, see: Crawford & McNab (2009); Dey et al. (2015); El Maatougui, Azuaje, Coelho, Cano, Yanez, Lopez, Yaziji, Carbajales & Sotelo (2012); Gould et al. (1998); Habeck & Krause (1999); Huck et al. (1995); Jie (2012); Mierina (2014); Mierina et al. (2015); Mohite & Bhat (2013); Novoa de Armas, Blaton, Peeters, De Ranter, Suarez, Ochoa, Verdecia & Salfran (2000); O'Leary & Wallis (2006); O'Leary et al. (2001); Pair et al. (2014); Sandhu et al. (2010); Sato et al. (1989); Trost & Maruniak (2013); Wilsily & Fillion (2009); Zeng (2010a, 2010b, 2011a, 2011b, 2011c, 2011d, 2011e, 2011f, 2013a); Zeng et al. (2013b); Zhang et al. (2013).

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: HKL SCALEPACK (Otwinovski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinovski & Minor, 1997); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure the title compound, showing 50% probability displacement ellipsoids and the atomic numbering
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

5-[4-(Diethylamino)benzylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione top

Crystal data top

C₁₇H₂₁NO₄	F(000) = 648
M_r = 303.35	D_x = 1.240 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15405 reflections
a = 7.8662 (2) Å	θ = 1.0–27.5°
b = 11.4601 (3) Å	µ = 0.09 mm⁻¹
c = 18.1517 (6) Å	T = 173 K
β = 96.858 (1)°	Plate, red
V = 1624.62 (8) Å³	0.26 × 0.19 × 0.09 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	2183 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 27.5°, θ_min = 2.3°
CCD scans	h = −10→10
6627 measured reflections	k = −14→13
3705 independent reflections	l = −23→23

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0534P)² + 0.0774P] where P = (F_o² + 2F_c²)/3
3705 reflections	(Δ/σ)_max < 0.001
203 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₇H₂₁NO₄	V = 1624.62 (8) Å³
M_r = 303.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8662 (2) Å	µ = 0.09 mm⁻¹
b = 11.4601 (3) Å	T = 173 K
c = 18.1517 (6) Å	0.26 × 0.19 × 0.09 mm
β = 96.858 (1)°

Data collection top

Nonius KappaCCD diffractometer	2183 reflections with I > 2σ(I)
6627 measured reflections	R_int = 0.054
3705 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
3705 reflections	Δρ_min = −0.19 e Å⁻³
203 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

	x	y	z	U_iso*/U_eq
O1	0.57779 (16)	0.16291 (12)	0.51388 (7)	0.0404 (4)
O19	0.65514 (15)	0.45154 (13)	0.40080 (8)	0.0407 (4)
O3	0.73309 (14)	0.27588 (11)	0.43789 (8)	0.0390 (4)
C8	0.2432 (2)	0.50423 (15)	0.40398 (10)	0.0252 (4)
C10	−0.0015 (2)	0.63516 (16)	0.37433 (10)	0.0266 (4)
H10	−0.1138	0.6545	0.3804	0.032*
O20	0.33160 (19)	0.21986 (13)	0.54631 (9)	0.0584 (5)
N14	0.02179 (17)	0.80169 (13)	0.29384 (9)	0.0307 (4)
C12	0.2607 (2)	0.66959 (17)	0.32158 (11)	0.0317 (5)
H12	0.3242	0.7124	0.2910	0.038*
C9	0.0729 (2)	0.53919 (16)	0.40930 (10)	0.0259 (4)
H9	0.0078	0.4944	0.4382	0.031*
C11	0.0910 (2)	0.70529 (16)	0.32900 (10)	0.0266 (4)
C4	0.6131 (2)	0.36263 (18)	0.42864 (11)	0.0310 (5)
C13	0.3340 (2)	0.57427 (17)	0.35789 (11)	0.0309 (5)
H13	0.4465	0.5550	0.3521	0.037*
C7	0.3028 (2)	0.40397 (16)	0.44569 (10)	0.0275 (4)
H7	0.2188	0.3745	0.4725	0.033*
C15	0.1135 (2)	0.86883 (18)	0.24297 (11)	0.0386 (5)
H15A	0.0311	0.9075	0.2070	0.046*
H15B	0.1801	0.8159	0.2161	0.046*
C5	0.4505 (2)	0.33863 (16)	0.45730 (10)	0.0292 (4)
C6	0.4436 (3)	0.23885 (18)	0.50801 (11)	0.0377 (5)
C2	0.6814 (2)	0.16029 (17)	0.45458 (12)	0.0363 (5)
C18	−0.2946 (2)	0.7988 (2)	0.25955 (13)	0.0473 (6)
H18A	−0.2752	0.8057	0.2085	0.071*
H18B	−0.3967	0.8406	0.2673	0.071*
H18C	−0.3077	0.7180	0.2716	0.071*
C17	−0.1429 (2)	0.84969 (17)	0.30887 (12)	0.0349 (5)
H17A	−0.1415	0.9336	0.3019	0.042*
H17B	−0.1577	0.8348	0.3603	0.042*
C21	0.8427 (3)	0.0962 (2)	0.48418 (14)	0.0551 (6)
H21A	0.8967	0.1357	0.5274	0.083*
H21B	0.9195	0.0943	0.4469	0.083*
H21C	0.8146	0.0179	0.4971	0.083*
C22	0.5872 (3)	0.1025 (2)	0.38720 (12)	0.0460 (6)
H22A	0.5555	0.0247	0.3997	0.069*
H22B	0.6600	0.0994	0.3484	0.069*
H22C	0.4860	0.1465	0.3706	0.069*
C16	0.2319 (3)	0.9596 (2)	0.28194 (14)	0.0533 (6)
H16A	0.1656	1.0166	0.3047	0.080*
H16B	0.2950	0.9971	0.2465	0.080*
H16C	0.3102	0.9224	0.3194	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0464 (8)	0.0385 (9)	0.0367 (8)	0.0179 (6)	0.0058 (6)	0.0069 (7)
O19	0.0303 (7)	0.0382 (9)	0.0546 (10)	0.0026 (6)	0.0093 (6)	0.0078 (7)
O3	0.0274 (7)	0.0354 (8)	0.0538 (9)	0.0093 (6)	0.0033 (6)	0.0008 (7)
C8	0.0267 (9)	0.0252 (10)	0.0236 (10)	0.0011 (7)	0.0025 (7)	−0.0030 (8)
C10	0.0229 (9)	0.0296 (11)	0.0276 (10)	0.0014 (7)	0.0039 (7)	−0.0005 (9)
O20	0.0643 (10)	0.0510 (11)	0.0666 (11)	0.0218 (8)	0.0352 (9)	0.0286 (9)
N14	0.0289 (8)	0.0294 (9)	0.0341 (10)	0.0030 (7)	0.0042 (7)	0.0077 (7)
C12	0.0287 (9)	0.0320 (12)	0.0357 (12)	−0.0004 (8)	0.0096 (8)	0.0068 (9)
C9	0.0263 (9)	0.0292 (11)	0.0229 (10)	−0.0026 (7)	0.0058 (7)	−0.0004 (8)
C11	0.0291 (9)	0.0257 (10)	0.0241 (10)	0.0014 (8)	−0.0003 (7)	−0.0027 (8)
C4	0.0285 (10)	0.0321 (12)	0.0315 (11)	0.0051 (8)	0.0000 (8)	−0.0043 (10)
C13	0.0243 (9)	0.0335 (11)	0.0359 (12)	0.0028 (8)	0.0077 (8)	0.0029 (9)
C7	0.0292 (9)	0.0266 (11)	0.0279 (11)	0.0007 (8)	0.0082 (7)	−0.0034 (9)
C15	0.0417 (11)	0.0358 (12)	0.0389 (12)	0.0026 (9)	0.0070 (9)	0.0156 (10)
C5	0.0303 (9)	0.0279 (11)	0.0293 (11)	0.0026 (8)	0.0033 (7)	−0.0022 (9)
C6	0.0430 (11)	0.0346 (12)	0.0364 (12)	0.0103 (9)	0.0086 (9)	0.0034 (10)
C2	0.0360 (11)	0.0324 (12)	0.0403 (13)	0.0108 (9)	0.0033 (9)	0.0005 (10)
C18	0.0347 (11)	0.0472 (14)	0.0580 (15)	0.0033 (9)	−0.0029 (10)	0.0115 (12)
C17	0.0342 (10)	0.0286 (11)	0.0421 (12)	0.0069 (8)	0.0057 (8)	0.0037 (10)
C21	0.0446 (12)	0.0548 (16)	0.0634 (17)	0.0220 (11)	−0.0038 (11)	0.0016 (13)
C22	0.0522 (12)	0.0397 (14)	0.0441 (14)	0.0123 (10)	−0.0023 (10)	−0.0057 (11)
C16	0.0518 (13)	0.0419 (14)	0.0670 (17)	−0.0090 (10)	0.0103 (11)	0.0091 (12)

Geometric parameters (Å, º) top

O1—C6	1.363 (2)	C7—H7	0.9300
O1—C2	1.426 (2)	C15—C16	1.514 (3)
O19—C4	1.201 (2)	C15—H15A	0.9700
O3—C4	1.368 (2)	C15—H15B	0.9700
O3—C2	1.429 (2)	C5—C6	1.473 (3)
C8—C9	1.413 (2)	C2—C22	1.506 (3)
C8—C13	1.413 (2)	C2—C21	1.509 (3)
C8—C7	1.424 (2)	C18—C17	1.519 (3)
C10—C9	1.366 (2)	C18—H18A	0.9600
C10—C11	1.413 (3)	C18—H18B	0.9600
C10—H10	0.9300	C18—H18C	0.9600
O20—C6	1.205 (2)	C17—H17A	0.9700
N14—C11	1.357 (2)	C17—H17B	0.9700
N14—C15	1.457 (2)	C21—H21A	0.9600
N14—C17	1.463 (2)	C21—H21B	0.9600
C12—C13	1.367 (3)	C21—H21C	0.9600
C12—C11	1.418 (2)	C22—H22A	0.9600
C12—H12	0.9300	C22—H22B	0.9600
C9—H9	0.9300	C22—H22C	0.9600
C4—C5	1.463 (2)	C16—H16A	0.9600
C13—H13	0.9300	C16—H16B	0.9600
C7—C5	1.377 (2)	C16—H16C	0.9600

C6—O1—C2	117.50 (15)	O20—C6—C5	125.78 (18)
C4—O3—C2	119.35 (14)	O1—C6—C5	117.29 (17)
C9—C8—C13	115.46 (16)	O1—C2—O3	110.09 (15)
C9—C8—C7	116.56 (16)	O1—C2—C22	110.63 (16)
C13—C8—C7	127.97 (16)	O3—C2—C22	111.13 (17)
C9—C10—C11	120.46 (16)	O1—C2—C21	105.88 (17)
C9—C10—H10	119.8	O3—C2—C21	106.15 (16)
C11—C10—H10	119.8	C22—C2—C21	112.74 (18)
C11—N14—C15	121.78 (15)	C17—C18—H18A	109.5
C11—N14—C17	122.20 (15)	C17—C18—H18B	109.5
C15—N14—C17	115.86 (15)	H18A—C18—H18B	109.5
C13—C12—C11	122.18 (17)	C17—C18—H18C	109.5
C13—C12—H12	118.9	H18A—C18—H18C	109.5
C11—C12—H12	118.9	H18B—C18—H18C	109.5
C10—C9—C8	123.61 (16)	N14—C17—C18	113.34 (17)
C10—C9—H9	118.2	N14—C17—H17A	108.9
C8—C9—H9	118.2	C18—C17—H17A	108.9
N14—C11—C10	122.12 (16)	N14—C17—H17B	108.9
N14—C11—C12	121.31 (16)	C18—C17—H17B	108.9
C10—C11—C12	116.57 (16)	H17A—C17—H17B	107.7
O19—C4—O3	116.57 (16)	C2—C21—H21A	109.5
O19—C4—C5	127.27 (17)	C2—C21—H21B	109.5
O3—C4—C5	116.09 (17)	H21A—C21—H21B	109.5
C12—C13—C8	121.68 (16)	C2—C21—H21C	109.5
C12—C13—H13	119.2	H21A—C21—H21C	109.5
C8—C13—H13	119.2	H21B—C21—H21C	109.5
C5—C7—C8	137.58 (17)	C2—C22—H22A	109.5
C5—C7—H7	111.2	C2—C22—H22B	109.5
C8—C7—H7	111.2	H22A—C22—H22B	109.5
N14—C15—C16	112.95 (18)	C2—C22—H22C	109.5
N14—C15—H15A	109.0	H22A—C22—H22C	109.5
C16—C15—H15A	109.0	H22B—C22—H22C	109.5
N14—C15—H15B	109.0	C15—C16—H16A	109.5
C16—C15—H15B	109.0	C15—C16—H16B	109.5
H15A—C15—H15B	107.8	H16A—C16—H16B	109.5
C7—C5—C4	126.92 (18)	C15—C16—H16C	109.5
C7—C5—C6	115.10 (16)	H16A—C16—H16C	109.5
C4—C5—C6	117.86 (16)	H16B—C16—H16C	109.5
O20—C6—O1	116.90 (18)

C11—C10—C9—C8	0.8 (3)	C8—C7—C5—C4	4.4 (4)
C13—C8—C9—C10	−1.4 (3)	C8—C7—C5—C6	−179.8 (2)
C7—C8—C9—C10	178.19 (17)	O19—C4—C5—C7	13.2 (3)
C15—N14—C11—C10	−175.52 (17)	O3—C4—C5—C7	−170.14 (18)
C17—N14—C11—C10	9.3 (3)	O19—C4—C5—C6	−162.49 (19)
C15—N14—C11—C12	4.1 (3)	O3—C4—C5—C6	14.2 (2)
C17—N14—C11—C12	−171.03 (17)	C2—O1—C6—O20	160.50 (19)
C9—C10—C11—N14	−179.51 (17)	C2—O1—C6—C5	−21.3 (2)
C9—C10—C11—C12	0.8 (3)	C7—C5—C6—O20	−10.3 (3)
C13—C12—C11—N14	178.48 (18)	C4—C5—C6—O20	166.0 (2)
C13—C12—C11—C10	−1.8 (3)	C7—C5—C6—O1	171.75 (17)
C2—O3—C4—O19	−165.89 (17)	C4—C5—C6—O1	−12.0 (3)
C2—O3—C4—C5	17.1 (2)	C6—O1—C2—O3	50.5 (2)
C11—C12—C13—C8	1.3 (3)	C6—O1—C2—C22	−72.7 (2)
C9—C8—C13—C12	0.4 (3)	C6—O1—C2—C21	164.84 (18)
C7—C8—C13—C12	−179.18 (18)	C4—O3—C2—O1	−48.8 (2)
C9—C8—C7—C5	179.1 (2)	C4—O3—C2—C22	74.2 (2)
C13—C8—C7—C5	−1.4 (4)	C4—O3—C2—C21	−162.94 (17)
C11—N14—C15—C16	−85.9 (2)	C11—N14—C17—C18	−89.7 (2)
C17—N14—C15—C16	89.6 (2)	C15—N14—C17—C18	94.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O19	0.93	2.13	2.915 (2)	141
C17—H17B···O20ⁱ	0.97	2.39	3.268 (3)	151

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O19	0.93	2.13	2.915 (2)	141
C17—H17B···O20ⁱ	0.97	2.39	3.268 (3)	151

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₇H₂₁NO₄
M_r	303.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	7.8662 (2), 11.4601 (3), 18.1517 (6)
β (°)	96.858 (1)
V (Å³)	1624.62 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.19 × 0.09

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6627, 3705, 2183
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.127, 1.00
No. of reflections	3705
No. of parameters	203
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: KappaCCD Server Software (Nonius, 1997), HKL SCALEPACK (Otwinovski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinovski & Minor, 1997), SIR2011 (Burla et al., 2012), ORTEP-3 for Windows (Farrugia, 2012), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

IM thanks the European Social Fund for a scholarship within the project `Support for the implementation of doctoral studies at Riga Technical University'.

References

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Volume 71| Part 10| October 2015| Pages 1242-1244

doi:10.1107/S2056989015017673

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of 5-[4-(di­ethyl­amino)­benzyl­­idene]-2,2-di­methyl-1,3-dioxane-4,6-dione

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of 5-[4-(diethylamino)benzylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione

3. Supramolecular features