2-{3-Cyano-5,5-dimethyl-4-[4-(piperidin-1-yl)buta-1,3-dien­yl]-2,5-dihydro­furan-2-yl­idene}malononitrile

Gainsford, G.J.; Bhuiyan, M.D.H.; Kay, A.J.; Spek, A.L.

doi:10.1107/S1600536808000548

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o503

doi:10.1107/S1600536808000548

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2-{3-Cyano-5,5-dimethyl-4-[4-(piperidin-1-yl)buta-1,3-dienyl]-2,5-dihydrofuran-2-ylidene}malononitrile

Graeme J. Gainsford,^a ^* M. Delower H. Bhuiyan,^a Andrew J. Kay ^a and Anthony L. Spek ^b

^aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand, and ^bUtrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
^*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 21 December 2007; accepted 7 January 2008; online 23 January 2008)

The title compound, C₁₉H₂₀N₄O, crystallizes as twinned crystals containing two independent molecules which pack into a three-dimensional matrix via several C—H⋯N(cyano) interactions, with a C⋯N range of 3.324 (8)–3.568 (8) Å and C—H⋯N angles in the range 147–166°.

Related literature

For general background, see: Kay et al. (2004 ); Gainsford et al. (2007 , 2008 ). For related structures, see: Bock et al. (1996 ); Marder et al. (1993 ); Reck & Dahne (2006 ); Allen (2002 ).

Experimental

Crystal data

C₁₉H₂₀N₄O
M_r = 320.39
Monoclinic, P 2₁ /c
a = 15.094 (4) Å
b = 18.994 (5) Å
c = 13.332 (4) Å
β = 116.193 (8)°
V = 3429.7 (16) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 119 (2) K
0.35 × 0.25 × 0.09 mm

Data collection

Bruker–Nonius APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.733, T_max = 1.0 (expected range = 0.728–0.993)
18712 measured reflections
11128 independent reflections
5766 reflections with I > 2σ(I)
R_int = 0.088

Refinement

R[F² > 2σ(F²)] = 0.079
wR(F²) = 0.203
S = 1.02
11128 reflections
424 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13′—H13′⋯N2ⁱ	0.95	2.49	3.324 (8)	147
C14—H14⋯N1′	0.95	2.58	3.498 (8)	161
C14′—H14′⋯N1ⁱⁱ	0.95	2.61	3.484 (8)	153
C16′—H16D⋯N2ⁱⁱ	0.99	2.55	3.477 (8)	156
C19—H19A⋯N2′ⁱⁱⁱ	0.99	2.60	3.568 (8)	166
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT and SADABS (Sheldrick, 2003 ); 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 PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808000548/gg3141sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000548/gg3141Isup2.hkl

checkCIF report

Comment top

We have previously reported on the synthesis of a number of high figure of merit chromophores for nonlinear optics (Kay et al., 2004), and the X-ray crystallographic and structural properties of crucial dye precursors used (Gainsford et al., 2007, 2008). As part of our ongoing studies of the structure of these highly polar materials, we report here the crystallographic data of another of the chromophore precursors.

The asymmetric unit contents of the title compound (I) is shown in Figures 1 (unprimed & primed independent molecules hereafter A & B) with hydrogen bond data in Table 1. The structures are almost superimposable with a weighted r.m.s. fit between A & inverted B molecules of 0.61Å (Spek, 2003). The only notable difference in bond lengths concerns those involving atoms C11 & C11'. Minor differences in orientations may be attributed to the packing interactions (Table 1). For example the polyene chains C4, C11—C14 are tilted at 7.1 (5)° & 3.4 (6)° to the "CDFP" 5-membered ring planes (O1, C4—C8) in molecules A & B respectively. Similarly the dicyanomethylene groups (N1,N2, C1—C3) are at 3.5 (4) and 7.7 (4)° to the CDFP ring in A & B, respectively. The piperidin-1-yl rings adopt a chair conformation.

The polyene-C—H···N interactions with adjacent cyano N atoms (C13', C14, C14') are commonly observed for these molecules (Gainsford et al., 2008) as is the methylene-C19—H19A interaction with N2' (entry 5, Table 1). Only once before has it been reported when the adjacent polyene C hydrogen atoms (on C13' & C14') are both H bonded to cyano N atoms (NEQHAT01, Reck & Dahne, 2006) from the Cambridge Structural Database (Version 5.29 with November 2007 updates; Allen, 2002). There are few meta-C(C16')—H···N(cyano) interactions reported: two examples exist in the somewhat related compounds YAMXEP (Marder et al., 1993) and ZOSZAI (Bock et al., 1996) with H···N, C—H···N 2.69 & 2.64 Å, 148° & 147°, respectively.

Related literature top

For general background, see: Kay et al. (2004); Gainsford et al. (2007, 2008). For related structures, see: Bock et al. (1996); Marder et al. (1993); Reck & Dahne (2006); Allen (2002).

Experimental top

To a solution of 5.8 mmole of {4-(4-Acetanilido-trans-1,3-butadienyl)-3-cyano-5,5-dimethyl-2(5H)-furanylidene} propanedinitrile (compound 11b, Kay et al., 2004) in 30 ml of ethanol was added an equimolar quantity of piperidine. The solution was refluxed 1 h, cooled and the product collected by filtration and washed with ethanol. Final crystallization was from ethanol.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005) and SADABS (Sheldrick, 2003); 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 PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top

Fig. 1. A view of the asymmetic unit; displacement ellipsoids are shown at the 30% probability level. All H atoms except H14 omitted for clarity; dotted line represents a hydrogen bond interaction (Table 1).

2-{3-Cyano-5,5-dimethyl-4-[4-(piperidin-1-yl)buta-1,3-dienyl]- 2,5-dihydrofuran-2-ylidene}malononitrile top

Crystal data top

C₁₉H₂₀N₄O	F(000) = 1360
M_r = 320.39	D_x = 1.241 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4176 reflections
a = 15.094 (4) Å	θ = 2.7–30.2°
b = 18.994 (5) Å	µ = 0.08 mm⁻¹
c = 13.332 (4) Å	T = 119 K
β = 116.193 (8)°	Plate, red
V = 3429.7 (16) Å³	0.35 × 0.25 × 0.09 mm
Z = 8

Data collection top

Bruker–Nonius APEXII CCD area-detector diffractometer	11128 independent reflections
Radiation source: fine-focus sealed tube	5766 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
Detector resolution: 8.192 pixels mm^-1	θ_max = 25.0°, θ_min = 2.0°
/f and /w scans	h = −16→17
Absorption correction: multi-scan (Blessing, 1995)	k = −22→22
T_min = 0.733, T_max = 1.0	l = −15→15
18712 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.079	H-atom parameters constrained
wR(F²) = 0.203	w = 1/[σ²(F_o²) + (0.041P)² + 5.943P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
11128 reflections	Δρ_max = 0.46 e Å⁻³
424 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (2)

Crystal data top

C₁₉H₂₀N₄O	V = 3429.7 (16) Å³
M_r = 320.39	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.094 (4) Å	µ = 0.08 mm⁻¹
b = 18.994 (5) Å	T = 119 K
c = 13.332 (4) Å	0.35 × 0.25 × 0.09 mm
β = 116.193 (8)°

Data collection top

Bruker–Nonius APEXII CCD area-detector diffractometer	11128 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	5766 reflections with I > 2σ(I)
T_min = 0.733, T_max = 1.0	R_int = 0.088
18712 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.079	0 restraints
wR(F²) = 0.203	H-atom parameters constrained
S = 1.02	Δρ_max = 0.46 e Å⁻³
11128 reflections	Δρ_min = −0.36 e Å⁻³
424 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. An extinction parameter was refined. Data above 2θ 50° were excluded on the basis of low intensity/error ratio. A total of 477 reflections were either not recorded or affected by the backstop within this θ limit (of 6035 expected). A further 13 reflections (and their Friedel opposites) were omitted from the refinement on the basis of being clearly outliers (with F_o<<F_c).

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	0.7393 (3)	0.8303 (2)	0.4515 (3)	0.0343 (10)
N1	0.9567 (4)	0.7590 (3)	0.2970 (5)	0.0422 (15)
N2	0.8344 (4)	0.9570 (3)	0.3440 (4)	0.0489 (15)
N3	0.8724 (4)	0.6091 (3)	0.4162 (5)	0.0473 (15)
N4	0.5250 (3)	0.5399 (2)	0.7252 (4)	0.0326 (12)
C1	0.9063 (4)	0.7849 (3)	0.3282 (5)	0.0356 (16)
C2	0.8470 (4)	0.8229 (3)	0.3707 (5)	0.0321 (14)
C3	0.8397 (4)	0.8966 (4)	0.3552 (5)	0.0362 (15)
C4	0.7276 (4)	0.7135 (3)	0.5029 (5)	0.0289 (15)
C5	0.6857 (4)	0.7869 (3)	0.4989 (5)	0.0311 (15)
C6	0.7962 (4)	0.7888 (3)	0.4209 (5)	0.0305 (14)
C7	0.7908 (4)	0.7191 (3)	0.4492 (5)	0.0283 (14)*
C8	0.5770 (4)	0.7903 (3)	0.4147 (5)	0.0395 (16)
H8A	0.5545	0.8394	0.4055	0.059*
H8B	0.5378	0.7621	0.4420	0.059*
H8C	0.5690	0.7718	0.3426	0.059*
C9	0.7073 (4)	0.8205 (3)	0.6121 (5)	0.0400 (17)
H9A	0.6905	0.8707	0.6015	0.060*
H9B	0.7776	0.8151	0.6630	0.060*
H9C	0.6677	0.7971	0.6440	0.060*
C10	0.8375 (4)	0.6601 (3)	0.4304 (5)	0.0336 (15)
C11	0.7080 (4)	0.6540 (3)	0.5476 (5)	0.0344 (16)
H11	0.7436	0.6126	0.5486	0.041*
C12	0.6398 (4)	0.6493 (3)	0.5920 (4)	0.0297 (14)
H12	0.6046	0.6906	0.5925	0.036*
C13	0.6206 (4)	0.5883 (3)	0.6352 (5)	0.0323 (15)
H13	0.6557	0.5462	0.6387	0.039*
C14	0.5483 (4)	0.5901 (3)	0.6736 (5)	0.0362 (16)
H14	0.5117	0.6327	0.6610	0.043*
C15	0.4434 (4)	0.5482 (3)	0.7556 (5)	0.0389 (16)
H15A	0.4120	0.5948	0.7305	0.047*
H15B	0.4690	0.5458	0.8379	0.047*
C16	0.3684 (4)	0.4911 (3)	0.7020 (5)	0.0438 (17)*
H16A	0.3393	0.4959	0.6197	0.053*
H16B	0.3147	0.4958	0.7250	0.053*
C17	0.4162 (4)	0.4197 (3)	0.7361 (5)	0.0448 (17)
H17A	0.3667	0.3824	0.6982	0.054*
H17B	0.4412	0.4135	0.8178	0.054*
C18	0.5018 (4)	0.4130 (3)	0.7040 (6)	0.0430 (17)*
H18A	0.5355	0.3673	0.7307	0.052*
H18B	0.4756	0.4143	0.6216	0.052*
C19	0.5750 (4)	0.4721 (3)	0.7545 (5)	0.0391 (16)
H19A	0.6084	0.4669	0.8368	0.047*
H19B	0.6259	0.4697	0.7267	0.047*
O1'	0.2394 (3)	0.8340 (2)	0.2535 (3)	0.0340 (10)
N1'	0.4636 (4)	0.7639 (3)	0.6209 (5)	0.0443 (15)
N2'	0.3455 (4)	0.9652 (3)	0.4508 (4)	0.0480 (15)
N3'	0.3582 (4)	0.6149 (3)	0.4407 (4)	0.0443 (15)
N4'	0.0597 (3)	0.5220 (2)	−0.2095 (4)	0.0313 (12)
C1'	0.4113 (4)	0.7928 (3)	0.5417 (5)	0.0347 (15)
C2'	0.3478 (4)	0.8300 (3)	0.4436 (5)	0.0288 (14)
C3'	0.3455 (4)	0.9041 (4)	0.4475 (5)	0.0334 (15)
C4'	0.2259 (4)	0.7152 (3)	0.1981 (5)	0.0269 (14)
C5'	0.1910 (4)	0.7881 (3)	0.1521 (5)	0.0320 (15)
C6'	0.2942 (4)	0.7932 (3)	0.3443 (5)	0.0311 (15)
C7'	0.2857 (4)	0.7224 (3)	0.3153 (5)	0.0295 (15)
C8'	0.0811 (4)	0.7979 (3)	0.1116 (5)	0.0465 (18)
H8'A	0.0653	0.8482	0.1026	0.070*
H8'B	0.0613	0.7778	0.1663	0.070*
H8'C	0.0456	0.7740	0.0396	0.070*
C9'	0.2278 (4)	0.8151 (3)	0.0713 (5)	0.0422 (17)
H9'A	0.2170	0.8660	0.0622	0.063*
H9'B	0.1918	0.7918	−0.0011	0.063*
H9'C	0.2984	0.8050	0.1002	0.063*
C10'	0.3282 (4)	0.6651 (3)	0.3876 (5)	0.0315 (15)
C11'	0.2043 (4)	0.6539 (3)	0.1390 (5)	0.0303 (14)
H11'	0.2299	0.6119	0.1804	0.036*
C12'	0.1479 (4)	0.6464 (3)	0.0229 (5)	0.0296 (14)
H12'	0.1188	0.6872	−0.0203	0.035*
C13'	0.1330 (4)	0.5823 (3)	−0.0312 (5)	0.0318 (15)
H13'	0.1608	0.5407	0.0103	0.038*
C14'	0.0770 (4)	0.5789 (3)	−0.1468 (5)	0.0330 (15)
H14'	0.0486	0.6217	−0.1841	0.040*
C15'	−0.0091 (4)	0.5216 (3)	−0.3290 (5)	0.0425 (18)
H15C	0.0259	0.5050	−0.3723	0.051*
H15D	−0.0324	0.5702	−0.3534	0.051*
C16'	−0.0964 (4)	0.4748 (3)	−0.3530 (5)	0.0440 (17)
H16C	−0.1387	0.4728	−0.4346	0.053*
H16D	−0.1362	0.4944	−0.3172	0.053*
C17'	−0.0618 (4)	0.4010 (3)	−0.3085 (5)	0.0444 (18)
H17C	−0.0300	0.3789	−0.3516	0.053*
H17D	−0.1194	0.3718	−0.3183	0.053*
C18'	0.0114 (4)	0.4035 (3)	−0.1846 (5)	0.0419 (18)
H18C	−0.0224	0.4209	−0.1406	0.050*
H18D	0.0362	0.3554	−0.1583	0.050*
C19'	0.0967 (4)	0.4509 (3)	−0.1666 (5)	0.0374 (15)
H19C	0.1422	0.4535	−0.0858	0.045*
H19D	0.1337	0.4317	−0.2060	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.041 (3)	0.032 (2)	0.036 (3)	0.000 (2)	0.023 (2)	0.003 (2)
N1	0.037 (3)	0.047 (4)	0.047 (4)	0.001 (3)	0.023 (3)	0.002 (3)
N2	0.066 (4)	0.047 (4)	0.037 (4)	−0.002 (3)	0.026 (3)	−0.004 (3)
N3	0.051 (4)	0.047 (4)	0.053 (4)	0.002 (3)	0.031 (3)	0.005 (3)
N4	0.028 (3)	0.036 (3)	0.034 (3)	0.000 (3)	0.014 (2)	0.002 (3)
C1	0.024 (4)	0.039 (4)	0.035 (4)	−0.001 (3)	0.005 (3)	0.002 (3)
C2	0.033 (3)	0.034 (4)	0.032 (4)	−0.004 (3)	0.016 (3)	−0.002 (3)
C3	0.036 (4)	0.044 (4)	0.028 (4)	−0.006 (4)	0.014 (3)	−0.004 (3)
C4	0.024 (3)	0.030 (4)	0.030 (4)	−0.008 (3)	0.010 (3)	−0.004 (3)
C5	0.037 (4)	0.029 (4)	0.035 (4)	−0.007 (3)	0.023 (3)	−0.002 (3)
C6	0.025 (3)	0.043 (4)	0.024 (3)	−0.001 (3)	0.012 (3)	−0.001 (3)
C8	0.033 (4)	0.047 (4)	0.040 (4)	0.005 (3)	0.017 (3)	0.005 (3)
C9	0.053 (4)	0.044 (4)	0.027 (4)	−0.004 (3)	0.021 (3)	−0.010 (3)
C10	0.030 (4)	0.042 (4)	0.027 (3)	−0.003 (3)	0.011 (3)	0.008 (3)
C11	0.028 (3)	0.041 (4)	0.034 (4)	−0.006 (3)	0.014 (3)	0.000 (3)
C12	0.023 (3)	0.035 (4)	0.027 (3)	−0.004 (3)	0.007 (3)	0.000 (3)
C13	0.030 (4)	0.031 (4)	0.035 (4)	−0.003 (3)	0.013 (3)	−0.001 (3)
C14	0.029 (4)	0.039 (4)	0.036 (4)	−0.006 (3)	0.010 (3)	0.002 (3)
C15	0.036 (4)	0.043 (4)	0.045 (4)	−0.007 (3)	0.024 (3)	0.001 (3)
C17	0.043 (4)	0.046 (4)	0.047 (4)	−0.013 (4)	0.020 (3)	−0.005 (4)
C19	0.034 (4)	0.047 (4)	0.039 (4)	0.008 (3)	0.018 (3)	0.010 (3)
O1'	0.038 (3)	0.037 (3)	0.022 (2)	0.001 (2)	0.0086 (19)	−0.005 (2)
N1'	0.045 (4)	0.045 (4)	0.034 (4)	0.003 (3)	0.010 (3)	−0.007 (3)
N2'	0.060 (4)	0.049 (4)	0.037 (4)	−0.004 (3)	0.023 (3)	−0.004 (3)
N3'	0.042 (3)	0.051 (4)	0.035 (3)	0.006 (3)	0.012 (3)	0.003 (3)
N4'	0.035 (3)	0.024 (3)	0.028 (3)	−0.001 (2)	0.008 (2)	−0.003 (2)
C1'	0.027 (4)	0.043 (4)	0.029 (4)	−0.004 (3)	0.007 (3)	−0.008 (3)
C2'	0.022 (3)	0.034 (4)	0.028 (3)	−0.001 (3)	0.009 (3)	−0.001 (3)
C3'	0.035 (4)	0.047 (4)	0.020 (3)	−0.004 (4)	0.014 (3)	−0.006 (3)
C4'	0.020 (3)	0.033 (4)	0.027 (3)	−0.001 (3)	0.009 (2)	−0.005 (3)
C5'	0.031 (4)	0.043 (4)	0.015 (3)	−0.005 (3)	0.004 (2)	−0.006 (3)
C6'	0.020 (3)	0.046 (4)	0.024 (3)	−0.001 (3)	0.008 (3)	−0.003 (3)
C7'	0.021 (3)	0.035 (4)	0.028 (4)	0.002 (3)	0.007 (3)	0.000 (3)
C8'	0.046 (4)	0.055 (4)	0.034 (4)	0.009 (4)	0.013 (3)	−0.001 (3)
C9'	0.059 (4)	0.039 (4)	0.030 (4)	0.002 (3)	0.020 (3)	0.006 (3)
C10'	0.026 (4)	0.037 (4)	0.030 (4)	−0.001 (3)	0.010 (3)	−0.006 (3)
C11'	0.024 (3)	0.036 (4)	0.026 (3)	0.004 (3)	0.007 (3)	0.000 (3)
C12'	0.031 (3)	0.028 (3)	0.031 (4)	0.003 (3)	0.015 (3)	0.000 (3)
C13'	0.026 (3)	0.038 (4)	0.028 (4)	−0.001 (3)	0.009 (3)	−0.002 (3)
C14'	0.034 (4)	0.028 (4)	0.036 (4)	−0.002 (3)	0.015 (3)	−0.006 (3)
C15'	0.051 (4)	0.045 (4)	0.021 (3)	0.008 (4)	0.007 (3)	0.000 (3)
C16'	0.036 (4)	0.054 (5)	0.035 (4)	0.000 (4)	0.009 (3)	−0.004 (3)
C17'	0.034 (4)	0.052 (5)	0.043 (4)	−0.007 (4)	0.014 (3)	−0.010 (3)
C18'	0.050 (4)	0.041 (4)	0.034 (4)	−0.005 (3)	0.017 (3)	−0.005 (3)
C19'	0.037 (4)	0.033 (4)	0.037 (4)	0.010 (3)	0.012 (3)	0.000 (3)

Geometric parameters (Å, º) top

O1—C6	1.355 (6)	O1'—C6'	1.365 (6)
O1—C5	1.478 (6)	O1'—C5'	1.500 (6)
N1—C1	1.128 (7)	N1'—C1'	1.141 (7)
N2—C3	1.156 (7)	N2'—C3'	1.161 (7)
N3—C10	1.157 (7)	N3'—C10'	1.154 (7)
N4—C14	1.310 (7)	N4'—C14'	1.320 (6)
N4—C19	1.458 (6)	N4'—C15'	1.468 (6)
N4—C15	1.466 (7)	N4'—C19'	1.477 (6)
C1—C2	1.446 (8)	C1'—C2'	1.422 (8)
C2—C6	1.381 (8)	C2'—C6'	1.396 (7)
C2—C3	1.412 (8)	C2'—C3'	1.410 (8)
C4—C11	1.370 (7)	C4'—C11'	1.362 (7)
C4—C7	1.426 (8)	C4'—C7'	1.425 (7)
C4—C5	1.523 (8)	C4'—C5'	1.511 (7)
C5—C8	1.527 (7)	C5'—C9'	1.503 (8)
C5—C9	1.534 (8)	C5'—C8'	1.512 (7)
C6—C7	1.390 (7)	C6'—C7'	1.390 (7)
C7—C10	1.404 (8)	C7'—C10'	1.407 (8)
C8—H8A	0.9800	C8'—H8'A	0.9800
C8—H8B	0.9800	C8'—H8'B	0.9800
C8—H8C	0.9800	C8'—H8'C	0.9800
C9—H9A	0.9800	C9'—H9'A	0.9800
C9—H9B	0.9800	C9'—H9'B	0.9800
C9—H9C	0.9800	C9'—H9'C	0.9800
C11—C12	1.398 (7)	C11'—C12'	1.405 (8)
C11—H11	0.9500	C11'—H11'	0.9500
C12—C13	1.380 (7)	C12'—C13'	1.382 (7)
C12—H12	0.9500	C12'—H12'	0.9500
C13—C14	1.396 (8)	C13'—C14'	1.395 (7)
C13—H13	0.9500	C13'—H13'	0.9500
C14—H14	0.9500	C14'—H14'	0.9500
C15—C16	1.501 (7)	C15'—C16'	1.503 (8)
C15—H15A	0.9900	C15'—H15C	0.9900
C15—H15B	0.9900	C15'—H15D	0.9900
C16—C17	1.509 (7)	C16'—C17'	1.522 (8)
C16—H16A	0.9900	C16'—H16C	0.9900
C16—H16B	0.9900	C16'—H16D	0.9900
C17—C18	1.536 (8)	C17'—C18'	1.530 (7)
C17—H17A	0.9900	C17'—H17C	0.9900
C17—H17B	0.9900	C17'—H17D	0.9900
C18—C19	1.508 (7)	C18'—C19'	1.501 (7)
C18—H18A	0.9900	C18'—H18C	0.9900
C18—H18B	0.9900	C18'—H18D	0.9900
C19—H19A	0.9900	C19'—H19C	0.9900
C19—H19B	0.9900	C19'—H19D	0.9900

C6—O1—C5	110.2 (4)	C6'—O1'—C5'	109.4 (4)
C14—N4—C19	123.9 (5)	C14'—N4'—C15'	122.6 (5)
C14—N4—C15	121.3 (5)	C14'—N4'—C19'	124.6 (5)
C19—N4—C15	114.8 (5)	C15'—N4'—C19'	112.4 (4)
N1—C1—C2	175.4 (7)	N1'—C1'—C2'	178.8 (7)
C6—C2—C3	120.7 (6)	C6'—C2'—C3'	121.4 (5)
C6—C2—C1	121.9 (5)	C6'—C2'—C1'	119.8 (5)
C3—C2—C1	117.4 (6)	C3'—C2'—C1'	118.7 (5)
N2—C3—C2	179.1 (8)	N2'—C3'—C2'	178.7 (7)
C11—C4—C7	126.9 (6)	C11'—C4'—C7'	126.2 (5)
C11—C4—C5	127.2 (5)	C11'—C4'—C5'	126.6 (5)
C7—C4—C5	105.9 (5)	C7'—C4'—C5'	107.2 (5)
O1—C5—C4	103.2 (4)	O1'—C5'—C9'	105.1 (4)
O1—C5—C8	106.0 (5)	O1'—C5'—C4'	102.9 (4)
C4—C5—C8	111.1 (5)	C9'—C5'—C4'	115.5 (5)
O1—C5—C9	105.7 (4)	O1'—C5'—C8'	105.8 (5)
C4—C5—C9	116.2 (5)	C9'—C5'—C8'	113.3 (5)
C8—C5—C9	113.5 (5)	C4'—C5'—C8'	112.8 (5)
O1—C6—C2	115.8 (5)	O1'—C6'—C7'	110.9 (5)
O1—C6—C7	110.5 (5)	O1'—C6'—C2'	115.4 (5)
C2—C6—C7	133.7 (6)	C7'—C6'—C2'	133.7 (6)
C6—C7—C10	128.1 (5)	C6'—C7'—C10'	126.9 (5)
C6—C7—C4	109.9 (5)	C6'—C7'—C4'	109.5 (5)
C10—C7—C4	122.0 (5)	C10'—C7'—C4'	123.6 (5)
C5—C8—H8A	109.5	C5'—C8'—H8'A	109.5
C5—C8—H8B	109.5	C5'—C8'—H8'B	109.5
H8A—C8—H8B	109.5	H8'A—C8'—H8'B	109.5
C5—C8—H8C	109.5	C5'—C8'—H8'C	109.5
H8A—C8—H8C	109.5	H8'A—C8'—H8'C	109.5
H8B—C8—H8C	109.5	H8'B—C8'—H8'C	109.5
C5—C9—H9A	109.5	C5'—C9'—H9'A	109.5
C5—C9—H9B	109.5	C5'—C9'—H9'B	109.5
H9A—C9—H9B	109.5	H9'A—C9'—H9'B	109.5
C5—C9—H9C	109.5	C5'—C9'—H9'C	109.5
H9A—C9—H9C	109.5	H9'A—C9'—H9'C	109.5
H9B—C9—H9C	109.5	H9'B—C9'—H9'C	109.5
N3—C10—C7	176.2 (6)	N3'—C10'—C7'	174.9 (6)
C4—C11—C12	125.3 (6)	C4'—C11'—C12'	126.7 (6)
C4—C11—H11	117.3	C4'—C11'—H11'	116.7
C12—C11—H11	117.3	C12'—C11'—H11'	116.7
C13—C12—C11	124.1 (6)	C13'—C12'—C11'	122.9 (6)
C13—C12—H12	118.0	C13'—C12'—H12'	118.5
C11—C12—H12	118.0	C11'—C12'—H12'	118.5
C12—C13—C14	118.4 (6)	C12'—C13'—C14'	119.8 (6)
C12—C13—H13	120.8	C12'—C13'—H13'	120.1
C14—C13—H13	120.8	C14'—C13'—H13'	120.1
N4—C14—C13	127.5 (6)	N4'—C14'—C13'	126.3 (6)
N4—C14—H14	116.3	N4'—C14'—H14'	116.9
C13—C14—H14	116.3	C13'—C14'—H14'	116.9
N4—C15—C16	109.8 (5)	N4'—C15'—C16'	111.6 (5)
N4—C15—H15A	109.7	N4'—C15'—H15C	109.3
C16—C15—H15A	109.7	C16'—C15'—H15C	109.3
N4—C15—H15B	109.7	N4'—C15'—H15D	109.3
C16—C15—H15B	109.7	C16'—C15'—H15D	109.3
H15A—C15—H15B	108.2	H15C—C15'—H15D	108.0
C15—C16—C17	110.3 (5)	C15'—C16'—C17'	110.2 (5)
C15—C16—H16A	109.6	C15'—C16'—H16C	109.6
C17—C16—H16A	109.6	C17'—C16'—H16C	109.6
C15—C16—H16B	109.6	C15'—C16'—H16D	109.6
C17—C16—H16B	109.6	C17'—C16'—H16D	109.6
H16A—C16—H16B	108.1	H16C—C16'—H16D	108.1
C16—C17—C18	109.8 (5)	C16'—C17'—C18'	110.6 (5)
C16—C17—H17A	109.7	C16'—C17'—H17C	109.5
C18—C17—H17A	109.7	C18'—C17'—H17C	109.5
C16—C17—H17B	109.7	C16'—C17'—H17D	109.5
C18—C17—H17B	109.7	C18'—C17'—H17D	109.5
H17A—C17—H17B	108.2	H17C—C17'—H17D	108.1
C19—C18—C17	110.8 (5)	C19'—C18'—C17'	110.6 (5)
C19—C18—H18A	109.5	C19'—C18'—H18C	109.5
C17—C18—H18A	109.5	C17'—C18'—H18C	109.5
C19—C18—H18B	109.5	C19'—C18'—H18D	109.5
C17—C18—H18B	109.5	C17'—C18'—H18D	109.5
H18A—C18—H18B	108.1	H18C—C18'—H18D	108.1
N4—C19—C18	110.3 (5)	N4'—C19'—C18'	109.6 (4)
N4—C19—H19A	109.6	N4'—C19'—H19C	109.8
C18—C19—H19A	109.6	C18'—C19'—H19C	109.8
N4—C19—H19B	109.6	N4'—C19'—H19D	109.8
C18—C19—H19B	109.6	C18'—C19'—H19D	109.8
H19A—C19—H19B	108.1	H19C—C19'—H19D	108.2

C6—O1—C5—C4	5.6 (5)	C6'—O1'—C5'—C9'	−121.2 (5)
C6—O1—C5—C8	−111.2 (5)	C6'—O1'—C5'—C4'	0.1 (6)
C6—O1—C5—C9	128.1 (5)	C6'—O1'—C5'—C8'	118.7 (5)
C11—C4—C5—O1	174.9 (5)	C11'—C4'—C5'—O1'	−178.6 (5)
C7—C4—C5—O1	−5.7 (6)	C7'—C4'—C5'—O1'	1.6 (6)
C11—C4—C5—C8	−71.9 (7)	C11'—C4'—C5'—C9'	−64.7 (8)
C7—C4—C5—C8	107.4 (5)	C7'—C4'—C5'—C9'	115.5 (5)
C11—C4—C5—C9	59.8 (7)	C11'—C4'—C5'—C8'	67.9 (8)
C7—C4—C5—C9	−120.8 (5)	C7'—C4'—C5'—C8'	−112.0 (5)
C5—O1—C6—C2	177.3 (5)	C5'—O1'—C6'—C7'	−1.7 (7)
C5—O1—C6—C7	−3.3 (6)	C5'—O1'—C6'—C2'	176.7 (5)
C3—C2—C6—O1	0.9 (8)	C3'—C2'—C6'—O1'	−0.9 (8)
C1—C2—C6—O1	−176.6 (5)	C1'—C2'—C6'—O1'	−176.6 (5)
C3—C2—C6—C7	−178.2 (6)	C3'—C2'—C6'—C7'	177.0 (7)
C1—C2—C6—C7	4.3 (11)	C1'—C2'—C6'—C7'	1.3 (11)
O1—C6—C7—C10	179.1 (5)	O1'—C6'—C7'—C10'	−177.2 (5)
C2—C6—C7—C10	−1.7 (11)	C2'—C6'—C7'—C10'	4.8 (11)
O1—C6—C7—C4	−0.6 (7)	O1'—C6'—C7'—C4'	2.8 (7)
C2—C6—C7—C4	178.5 (6)	C2'—C6'—C7'—C4'	−175.2 (6)
C11—C4—C7—C6	−176.5 (5)	C11'—C4'—C7'—C6'	177.5 (6)
C5—C4—C7—C6	4.1 (7)	C5'—C4'—C7'—C6'	−2.7 (6)
C11—C4—C7—C10	3.8 (10)	C11'—C4'—C7'—C10'	−2.5 (10)
C5—C4—C7—C10	−175.6 (5)	C5'—C4'—C7'—C10'	177.3 (5)
C7—C4—C11—C12	−174.8 (6)	C7'—C4'—C11'—C12'	−177.9 (6)
C5—C4—C11—C12	4.4 (10)	C5'—C4'—C11'—C12'	2.3 (10)
C4—C11—C12—C13	179.1 (5)	C4'—C11'—C12'—C13'	177.1 (6)
C11—C12—C13—C14	−177.9 (6)	C11'—C12'—C13'—C14'	−179.4 (5)
C19—N4—C14—C13	1.9 (10)	C15'—N4'—C14'—C13'	173.0 (6)
C15—N4—C14—C13	−176.8 (6)	C19'—N4'—C14'—C13'	0.6 (10)
C12—C13—C14—N4	−174.1 (5)	C12'—C13'—C14'—N4'	177.6 (5)
C14—N4—C15—C16	121.5 (6)	C14'—N4'—C15'—C16'	−115.0 (6)
C19—N4—C15—C16	−57.3 (6)	C19'—N4'—C15'—C16'	58.3 (7)
N4—C15—C16—C17	57.2 (7)	N4'—C15'—C16'—C17'	−55.0 (7)
C15—C16—C17—C18	−57.4 (7)	C15'—C16'—C17'—C18'	53.9 (7)
C16—C17—C18—C19	55.7 (7)	C16'—C17'—C18'—C19'	−55.8 (7)
C14—N4—C19—C18	−123.2 (6)	C14'—N4'—C19'—C18'	114.3 (6)
C15—N4—C19—C18	55.5 (7)	C15'—N4'—C19'—C18'	−58.9 (7)
C17—C18—C19—N4	−53.5 (7)	C17'—C18'—C19'—N4'	57.2 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13′—H13′···N2ⁱ	0.95	2.49	3.324 (8)	147
C14—H14···N1′	0.95	2.58	3.498 (8)	161
C14′—H14′···N1ⁱⁱ	0.95	2.61	3.484 (8)	153
C16′—H16D···N2ⁱⁱ	0.99	2.55	3.477 (8)	156
C19—H19A···N2′ⁱⁱⁱ	0.99	2.60	3.568 (8)	166

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₂₀N₄O
M_r	320.39
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	119
a, b, c (Å)	15.094 (4), 18.994 (5), 13.332 (4)
β (°)	116.193 (8)
V (Å³)	3429.7 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.35 × 0.25 × 0.09

Data collection
Diffractometer	Bruker–Nonius APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.733, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	18712, 11128, 5766
R_int	0.088
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.079, 0.203, 1.02
No. of reflections	11128
No. of parameters	424
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.36

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005) and SADABS (Sheldrick, 2003), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13'—H13'···N2ⁱ	0.95	2.49	3.324 (8)	147
C14—H14···N1'	0.95	2.58	3.498 (8)	161
C14'—H14'···N1ⁱⁱ	0.95	2.61	3.484 (8)	153
C16'—H16D···N2ⁱⁱ	0.99	2.55	3.477 (8)	156
C19—H19A···N2'ⁱⁱⁱ	0.99	2.60	3.568 (8)	166

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1, −y+3/2, z−1/2; (iii) −x+1, y−1/2, −z+3/2.

Acknowledgements

We thank Professor Ward T. Robinson and Dr J. Wikaira of the University of Canterbury for their assistance in data collection.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bock, H., Nick, S., Seitz, W., Nather, C. & Bats, J. W. (1996). Z. Naturforsch. Teil B Chem. Sci. 51, 153–171. CAS Google Scholar
Bruker (2005). APEX2 (Version 2.0-2) and SAINT (Version 7.12A). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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Gainsford, G. J., Bhuiyan, M. D. H. & Kay, A. J. (2008). Acta Cryst. C64. Submitted. Google Scholar
Kay, A. J., Woolhouse, A. D., Zhao, Y. & Clays, K. (2004). J. Mater. Chem. 14, 1321–1330. Web of Science CrossRef CAS Google Scholar
Marder, S. R., Perry, J. W., Tiemann, B. G., Gorman, C. B., Gilmour, S., Biddle, S. L. & Bourhill, G. (1993). J. Am. Chem. Soc. 115, 2524–2526. CSD CrossRef CAS Web of Science Google Scholar
Reck, G. & Dahne, L. (2006). Private communication (refcode NEQHAT01). CCDC, Union Road, Cambridge, England. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.08. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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

2-{3-Cyano-5,5-di­methyl-4-[4-(piperidin-1-yl)buta-1,3-dien­yl]-2,5-di­hydro­furan-2-yl­­idene}malono­nitrile

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-{3-Cyano-5,5-dimethyl-4-[4-(piperidin-1-yl)buta-1,3-dienyl]-2,5-dihydrofuran-2-ylidene}malononitrile