2-(4-{3-[1-(3-Bromo­prop­yl)-3,3-dimethyl-2,3-dihydro-1H-indol-2-yl­idene]prop-1-en­yl}-3-cyano-5,5-dimethyl-2,5-dihydro­furan-2-yl­idene)malononitrile

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

doi:10.1107/S1600536809017747

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1315

doi:10.1107/S1600536809017747

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2-(4-{3-[1-(3-Bromopropyl)-3,3-dimethyl-2,3-dihydro-1H-indol-2-ylidene]prop-1-enyl}-3-cyano-5,5-dimethyl-2,5-dihydrofuran-2-ylidene)malononitrile

Graeme J. Gainsford,^a ^* M. Delower H. Bhuiyan ^a and Andrew J. Kay ^a

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

(Received 11 May 2009; accepted 11 May 2009; online 20 May 2009)

The backbone of the title molecule, C₂₆H₂₅BrN₄O, is approximately planar: the dihedral angle between the planes of the indoline ring system and the furan ring is 7.68 (14)°. In the crystal, layers lying parallel to (10 $[\overline{2}]$ ) occur, with the molecules interacting via weak C—H⋯N(cyano) and C—H⋯Br bonds and short N(cyano)⋯Br contacts [3.345 (4) Å].

Related literature

For general background to zwitterionic dyes and their applications, see: Dalton (2002 ); Gainsford et al. (2007 , 2008 ); Kay et al. (2004 ). For related structures, see: Li et al. (2005 ); Marder et al. (1993 ); Mushkalo & Sogulayaev (1986 ); Wang et al. (2007 ). For a description of the Cambridge Stuctural Database, see: Allen (2002 ).

Experimental

Crystal data

C₂₆H₂₅BrN₄O
M_r = 489.41
Monoclinic, P 2₁ /c
a = 10.2349 (4) Å
b = 9.4017 (4) Å
c = 24.4524 (10) Å
β = 96.175 (2)°
V = 2339.29 (17) Å³
Z = 4
Mo Kα radiation
μ = 1.78 mm⁻¹
T = 122 K
0.85 × 0.36 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.549, T_max = 0.746 (expected range = 0.616–0.837)
56895 measured reflections
6791 independent reflections
5482 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.156
S = 1.19
6791 reflections
293 parameters
H-atom parameters constrained
Δρ_max = 3.08 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯N1ⁱ	0.98	2.59	3.449 (5)	147
C23—H23B⋯Br1ⁱⁱ	0.98	2.99	3.962 (4)	171
C26—H26B⋯Br1ⁱⁱⁱ	0.99	2.95	3.815 (4)	147
Symmetry codes: (i) x, y-1, z; (ii) x, y+1, z; (iii) -x+2, -y, -z+1.

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 ), PLATON (Spek, 2009 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809017747/hb2973sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017747/hb2973Isup2.hkl

checkCIF report

Comment top

The X-ray crystallographic and structural properties of zwitterionic dyes and their precursors have been a subject of some interest to us (Gainsford et al., 2007, 2008) due to their potential application in a number of photonic and optoelectronic devices (Dalton, 2002; Kay et al., 2004). The title compound was unintentionally synthesized en route to 2-{3-Cyano-4-[2-(10,10-dimethyl-6,7,8,10-tetrahydro-pyrido[1,2-a] indol-9-yl)-vinyl]-5,5-dimethyl-5H-furan-2-ylidene}-malononitrile. Compound REFCODES are from the C.S.D. (Version 5.30, with February 2009 updates; Allen, 2002)

The asymmetric unit contents are shown in Figure 1. The 5-membered ring plane of atoms O1,C4—C7 (hereafter "CDFP", [3-Cyano-5,5-Dimethyl-2,5-dihydrofuran-2-ylidene]propanedinitrile) can also be regarded as planar in this case (r.m.s. deviations 0.024 (3) Å). The dicyano group (N1,C1,C2,C3,N2) is planar (r.m.s.d. 0.008 (3) Å) but twisted by 6.6 (2)° with respect to the "CDFP" group; this is similar to the twist in related compound NOJKUT (Gainsford et al., 2008) of 5.69 (17)°. The fused indolylidene system (atoms N4, C14 to C21) is also essentially planar (r.m.s.d. 0.017 (3) Å) and makes a dihedral angle with the "CDFP" ring of 7.68 (14)°. This reflects a twist in the C11–C14 polyene chain beginning at C11: the plane through C11–C14 subtends 5.4 (3)° with the "CDFP" plane. There is considerable delocalization of charge along the polyene /"CDFP" chain with a bond length alternation (BLA) value (Marder et al., 1993) of 0.012Å compared with the free "CDFP" value of 0.108Å (Li et al., 2005) and 0.060Å in GIMQAV (Gainsford et al., 2007).

The almost planar molecules are arranged into nearly coplanar layers parallel to the (1,0,-2) plane with only C–H···N(cyano), C–H···Br and N(cyano)···Br contacts. The (methyl)C–H···N(cyano) contact (Table 1) is similar to that observed in several structures (Allen, 2002), where the methyl group is constrained by other interactions e.g. in JETGEV (Wang et al. 2007; N···H 2.57 Å, C–H···N 157°) the cyano nitrogen involved is bifurcated by a polyene C–H···N interation (H···N 2.72 Å, C–H···N 157°). Here the distance to the equivalent polyene H (H11) is 2.75 Å, with C–H···N 161°. In NOJKUT, a similar interaction is observed: H···N 2.45 Å, C–H···N 156°. The bromine atoms provide weak linking interactions: N2···Br1 3.345 (4)Å (Br1 at x - 1,1/2 - y,z - 1/2) and two C–H···Br interactions (Table 1). A final interaction is noted for completeness that would complete a weak interacting chain (N2···H23C(C23)H23B···Br1···N2) with H23C···N2 (N2 at 1 - x, y - 1/2,1/2 - z) and provide a weak interplanar link (see also Figure 2).

Related literature top

For general background to zwitterionic dyes and their applications, see: Dalton (2002); Gainsford et al. (2007, 2008); Kay et al. (2004). For related structures, see: Li et al. (2005); Marder et al. (1993); Mushkalo & Sogulayaev (1986); Wang et al. (2007). For a description of the Cambridge Stuctural Database, see: Allen (2002).

Experimental top

A mixture of 1 g (2.77 mmol) of 1-(3-bromopropyl)-2,3,3-trimethyl-3H-indolium bromide (Mushkalo & Sogulayaev, 1986), 883 mg (2.21 mmol) of {4-(2-acetanilidoethenyl)-3-cyano-5,5-dimethyl-2(5H)-furanylidene} propanedinitrile (compound 11a; Kay et al., 2004) and triethylamine as a catalyst in 30 ml me thanol was refluxed for 3 h. After cooling to room temperature, the precipitate was filtered and washed with copious quantities of hot water, followed by small portions of cold methanol to afford the target molecule as a red-purple powder (720 mg, 67%). Platy crystals, of limited quality, were grown from a 2:1 dichloromethane/hexanes mixture. Mp: 264–266 °C; ¹H NMR (500 MHz, CDCl₃) δ 1.61 (6 H, s, 2 x CH₃), 1.72 (6 H, s, 2 x CH₃), 2.34 (2 H, qn, CH₂), 3.50 (2 H, t, J 5.7 Hz, CH₂), 4.06 (2 H, t, J 7.2 Hz, CH₂), 5.78 (1 H, d, J 12.9 Hz, CH), 5.85 (1 H, d, J 12.9 Hz, CH), 7.04 (1 H, d, J 7.8 Hz, ArH), 7.16–7.21 (1 H, m, ArH), 7.31–7.37 (2 H, m, ArH), 8.78 (1H, br s, ArH); ¹³C NMR (125 MHz, CDCl₃) δ 26.4, 27.7, 29.8, 29.9, 41.8, 48.9, 95.7, 99.9, 107.3, 109.3, 112.9, 113.8, 122.4, 124.6, 128.6, 140.4, 142.0, 147.3, 172.7, 177.4.

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), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Molecular structure of the asymmetric unit (Farrugia, 1997); displacement ellipsoids are shown at the 30% probability level.
	Fig. 2. Packing diagram of the unit cell. Contact atoms are shown as balls; not all interactions and labels are shown for clarity (see text). Symmetry (i) x - 1,1/2 - y, z - 1/2 (ii) x, 1 + y, z (iii) 1 - x, y - 1/2,1/2 - z.

2-(4-{3-[1-(3-Bromopropyl)-3,3-dimethyl-2,3-dihydro-1H-indol-2- ylidene]prop-1-enyl}-3-cyano-5,5-dimethyl-2,5-dihydrofuran-2- ylidene)malononitrile top

Crystal data top

C₂₆H₂₅BrN₄O	F(000) = 1008
M_r = 489.41	D_x = 1.390 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9973 reflections
a = 10.2349 (4) Å	θ = 2.3–29.3°
b = 9.4017 (4) Å	µ = 1.78 mm⁻¹
c = 24.4524 (10) Å	T = 122 K
β = 96.175 (2)°	Block, red
V = 2339.29 (17) Å³	0.85 × 0.36 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	6791 independent reflections
Radiation source: fine-focus sealed tube	5482 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 8.333 pixels mm^-1	θ_max = 30.0°, θ_min = 2.5°
ϕ and ω scans	h = −14→14
Absorption correction: multi-scan (Blessing, 1995)	k = −13→13
T_min = 0.549, T_max = 0.746	l = −34→34
56895 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.0596P)² + 4.5665P] where P = (F_o² + 2F_c²)/3
6791 reflections	(Δ/σ)_max = 0.001
293 parameters	Δρ_max = 3.08 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

C₂₆H₂₅BrN₄O	V = 2339.29 (17) Å³
M_r = 489.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.2349 (4) Å	µ = 1.78 mm⁻¹
b = 9.4017 (4) Å	T = 122 K
c = 24.4524 (10) Å	0.85 × 0.36 × 0.10 mm
β = 96.175 (2)°

Data collection top

Bruker APEXII CCD diffractometer	6791 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	5482 reflections with I > 2σ(I)
T_min = 0.549, T_max = 0.746	R_int = 0.044
56895 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.19	Δρ_max = 3.08 e Å⁻³
6791 reflections	Δρ_min = −0.60 e Å⁻³
293 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
Br1	1.04264 (4)	−0.19667 (4)	0.464951 (13)	0.03123 (11)
O1	0.4789 (2)	0.4651 (2)	0.11618 (9)	0.0259 (5)
N1	0.5733 (4)	0.9332 (3)	0.18253 (17)	0.0487 (9)
N2	0.3317 (4)	0.7471 (5)	0.04014 (15)	0.0487 (9)
N3	0.7924 (3)	0.6919 (3)	0.24466 (12)	0.0302 (6)
N4	1.0399 (2)	0.1410 (3)	0.36430 (10)	0.0183 (4)
C1	0.5374 (4)	0.8345 (4)	0.15816 (16)	0.0330 (7)
C2	0.4909 (3)	0.7121 (3)	0.12784 (14)	0.0258 (6)
C3	0.4020 (3)	0.7300 (4)	0.07938 (15)	0.0317 (7)
C4	0.6310 (3)	0.3831 (3)	0.18773 (11)	0.0186 (5)
C5	0.5308 (3)	0.3319 (3)	0.14217 (12)	0.0210 (6)
C6	0.5325 (3)	0.5769 (3)	0.14380 (12)	0.0210 (5)
C7	0.6286 (3)	0.5313 (3)	0.18679 (12)	0.0195 (5)
C8	0.5913 (3)	0.2449 (4)	0.09903 (13)	0.0263 (6)
H8A	0.5238	0.2225	0.0688	0.040*
H8B	0.6274	0.1564	0.1156	0.040*
H8C	0.6619	0.2997	0.0849	0.040*
C9	0.4168 (3)	0.2573 (4)	0.16424 (16)	0.0308 (7)
H9A	0.3757	0.3215	0.1890	0.046*
H9B	0.4486	0.1720	0.1845	0.046*
H9C	0.3520	0.2300	0.1336	0.046*
C10	0.7165 (3)	0.6235 (3)	0.21904 (12)	0.0213 (5)
C11	0.7057 (3)	0.2857 (3)	0.22079 (12)	0.0208 (5)
H11	0.6935	0.1877	0.2123	0.025*
C12	0.7964 (3)	0.3200 (3)	0.26505 (12)	0.0213 (6)
H12	0.8067	0.4170	0.2755	0.026*
C13	0.8724 (3)	0.2188 (3)	0.29458 (12)	0.0209 (5)
H13	0.8588	0.1224	0.2838	0.025*
C14	0.9674 (3)	0.2454 (3)	0.33870 (11)	0.0182 (5)
C15	1.1325 (3)	0.1961 (3)	0.40603 (11)	0.0201 (5)
C16	1.2270 (3)	0.1236 (3)	0.43992 (12)	0.0214 (5)
H16	1.2363	0.0233	0.4377	0.026*
C17	1.3078 (3)	0.2043 (4)	0.47734 (13)	0.0280 (6)
H17	1.3740	0.1583	0.5012	0.034*
C18	1.2933 (3)	0.3511 (4)	0.48045 (14)	0.0293 (7)
H18	1.3500	0.4040	0.5063	0.035*
C19	1.1968 (3)	0.4214 (4)	0.44613 (13)	0.0267 (6)
H19	1.1860	0.5215	0.4485	0.032*
C20	1.1171 (3)	0.3418 (3)	0.40854 (12)	0.0203 (5)
C21	1.0071 (3)	0.3868 (3)	0.36571 (11)	0.0193 (5)
C22	1.0602 (3)	0.4925 (3)	0.32554 (14)	0.0272 (6)
H22A	1.1278	0.4459	0.3064	0.041*
H22B	1.0984	0.5748	0.3460	0.041*
H22C	0.9882	0.5241	0.2986	0.041*
C23	0.8931 (3)	0.4525 (4)	0.39357 (13)	0.0263 (6)
H23A	0.8224	0.4806	0.3654	0.039*
H23B	0.9248	0.5363	0.4148	0.039*
H23C	0.8596	0.3823	0.4182	0.039*
C24	1.0321 (3)	−0.0092 (3)	0.34754 (12)	0.0206 (5)
H24A	1.1117	−0.0592	0.3643	0.025*
H24B	1.0317	−0.0147	0.3071	0.025*
C25	0.9108 (3)	−0.0860 (3)	0.36403 (12)	0.0237 (6)
H25A	0.8316	−0.0389	0.3455	0.028*
H25B	0.9116	−0.1849	0.3502	0.028*
C26	0.8990 (3)	−0.0903 (4)	0.42482 (13)	0.0281 (6)
H26A	0.8143	−0.1349	0.4311	0.034*
H26B	0.8990	0.0082	0.4392	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0428 (2)	0.02650 (17)	0.02325 (16)	−0.00417 (14)	−0.00169 (12)	0.00277 (13)
O1	0.0256 (10)	0.0217 (10)	0.0283 (11)	0.0037 (8)	−0.0076 (8)	0.0013 (9)
N1	0.061 (2)	0.0208 (15)	0.061 (2)	0.0085 (15)	−0.0063 (18)	−0.0004 (15)
N2	0.0389 (18)	0.065 (2)	0.0400 (19)	0.0197 (17)	−0.0053 (15)	0.0059 (17)
N3	0.0309 (14)	0.0266 (14)	0.0326 (14)	0.0013 (11)	0.0015 (11)	−0.0061 (12)
N4	0.0171 (10)	0.0198 (11)	0.0173 (11)	−0.0004 (9)	−0.0010 (8)	0.0007 (9)
C1	0.0345 (17)	0.0250 (16)	0.0390 (19)	0.0095 (13)	0.0019 (14)	0.0068 (14)
C2	0.0247 (14)	0.0243 (15)	0.0280 (15)	0.0087 (12)	0.0012 (11)	0.0049 (12)
C3	0.0285 (16)	0.0319 (18)	0.0348 (18)	0.0122 (13)	0.0032 (13)	0.0056 (14)
C4	0.0176 (12)	0.0212 (13)	0.0169 (12)	0.0015 (10)	0.0013 (9)	−0.0016 (10)
C5	0.0188 (12)	0.0187 (13)	0.0242 (14)	0.0030 (10)	−0.0044 (10)	0.0021 (10)
C6	0.0196 (12)	0.0221 (14)	0.0210 (13)	0.0046 (10)	0.0017 (10)	0.0015 (11)
C7	0.0198 (12)	0.0193 (13)	0.0193 (13)	0.0032 (10)	0.0012 (10)	−0.0007 (10)
C8	0.0299 (16)	0.0261 (15)	0.0221 (14)	0.0014 (12)	−0.0016 (12)	−0.0022 (12)
C9	0.0172 (13)	0.0291 (16)	0.046 (2)	0.0003 (12)	0.0014 (13)	0.0062 (14)
C10	0.0228 (13)	0.0179 (13)	0.0232 (14)	0.0042 (10)	0.0034 (10)	−0.0013 (11)
C11	0.0215 (13)	0.0190 (13)	0.0212 (13)	0.0018 (10)	−0.0016 (10)	0.0005 (10)
C12	0.0209 (13)	0.0216 (14)	0.0210 (13)	0.0000 (10)	0.0004 (10)	−0.0001 (10)
C13	0.0226 (13)	0.0192 (13)	0.0200 (13)	−0.0012 (10)	−0.0021 (10)	0.0001 (10)
C14	0.0178 (12)	0.0204 (13)	0.0165 (12)	0.0000 (10)	0.0018 (10)	0.0025 (10)
C15	0.0159 (11)	0.0288 (14)	0.0155 (12)	−0.0019 (11)	0.0017 (9)	0.0028 (11)
C16	0.0188 (12)	0.0238 (14)	0.0212 (13)	−0.0010 (10)	0.0002 (10)	0.0026 (11)
C17	0.0198 (13)	0.0391 (18)	0.0237 (14)	−0.0021 (13)	−0.0043 (11)	0.0043 (13)
C18	0.0241 (14)	0.0344 (17)	0.0271 (15)	−0.0080 (13)	−0.0074 (12)	−0.0015 (13)
C19	0.0272 (14)	0.0232 (15)	0.0283 (15)	−0.0074 (12)	−0.0040 (12)	0.0001 (12)
C20	0.0194 (12)	0.0221 (13)	0.0188 (13)	−0.0042 (10)	−0.0008 (10)	0.0024 (10)
C21	0.0201 (12)	0.0191 (13)	0.0179 (12)	−0.0038 (10)	−0.0011 (10)	0.0024 (10)
C22	0.0296 (15)	0.0215 (14)	0.0296 (15)	−0.0067 (12)	−0.0014 (12)	0.0065 (12)
C23	0.0253 (14)	0.0252 (15)	0.0278 (15)	−0.0004 (12)	0.0009 (11)	−0.0057 (12)
C24	0.0237 (13)	0.0194 (13)	0.0184 (13)	0.0011 (10)	0.0012 (10)	−0.0014 (10)
C25	0.0253 (14)	0.0222 (14)	0.0227 (14)	−0.0060 (11)	−0.0021 (11)	−0.0002 (11)
C26	0.0278 (15)	0.0312 (17)	0.0261 (15)	−0.0029 (13)	0.0061 (12)	0.0006 (13)

Geometric parameters (Å, º) top

Br1—C26	1.953 (3)	C13—H13	0.9500
O1—C6	1.336 (4)	C14—C21	1.520 (4)
O1—C5	1.476 (3)	C15—C20	1.382 (4)
N1—C1	1.142 (5)	C15—C16	1.383 (4)
N2—C3	1.147 (5)	C16—C17	1.390 (4)
N3—C10	1.142 (4)	C16—H16	0.9500
N4—C14	1.344 (4)	C17—C18	1.392 (5)
N4—C15	1.414 (4)	C17—H17	0.9500
N4—C24	1.470 (4)	C18—C19	1.393 (4)
C1—C2	1.423 (5)	C18—H18	0.9500
C2—C6	1.383 (4)	C19—C20	1.382 (4)
C2—C3	1.424 (5)	C19—H19	0.9500
C4—C7	1.394 (4)	C20—C21	1.513 (4)
C4—C11	1.395 (4)	C21—C22	1.537 (4)
C4—C5	1.510 (4)	C21—C23	1.542 (4)
C5—C9	1.510 (4)	C22—H22A	0.9800
C5—C8	1.519 (4)	C22—H22B	0.9800
C6—C7	1.426 (4)	C22—H22C	0.9800
C7—C10	1.424 (4)	C23—H23A	0.9800
C8—H8A	0.9800	C23—H23B	0.9800
C8—H8B	0.9800	C23—H23C	0.9800
C8—H8C	0.9800	C24—C25	1.528 (4)
C9—H9A	0.9800	C24—H24A	0.9900
C9—H9B	0.9800	C24—H24B	0.9900
C9—H9C	0.9800	C25—C26	1.505 (4)
C11—C12	1.386 (4)	C25—H25A	0.9900
C11—H11	0.9500	C25—H25B	0.9900
C12—C13	1.383 (4)	C26—H26A	0.9900
C12—H12	0.9500	C26—H26B	0.9900
C13—C14	1.395 (4)

C6—O1—C5	109.9 (2)	C15—C16—C17	117.0 (3)
C14—N4—C15	111.2 (2)	C15—C16—H16	121.5
C14—N4—C24	124.2 (2)	C17—C16—H16	121.5
C15—N4—C24	124.4 (2)	C16—C17—C18	121.2 (3)
N1—C1—C2	179.2 (4)	C16—C17—H17	119.4
C6—C2—C1	121.4 (3)	C18—C17—H17	119.4
C6—C2—C3	119.5 (3)	C17—C18—C19	120.7 (3)
C1—C2—C3	119.1 (3)	C17—C18—H18	119.7
N2—C3—C2	178.6 (4)	C19—C18—H18	119.7
C7—C4—C11	132.4 (3)	C20—C19—C18	118.3 (3)
C7—C4—C5	107.3 (2)	C20—C19—H19	120.9
C11—C4—C5	120.3 (3)	C18—C19—H19	120.9
O1—C5—C4	103.4 (2)	C15—C20—C19	120.3 (3)
O1—C5—C9	107.0 (2)	C15—C20—C21	109.1 (2)
C4—C5—C9	112.0 (3)	C19—C20—C21	130.6 (3)
O1—C5—C8	108.2 (2)	C20—C21—C14	101.6 (2)
C4—C5—C8	112.9 (2)	C20—C21—C22	109.6 (2)
C9—C5—C8	112.7 (3)	C14—C21—C22	112.6 (2)
O1—C6—C2	118.9 (3)	C20—C21—C23	110.4 (2)
O1—C6—C7	110.4 (2)	C14—C21—C23	111.2 (2)
C2—C6—C7	130.6 (3)	C22—C21—C23	111.1 (3)
C4—C7—C10	126.2 (3)	C21—C22—H22A	109.5
C4—C7—C6	108.8 (3)	C21—C22—H22B	109.5
C10—C7—C6	124.7 (3)	H22A—C22—H22B	109.5
C5—C8—H8A	109.5	C21—C22—H22C	109.5
C5—C8—H8B	109.5	H22A—C22—H22C	109.5
H8A—C8—H8B	109.5	H22B—C22—H22C	109.5
C5—C8—H8C	109.5	C21—C23—H23A	109.5
H8A—C8—H8C	109.5	C21—C23—H23B	109.5
H8B—C8—H8C	109.5	H23A—C23—H23B	109.5
C5—C9—H9A	109.5	C21—C23—H23C	109.5
C5—C9—H9B	109.5	H23A—C23—H23C	109.5
H9A—C9—H9B	109.5	H23B—C23—H23C	109.5
C5—C9—H9C	109.5	N4—C24—C25	113.6 (2)
H9A—C9—H9C	109.5	N4—C24—H24A	108.8
H9B—C9—H9C	109.5	C25—C24—H24A	108.8
N3—C10—C7	176.1 (3)	N4—C24—H24B	108.8
C12—C11—C4	125.4 (3)	C25—C24—H24B	108.8
C12—C11—H11	117.3	H24A—C24—H24B	107.7
C4—C11—H11	117.3	C26—C25—C24	115.3 (2)
C13—C12—C11	122.7 (3)	C26—C25—H25A	108.5
C13—C12—H12	118.7	C24—C25—H25A	108.5
C11—C12—H12	118.7	C26—C25—H25B	108.5
C12—C13—C14	125.9 (3)	C24—C25—H25B	108.5
C12—C13—H13	117.0	H25A—C25—H25B	107.5
C14—C13—H13	117.0	C25—C26—Br1	112.0 (2)
N4—C14—C13	122.2 (3)	C25—C26—H26A	109.2
N4—C14—C21	109.2 (2)	Br1—C26—H26A	109.2
C13—C14—C21	128.6 (3)	C25—C26—H26B	109.2
C20—C15—C16	122.5 (3)	Br1—C26—H26B	109.2
C20—C15—N4	108.9 (2)	H26A—C26—H26B	107.9
C16—C15—N4	128.5 (3)

C6—O1—C5—C4	−3.6 (3)	C12—C13—C14—C21	2.0 (5)
C6—O1—C5—C9	114.8 (3)	C14—N4—C15—C20	1.6 (3)
C6—O1—C5—C8	−123.5 (3)	C24—N4—C15—C20	176.2 (2)
C7—C4—C5—O1	1.8 (3)	C14—N4—C15—C16	−177.6 (3)
C11—C4—C5—O1	−177.6 (3)	C24—N4—C15—C16	−3.0 (4)
C7—C4—C5—C9	−113.0 (3)	C20—C15—C16—C17	−0.1 (4)
C11—C4—C5—C9	67.6 (3)	N4—C15—C16—C17	179.0 (3)
C7—C4—C5—C8	118.5 (3)	C15—C16—C17—C18	0.2 (5)
C11—C4—C5—C8	−60.9 (4)	C16—C17—C18—C19	0.3 (5)
C5—O1—C6—C2	−176.3 (3)	C17—C18—C19—C20	−0.8 (5)
C5—O1—C6—C7	4.1 (3)	C16—C15—C20—C19	−0.5 (4)
C1—C2—C6—O1	175.3 (3)	N4—C15—C20—C19	−179.7 (3)
C3—C2—C6—O1	−6.1 (5)	C16—C15—C20—C21	179.2 (3)
C1—C2—C6—C7	−5.1 (5)	N4—C15—C20—C21	0.0 (3)
C3—C2—C6—C7	173.4 (3)	C18—C19—C20—C15	0.9 (5)
C11—C4—C7—C10	6.0 (5)	C18—C19—C20—C21	−178.7 (3)
C5—C4—C7—C10	−173.3 (3)	C15—C20—C21—C14	−1.4 (3)
C11—C4—C7—C6	179.7 (3)	C19—C20—C21—C14	178.3 (3)
C5—C4—C7—C6	0.5 (3)	C15—C20—C21—C22	−120.6 (3)
O1—C6—C7—C4	−2.9 (3)	C19—C20—C21—C22	59.1 (4)
C2—C6—C7—C4	177.6 (3)	C15—C20—C21—C23	116.7 (3)
O1—C6—C7—C10	171.0 (3)	C19—C20—C21—C23	−63.6 (4)
C2—C6—C7—C10	−8.6 (5)	N4—C14—C21—C20	2.3 (3)
C7—C4—C11—C12	3.6 (5)	C13—C14—C21—C20	−177.8 (3)
C5—C4—C11—C12	−177.2 (3)	N4—C14—C21—C22	119.4 (3)
C4—C11—C12—C13	−176.6 (3)	C13—C14—C21—C22	−60.7 (4)
C11—C12—C13—C14	178.5 (3)	N4—C14—C21—C23	−115.1 (3)
C15—N4—C14—C13	177.6 (3)	C13—C14—C21—C23	64.8 (4)
C24—N4—C14—C13	2.9 (4)	C14—N4—C24—C25	−76.2 (3)
C15—N4—C14—C21	−2.5 (3)	C15—N4—C24—C25	109.9 (3)
C24—N4—C14—C21	−177.1 (2)	N4—C24—C25—C26	−60.1 (4)
C12—C13—C14—N4	−178.1 (3)	C24—C25—C26—Br1	−63.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···N1ⁱ	0.98	2.59	3.449 (5)	147
C23—H23B···Br1ⁱⁱ	0.98	2.99	3.962 (4)	171
C26—H26B···Br1ⁱⁱⁱ	0.99	2.95	3.815 (4)	147

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

Experimental details

Crystal data
Chemical formula	C₂₆H₂₅BrN₄O
M_r	489.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	122
a, b, c (Å)	10.2349 (4), 9.4017 (4), 24.4524 (10)
β (°)	96.175 (2)
V (Å³)	2339.29 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.78
Crystal size (mm)	0.85 × 0.36 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.549, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	56895, 6791, 5482
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.156, 1.19
No. of reflections	6791
No. of parameters	293
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.08, −0.60

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SAINT and SADABS (Bruker, 2005), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···N1ⁱ	0.98	2.59	3.449 (5)	147
C23—H23B···Br1ⁱⁱ	0.98	2.99	3.962 (4)	171
C26—H26B···Br1ⁱⁱⁱ	0.99	2.95	3.815 (4)	147

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

Acknowledgements

We thank Drs J. Wikaira and C. Fitchett of the University of Canterbury, New Zealand, for their assistance with the data collection.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Dalton, L. (2002). Polymers for Photonics Applications 1, Advances in Polymer Science, edited by K. S. Lee, pp. 1–86, Berlin/Heidelberg: Springer-Verlag. Google Scholar
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Mushkalo, I. L. & Sogulayaev, Yu. A. (1986). Sov. Progr. Chem. 52, 509–513. Google Scholar
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Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, H., Lu, Z., Lord, S. J., Willets, K. A., Bertke, J. A., Bunge, S. F., Moerner, W. E. & Twieg, R. J. (2007). Tetrahedron, 63, 103–114. Web of Science CSD CrossRef CAS Google Scholar

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Volume 65| Part 6| June 2009| Page o1315

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

2-(4-{3-[1-(3-Bromo­prop­yl)-3,3-di­methyl-2,3-di­hydro-1H-indol-2-yl­­idene]prop-1-en­yl}-3-cyano-5,5-di­methyl-2,5-di­hydro­furan-2-yl­­idene)malono­nitrile

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2-(4-{3-[1-(3-Bromopropyl)-3,3-dimethyl-2,3-dihydro-1H-indol-2-ylidene]prop-1-enyl}-3-cyano-5,5-dimethyl-2,5-dihydrofuran-2-ylidene)malononitrile