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Acta Cryst. (2009). E65, o1315    [ doi:10.1107/S1600536809017747 ]

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

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

Abstract top

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].

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.

Refinement top

The final residual map peak is 1.19Å from Br1. On the basis of average I/σ(I) analysis, data was excluded for θ > 30°. Four reflections affected by the backstop and 19 others which were clearly outlier data presumably affected by residual material (with Fo >>Fc and Δ(Fo2)/σ(Fo2) > 4.9) were omitted from the refinements (using OMIT). All methyl and tertiary H atoms were refined with Uiso 1.5 & 1.2 times respectively that of the Ueq of their parent atom. All H atoms bound to carbon were constrained to their expected geometries (C—H 0.95, 0.98 & 1.00 Å).

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
[Figure 1] Fig. 1. Molecular structure of the asymmetric unit (Farrugia, 1997); displacement ellipsoids are shown at the 30% probability level.
[Figure 2] 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
C26H25BrN4OF000 = 1008
Mr = 489.41Dx = 1.390 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 9973 reflections
a = 10.2349 (4) Åθ = 2.3–29.3º
b = 9.4017 (4) ŵ = 1.78 mm−1
c = 24.4524 (10) ÅT = 122 K
β = 96.175 (2)ºBlock, red
V = 2339.29 (17) Å30.85 × 0.36 × 0.10 mm
Z = 4
Data collection top
Bruker APEXII CCD
diffractometer		6791 independent reflections
Radiation source: fine-focus sealed tube5482 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.044
Detector resolution: 8.333 pixels mm-1θmax = 30.0º
T = 122 Kθmin = 2.5º
φ and ω scansh = −14→14
Absorption correction: multi-scan
(Blessing, 1995)		k = −13→13
Tmin = 0.549, Tmax = 0.746l = −34→34
56895 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.156  w = 1/[σ2(Fo2) + (0.0596P)2 + 4.5665P]
where P = (Fo2 + 2Fc2)/3
S = 1.19(Δ/σ)max = 0.001
6791 reflectionsΔρmax = 3.08 e Å−3
293 parametersΔρmin = −0.60 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C26H25BrN4OV = 2339.29 (17) Å3
Mr = 489.41Z = 4
Monoclinic, P21/cMo Kα
a = 10.2349 (4) ŵ = 1.78 mm−1
b = 9.4017 (4) ÅT = 122 K
c = 24.4524 (10) Å0.85 × 0.36 × 0.10 mm
β = 96.175 (2)º
Data collection top
Bruker APEXII CCD
diffractometer		6791 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)		5482 reflections with I > 2σ(I)
Tmin = 0.549, Tmax = 0.746Rint = 0.044
56895 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.059293 parameters
wR(F2) = 0.156H-atom parameters constrained
S = 1.19Δρmax = 3.08 e Å−3
6791 reflectionsΔρmin = −0.60 e Å−3
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*/Ueq
Br11.04264 (4)−0.19667 (4)0.464951 (13)0.03123 (11)
O10.4789 (2)0.4651 (2)0.11618 (9)0.0259 (5)
N10.5733 (4)0.9332 (3)0.18253 (17)0.0487 (9)
N20.3317 (4)0.7471 (5)0.04014 (15)0.0487 (9)
N30.7924 (3)0.6919 (3)0.24466 (12)0.0302 (6)
N41.0399 (2)0.1410 (3)0.36430 (10)0.0183 (4)
C10.5374 (4)0.8345 (4)0.15816 (16)0.0330 (7)
C20.4909 (3)0.7121 (3)0.12784 (14)0.0258 (6)
C30.4020 (3)0.7300 (4)0.07938 (15)0.0317 (7)
C40.6310 (3)0.3831 (3)0.18773 (11)0.0186 (5)
C50.5308 (3)0.3319 (3)0.14217 (12)0.0210 (6)
C60.5325 (3)0.5769 (3)0.14380 (12)0.0210 (5)
C70.6286 (3)0.5313 (3)0.18679 (12)0.0195 (5)
C80.5913 (3)0.2449 (4)0.09903 (13)0.0263 (6)
H8A0.52380.22250.06880.040*
H8B0.62740.15640.11560.040*
H8C0.66190.29970.08490.040*
C90.4168 (3)0.2573 (4)0.16424 (16)0.0308 (7)
H9A0.37570.32150.18900.046*
H9B0.44860.17200.18450.046*
H9C0.35200.23000.13360.046*
C100.7165 (3)0.6235 (3)0.21904 (12)0.0213 (5)
C110.7057 (3)0.2857 (3)0.22079 (12)0.0208 (5)
H110.69350.18770.21230.025*
C120.7964 (3)0.3200 (3)0.26505 (12)0.0213 (6)
H120.80670.41700.27550.026*
C130.8724 (3)0.2188 (3)0.29458 (12)0.0209 (5)
H130.85880.12240.28380.025*
C140.9674 (3)0.2454 (3)0.33870 (11)0.0182 (5)
C151.1325 (3)0.1961 (3)0.40603 (11)0.0201 (5)
C161.2270 (3)0.1236 (3)0.43992 (12)0.0214 (5)
H161.23630.02330.43770.026*
C171.3078 (3)0.2043 (4)0.47734 (13)0.0280 (6)
H171.37400.15830.50120.034*
C181.2933 (3)0.3511 (4)0.48045 (14)0.0293 (7)
H181.35000.40400.50630.035*
C191.1968 (3)0.4214 (4)0.44613 (13)0.0267 (6)
H191.18600.52150.44850.032*
C201.1171 (3)0.3418 (3)0.40854 (12)0.0203 (5)
C211.0071 (3)0.3868 (3)0.36571 (11)0.0193 (5)
C221.0602 (3)0.4925 (3)0.32554 (14)0.0272 (6)
H22A1.12780.44590.30640.041*
H22B1.09840.57480.34600.041*
H22C0.98820.52410.29860.041*
C230.8931 (3)0.4525 (4)0.39357 (13)0.0263 (6)
H23A0.82240.48060.36540.039*
H23B0.92480.53630.41480.039*
H23C0.85960.38230.41820.039*
C241.0321 (3)−0.0092 (3)0.34754 (12)0.0206 (5)
H24A1.1117−0.05920.36430.025*
H24B1.0317−0.01470.30710.025*
C250.9108 (3)−0.0860 (3)0.36403 (12)0.0237 (6)
H25A0.8316−0.03890.34550.028*
H25B0.9116−0.18490.35020.028*
C260.8990 (3)−0.0903 (4)0.42482 (13)0.0281 (6)
H26A0.8143−0.13490.43110.034*
H26B0.89900.00820.43920.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0428 (2)0.02650 (17)0.02325 (16)−0.00417 (14)−0.00169 (12)0.00277 (13)
O10.0256 (10)0.0217 (10)0.0283 (11)0.0037 (8)−0.0076 (8)0.0013 (9)
N10.061 (2)0.0208 (15)0.061 (2)0.0085 (15)−0.0063 (18)−0.0004 (15)
N20.0389 (18)0.065 (2)0.0400 (19)0.0197 (17)−0.0053 (15)0.0059 (17)
N30.0309 (14)0.0266 (14)0.0326 (14)0.0013 (11)0.0015 (11)−0.0061 (12)
N40.0171 (10)0.0198 (11)0.0173 (11)−0.0004 (9)−0.0010 (8)0.0007 (9)
C10.0345 (17)0.0250 (16)0.0390 (19)0.0095 (13)0.0019 (14)0.0068 (14)
C20.0247 (14)0.0243 (15)0.0280 (15)0.0087 (12)0.0012 (11)0.0049 (12)
C30.0285 (16)0.0319 (18)0.0348 (18)0.0122 (13)0.0032 (13)0.0056 (14)
C40.0176 (12)0.0212 (13)0.0169 (12)0.0015 (10)0.0013 (9)−0.0016 (10)
C50.0188 (12)0.0187 (13)0.0242 (14)0.0030 (10)−0.0044 (10)0.0021 (10)
C60.0196 (12)0.0221 (14)0.0210 (13)0.0046 (10)0.0017 (10)0.0015 (11)
C70.0198 (12)0.0193 (13)0.0193 (13)0.0032 (10)0.0012 (10)−0.0007 (10)
C80.0299 (16)0.0261 (15)0.0221 (14)0.0014 (12)−0.0016 (12)−0.0022 (12)
C90.0172 (13)0.0291 (16)0.046 (2)0.0003 (12)0.0014 (13)0.0062 (14)
C100.0228 (13)0.0179 (13)0.0232 (14)0.0042 (10)0.0034 (10)−0.0013 (11)
C110.0215 (13)0.0190 (13)0.0212 (13)0.0018 (10)−0.0016 (10)0.0005 (10)
C120.0209 (13)0.0216 (14)0.0210 (13)0.0000 (10)0.0004 (10)−0.0001 (10)
C130.0226 (13)0.0192 (13)0.0200 (13)−0.0012 (10)−0.0021 (10)0.0001 (10)
C140.0178 (12)0.0204 (13)0.0165 (12)0.0000 (10)0.0018 (10)0.0025 (10)
C150.0159 (11)0.0288 (14)0.0155 (12)−0.0019 (11)0.0017 (9)0.0028 (11)
C160.0188 (12)0.0238 (14)0.0212 (13)−0.0010 (10)0.0002 (10)0.0026 (11)
C170.0198 (13)0.0391 (18)0.0237 (14)−0.0021 (13)−0.0043 (11)0.0043 (13)
C180.0241 (14)0.0344 (17)0.0271 (15)−0.0080 (13)−0.0074 (12)−0.0015 (13)
C190.0272 (14)0.0232 (15)0.0283 (15)−0.0074 (12)−0.0040 (12)0.0001 (12)
C200.0194 (12)0.0221 (13)0.0188 (13)−0.0042 (10)−0.0008 (10)0.0024 (10)
C210.0201 (12)0.0191 (13)0.0179 (12)−0.0038 (10)−0.0011 (10)0.0024 (10)
C220.0296 (15)0.0215 (14)0.0296 (15)−0.0067 (12)−0.0014 (12)0.0065 (12)
C230.0253 (14)0.0252 (15)0.0278 (15)−0.0004 (12)0.0009 (11)−0.0057 (12)
C240.0237 (13)0.0194 (13)0.0184 (13)0.0011 (10)0.0012 (10)−0.0014 (10)
C250.0253 (14)0.0222 (14)0.0227 (14)−0.0060 (11)−0.0021 (11)−0.0002 (11)
C260.0278 (15)0.0312 (17)0.0261 (15)−0.0029 (13)0.0061 (12)0.0006 (13)
Geometric parameters (Å, °) top
Br1—C261.953 (3)C13—H130.9500
O1—C61.336 (4)C14—C211.520 (4)
O1—C51.476 (3)C15—C201.382 (4)
N1—C11.142 (5)C15—C161.383 (4)
N2—C31.147 (5)C16—C171.390 (4)
N3—C101.142 (4)C16—H160.9500
N4—C141.344 (4)C17—C181.392 (5)
N4—C151.414 (4)C17—H170.9500
N4—C241.470 (4)C18—C191.393 (4)
C1—C21.423 (5)C18—H180.9500
C2—C61.383 (4)C19—C201.382 (4)
C2—C31.424 (5)C19—H190.9500
C4—C71.394 (4)C20—C211.513 (4)
C4—C111.395 (4)C21—C221.537 (4)
C4—C51.510 (4)C21—C231.542 (4)
C5—C91.510 (4)C22—H22A0.9800
C5—C81.519 (4)C22—H22B0.9800
C6—C71.426 (4)C22—H22C0.9800
C7—C101.424 (4)C23—H23A0.9800
C8—H8A0.9800C23—H23B0.9800
C8—H8B0.9800C23—H23C0.9800
C8—H8C0.9800C24—C251.528 (4)
C9—H9A0.9800C24—H24A0.9900
C9—H9B0.9800C24—H24B0.9900
C9—H9C0.9800C25—C261.505 (4)
C11—C121.386 (4)C25—H25A0.9900
C11—H110.9500C25—H25B0.9900
C12—C131.383 (4)C26—H26A0.9900
C12—H120.9500C26—H26B0.9900
C13—C141.395 (4)
C6—O1—C5109.9 (2)C15—C16—C17117.0 (3)
C14—N4—C15111.2 (2)C15—C16—H16121.5
C14—N4—C24124.2 (2)C17—C16—H16121.5
C15—N4—C24124.4 (2)C16—C17—C18121.2 (3)
N1—C1—C2179.2 (4)C16—C17—H17119.4
C6—C2—C1121.4 (3)C18—C17—H17119.4
C6—C2—C3119.5 (3)C17—C18—C19120.7 (3)
C1—C2—C3119.1 (3)C17—C18—H18119.7
N2—C3—C2178.6 (4)C19—C18—H18119.7
C7—C4—C11132.4 (3)C20—C19—C18118.3 (3)
C7—C4—C5107.3 (2)C20—C19—H19120.9
C11—C4—C5120.3 (3)C18—C19—H19120.9
O1—C5—C4103.4 (2)C15—C20—C19120.3 (3)
O1—C5—C9107.0 (2)C15—C20—C21109.1 (2)
C4—C5—C9112.0 (3)C19—C20—C21130.6 (3)
O1—C5—C8108.2 (2)C20—C21—C14101.6 (2)
C4—C5—C8112.9 (2)C20—C21—C22109.6 (2)
C9—C5—C8112.7 (3)C14—C21—C22112.6 (2)
O1—C6—C2118.9 (3)C20—C21—C23110.4 (2)
O1—C6—C7110.4 (2)C14—C21—C23111.2 (2)
C2—C6—C7130.6 (3)C22—C21—C23111.1 (3)
C4—C7—C10126.2 (3)C21—C22—H22A109.5
C4—C7—C6108.8 (3)C21—C22—H22B109.5
C10—C7—C6124.7 (3)H22A—C22—H22B109.5
C5—C8—H8A109.5C21—C22—H22C109.5
C5—C8—H8B109.5H22A—C22—H22C109.5
H8A—C8—H8B109.5H22B—C22—H22C109.5
C5—C8—H8C109.5C21—C23—H23A109.5
H8A—C8—H8C109.5C21—C23—H23B109.5
H8B—C8—H8C109.5H23A—C23—H23B109.5
C5—C9—H9A109.5C21—C23—H23C109.5
C5—C9—H9B109.5H23A—C23—H23C109.5
H9A—C9—H9B109.5H23B—C23—H23C109.5
C5—C9—H9C109.5N4—C24—C25113.6 (2)
H9A—C9—H9C109.5N4—C24—H24A108.8
H9B—C9—H9C109.5C25—C24—H24A108.8
N3—C10—C7176.1 (3)N4—C24—H24B108.8
C12—C11—C4125.4 (3)C25—C24—H24B108.8
C12—C11—H11117.3H24A—C24—H24B107.7
C4—C11—H11117.3C26—C25—C24115.3 (2)
C13—C12—C11122.7 (3)C26—C25—H25A108.5
C13—C12—H12118.7C24—C25—H25A108.5
C11—C12—H12118.7C26—C25—H25B108.5
C12—C13—C14125.9 (3)C24—C25—H25B108.5
C12—C13—H13117.0H25A—C25—H25B107.5
C14—C13—H13117.0C25—C26—Br1112.0 (2)
N4—C14—C13122.2 (3)C25—C26—H26A109.2
N4—C14—C21109.2 (2)Br1—C26—H26A109.2
C13—C14—C21128.6 (3)C25—C26—H26B109.2
C20—C15—C16122.5 (3)Br1—C26—H26B109.2
C20—C15—N4108.9 (2)H26A—C26—H26B107.9
C16—C15—N4128.5 (3)
C6—O1—C5—C4−3.6 (3)C12—C13—C14—C212.0 (5)
C6—O1—C5—C9114.8 (3)C14—N4—C15—C201.6 (3)
C6—O1—C5—C8−123.5 (3)C24—N4—C15—C20176.2 (2)
C7—C4—C5—O11.8 (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—C967.6 (3)N4—C15—C16—C17179.0 (3)
C7—C4—C5—C8118.5 (3)C15—C16—C17—C180.2 (5)
C11—C4—C5—C8−60.9 (4)C16—C17—C18—C190.3 (5)
C5—O1—C6—C2−176.3 (3)C17—C18—C19—C20−0.8 (5)
C5—O1—C6—C74.1 (3)C16—C15—C20—C19−0.5 (4)
C1—C2—C6—O1175.3 (3)N4—C15—C20—C19−179.7 (3)
C3—C2—C6—O1−6.1 (5)C16—C15—C20—C21179.2 (3)
C1—C2—C6—C7−5.1 (5)N4—C15—C20—C210.0 (3)
C3—C2—C6—C7173.4 (3)C18—C19—C20—C150.9 (5)
C11—C4—C7—C106.0 (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—C6179.7 (3)C19—C20—C21—C14178.3 (3)
C5—C4—C7—C60.5 (3)C15—C20—C21—C22−120.6 (3)
O1—C6—C7—C4−2.9 (3)C19—C20—C21—C2259.1 (4)
C2—C6—C7—C4177.6 (3)C15—C20—C21—C23116.7 (3)
O1—C6—C7—C10171.0 (3)C19—C20—C21—C23−63.6 (4)
C2—C6—C7—C10−8.6 (5)N4—C14—C21—C202.3 (3)
C7—C4—C11—C123.6 (5)C13—C14—C21—C20−177.8 (3)
C5—C4—C11—C12−177.2 (3)N4—C14—C21—C22119.4 (3)
C4—C11—C12—C13−176.6 (3)C13—C14—C21—C22−60.7 (4)
C11—C12—C13—C14178.5 (3)N4—C14—C21—C23−115.1 (3)
C15—N4—C14—C13177.6 (3)C13—C14—C21—C2364.8 (4)
C24—N4—C14—C132.9 (4)C14—N4—C24—C25−76.2 (3)
C15—N4—C14—C21−2.5 (3)C15—N4—C24—C25109.9 (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, °) top
D—H···AD—HH···AD···AD—H···A
C9—H9B···N1i0.982.593.449 (5)147
C23—H23B···Br1ii0.982.993.962 (4)171
C26—H26B···Br1iii0.992.953.815 (4)147
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+2, −y, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C9—H9B···N1i0.982.593.449 (5)147
C23—H23B···Br1ii0.982.993.962 (4)171
C26—H26B···Br1iii0.992.953.815 (4)147
Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z; (iii) −x+2, −y, −z+1.
Acknowledgements top

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

references
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