Geometry and bond-length alternation in nonlinear optical materials. III. Structural parameters of two chromophores containing aromatizable donors

The planar component of 2-{3-cyano-4-[3-(1-decyl-1,4-dihydro­quinolin-4-yl­idene)prop-1-enyl]-5,5-dimethyl-2,5-di­hydrofuran-2-yl­idene}malononitrile, C₃₂H₄₆N₄O, (I), forms into layers parallel to the (01) plane. The larger of the two spaces between layers is filled by the alkyl chains, giving a `sandwich stack' appearance. The packing of 2-{3-cyano-4-[5-(1-decyl-1,4-dihydro­quinolin-4-yl­idene)penta-1,3-dienyl]-5,5-dimethyl-2,5-dihydro­furan-2-yl­idene}malononitrile, C<sub>34</sub>H<sub>38</sub>N<sub>4</sub>O, (II), which has partial disorder in the 1-decyl group, utilizes weak C—H...N, C—H...O and C—N...π inter­actions in a three-dimensional `herring-bone' array with mol­ecular segments parallel to the (111) and (1) planes. Different rotational isomers with respect to the polyene chain and the 5,5-dimethyl-2,5-dihydro­furan-2-yl­idene link are observed in the two structures. The significance of the study lies in the delocalization of charge along the polyene chain and the supra­molecular aggregation present, which highlight the difficulty in obtaining the noncentrosymmetric alignment required for high nonlinear optical (NLO) responses in zwitterionic chromophores.

S1. Comment

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, Gainsford et al., 2008a,b; Gainsford et al., 2008) due to their potential application in a number of photonic and optoelectronic devices (Dalton, 2002; Kay et al., 2004). Basic structural parameters for a series of zwitterionic chromophores and their precursors were presented at a recent conference (Kay et al., 2008) and we report here the complete crystallographic data for two of these compounds, 2-{3-cyano-4-[3-(4-decyl-1,4-dihydroquinolin-1-ylidene)propenyl]-5,5-dimethyl-2,5-dihydrofuran-2-ylidene}malononitrile, (I), and 2-{3-cyano-4-[5-(4-decyl-1,4-dihydroquinolin-1-ylidene)penta-1,3-dienyl]-5,5-dimethyl-2,5-dihydrofuran-2-ylidene}malononitrile, (II), as part of our ongoing studies into how changes in bond order brought about by charge delocalization impact on the magnitude of the nonlinear optical (NLO) response. Given that such molecules are prone to aggregation, we were also very interested to know through structural study whether modifications to the polyene chain length or the substituent on the donor N atom could mitigate this potentially deleterious effect.

The asymmetric unit contents of compound (I) are shown in Fig. 1. Excluding the alkyl(1-decyl) chain atoms (C23–C32), the terminal cyano atoms N1 and C1, and the methyl groups C8 and C9 and their associated H atoms, the molecule is close to planar, with an r.m.s. deviation of 0.023 (2) Å for the 23 atoms. In the quinoline part, rings C17–C22 and C14–C16/N4/C17/C22 are each rigorously planar [r.m.s. deviations 0.003 (2) and 0.006 (2) Å, respectively], with a dihedral angle between them of 1.69 (12)° and a puckering amplitude of 0.045 (3) Å (PLATON; Spek, 2003) The five-membered ring plane of atoms C4/C5/O1/C6/C7 [the (3-cyano-5,5-dimethyl-2,5-dihydrofuran-2-ylidine)propanedinitrile part, hereinafter CDFP] can also be regarded as planar in this case [r.m.s. deviation 0.009 (2) Å]. The dicyano group (N1/C1–C3/N2) is planar but twisted by 5.69 (17)° with respect to the CDFP group.

The almost-planar components of the molecules in (I) (excluding the alkyl chain atoms C23–C32) are arranged into nearly planar layers parallel to the (101) plane, with only weak and possibly adventitious contacts C—H···N(cyano) between them (Table 1). The larger of the unequal spaces between the layers (~10.3 Å, compared with ~3.4 Å for the smaller) are filled by the alkyl chains, resulting in a `sandwich stack' appearance, with the alkyl chains providing the filling (Fig. 2).

Compound (II) crystallizes as the alternative (transoid) rotamer (by rotation about the C4—C7 bond), as shown in Figs. 1 and 3 and quantified by the C7—C4—C11—C12 torsion angles (Table 3). Gas-phase density functional theory calculations using the Amsterdam Density Functional program system, ADF (SCM, 2007), indicate that the cisoid rotamer of (II) is very similar in energy to its transoid isomer (differing by less than 0.6 kcal mol^-1; 1 kcal mol^-1 = 4.184 kJ mol^-1). By contrast, the transoid rotamer for (I) is calculated to be some 4 kcal mol^-1 more stable than its cisoid counterpart. This implies that the observed structure in (I) is possibly determined by crystal packing forces. Also unlike (I), the non-alkyl chain atoms in (II) are twisted from planarity; this is shown by the dihedral angles between the CDFP ring and the polyene and quinoline planes (Table 3, entries 1 and 2). The CDFP ring is planar [r.m.s. deviation 0.017 (2) Å] but has some bond distance deviations from those in (I), notably in the atoms bound to C7 (Table 3). The dicyano group (N1/C1–C3/N2) has a twist from the CDFP plane of 6.74 (16)°, similar to (I). Data for the parent CDFP structure, (III), 2-dicyanomethylene-4,5,5-trimethylene-4,5,5-trimethyl-2,5-dihydrofuran-3-carbonitrile [Cambridge Structural Database (Allen, 2002) refcode PANLUM (Li et al., 2005)] are also given in Table 3.

In (II), there are hydrogen-bond interactions (Fig. 4) between CDFP atom O1 and quinoline atom H21, between polyene atom H12 and cyano atom N1, and between quinoline atom H18 and cyano atom N2 [Please check rephrasing and added atom labels], as well as a weak interaction between the π orbitals of the adjacent quinoline ring and one set of CDFP cyano atoms (last entry, Table 2: Cg2 is the centroid of atoms C16–C18/N4/C19/C24). The packing has elements of the well known `herring-bone' structure, with the π and N2···H18 links (Table 2) binding adjacent molecules parallel to the (111) plane, and the H21···O1 and N1···H12 interactions providing crosslinks to the other herring-bone set which are parallel to the (111) plane.

Both (I) and (II) show considerable delocalization of charge along the polyene/CDFP chain, with bond length alternation (BLA) values (Marder et al., 1993) of -0.015 and -0.042 Å, respectively, compared with the free CDFP value of 0.108 Å in (III) (Li et al., 2005). It should be noted that the BLA values were calculated by considering the bonds C2—C6 to C12—C13 in (I) and C2—C6 to C14—C15 in (II), inclusive. The degrees of BLA in (I) and (II) are considerably different from the values found for analogous compounds with far weaker donors, such as those derived from acetanilide and piperidine (see scheme): 0.073 Å in (IV) (Gainsford et al., 2008a); 0.060 Å in (V) (Gainsford et al., 2007); 0.000 Å in (VI) (Gainsford et al., 2008a). This is to be expected because compounds (I) and (II) here, with their dihydroquinolinylidene aromatic donor systems, will allow additional charge delocalization to occur in concert with their aromaticity. We note that the first hyperpolarizabilities of two analogues of (I) and (II) (N-methyl rather than N-decyl) have been reported (Kay et al., 2004) as 440 and 560 × 10^-30 esu, respectively. Thus, our findings for (I) and (II) are in line with the theory that the closer variances in BLA are to approximately -0.05 Å, the greater the NLO response (Marder et al., 1993).

Our final comment concerns the intramolecular parameters affected by the alternative cisoid/transoid conformations. In the crystal structures of 12 compounds containing the CDFP/polyene moiety which we have studied, the transoid conformation is found in seven. The average of the close methyl-H···polyene-H intramolecular interactions [e.g. H12···H9B in (II)] for well characterized models is 2.27 (5) Å for the transoid and 2.51 (4) Å for the cisoid [e.g. H11···H8B in (I)]. The interaction distances of the C11 polyene H atom with the cyano atom C10 average to 2.68 (4) and 2.54 (6) Å, respectively. We conclude that the shorter contact distances observed in the transoid molecules are not close enough to encourage the molecules into favouring the cisoid conformation.

Related literature

For related literature, see: Allen (2002); Ashwell et al. (1990); Dalton (2002); Gainsford et al. (2007, 2008, 2008a, 2008b); Kay et al. (2004, 2008); Li et al. (2005); Marder et al. (1993); SCM (2007); Sheldrick (2008); Spek (2003).

S2. Experimental

Compounds (I) and (II) were prepared via condensation of 1-decyl-4-methylquinolinium bromide (Ashwell et al., 1990) with either [4-(2-acetanilidoethenyl)-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile (compound 11a) or [4-(2-acetanilido-trans-1,3-butadienyl)-3-cyano-5,5-dimethyl-2(5H)-furanylidene]propanedinitrile (compound 11b) using the procedure previously described by Kay et al. (2004), method B, methanol as solvent. The resultant powders were washed with copious quantities of hot water, followed by small portions of cold methanol to afford the target molecules as coloured powders. Recrystallization for (I) was from methanol–dichloromethane [Solvent ratio?] and for (II) was from acetone.

S3. Refinement

On the basis of average I/σ(I) analysis, data were excluded for θ > 30° for (I) and θ > 25° for (II). For (I) and (II), respectively, 8 or 17 reflections affected by the backstop or clearly outlier data were omitted from the refinements using OMIT (SHELXL97; Sheldrick, 2008), and a further 5 or 7 reflections within θ ≤ 25° were either not measured or failed to meet processing requirements.

All methyl and tertiary H atoms were treated as riding, with C—H = 0.95–0.99 Å and with U_iso(H) = 1.5 or 1.2, respectively, times U_eq of their parent atom. [Please check added text]

All non-H atoms were refined with anisotropic displacement parameters in (I). In compound (II), the alkyl atom chain was disordered into two `strands', starting at C29 and ending at C34. Each strand, A or B, was refined with a common complementary occupancy to 0.683 (4):0.317 (4), with all B strand atoms and C33A and C34A refined with isotropic displacement parameters. Atom C31B was given a fixed U of 0.14 Ų (the average U value of adjacent B strand atoms). Finally, the bond distances between identical atoms in the two strands (e.g. C33A—C34A and C33B—C34B) and the C—C—C angles (e.g. C31A—C32A—C33A and C31B—C32B—C33B) were restrained to the same common values with an s.u. of 0.02 using the SHELXL97 SADI command. In total, 24 restraints were used in (II).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEP-3 in WinGX (Farrugia, 1997) for (I); ORTEP-3 in WinGX (Farrugia, 1997) and Mercury (Macrae et al., 2006) for (II). For both compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of the asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A `sandwich' packing diagram (see text) of the cell of (I), viewed approximately down the b axis. For clarity, stick bonding is used, with all H atoms excluded. N and O atoms are depicted as open and filled circles, respectively. Three asymmetric unit atom labels are given.
	Fig. 3. The molecular structure of the asymmetric unit of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Only the major conformer atoms (set A) are shown.
	Fig. 4. A partial packing diagram of the cell of (II), viewed approximately down the a axis, showing key intermolecular interactions. For clarity, only H atoms involved in hydrogen bonds (dashed lines) and disordered atom set A are pictured. All labelled contact atoms and other atoms are shown in ball and stick forms, respectively (see Table 2). [Symmetry codes: (i) x - 1, y +1, z; (ii) 1/2 + x, 1/2 - y, 1/2 + z; (iii) 3/2 - x,1/2 + y, 1/2 - z.]

(I) 2-{3-cyano-4-[3-(1-decyl-1,4-dihydroquinolin-4-ylidene)prop-1-enyl]- 5,5-dimethyl-2,5-dihydrofuran-2-ylidene}malononitrile

Crystal data

C32H36N4O	F(000) = 1056
Mr = 492.65	Dx = 1.162 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7435 reflections
a = 11.9830 (6) Å	θ = 2.3–30.4°
b = 17.5374 (8) Å	µ = 0.07 mm^−1
c = 14.0363 (7) Å	T = 106 K
β = 107.289 (3)°	Plate, blue
V = 2816.5 (2) Å^3	0.90 × 0.70 × 0.03 mm
Z = 4

Data collection

Bruker Nonius APEXII CCD area-detector diffractometer	3764 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.128
Graphite monochromator	θmax = 30.0°, θmin = 2.1°
Detector resolution: 8.333 pixels mm^-1	h = −16→16
ϕ and ω scans	k = −24→22
53106 measured reflections	l = −19→19
8166 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.203	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0737P)^2 + 1.2326P] where P = (Fo^2 + 2Fc^2)/3
8166 reflections	(Δ/σ)max < 0.001
337 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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. 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.51764 (15)	0.06884 (8)	0.35108 (12)	0.0208 (4)
N1	0.7848 (2)	0.04454 (13)	0.67766 (18)	0.0362 (6)
N2	0.6042 (2)	−0.11393 (12)	0.44304 (17)	0.0308 (5)
N3	0.7504 (2)	0.22987 (13)	0.60442 (18)	0.0401 (7)
N4	0.71664 (18)	0.59951 (11)	0.56341 (15)	0.0204 (4)
C1	0.7240 (2)	0.03682 (13)	0.59757 (19)	0.0242 (6)
C2	0.6482 (2)	0.02529 (13)	0.50002 (17)	0.0194 (5)
C3	0.6226 (2)	−0.05131 (13)	0.46737 (18)	0.0202 (5)
C4	0.5335 (2)	0.20254 (13)	0.36900 (17)	0.0192 (5)
C5	0.4692 (2)	0.14007 (12)	0.29882 (17)	0.0192 (5)
C6	0.5957 (2)	0.08578 (13)	0.43892 (17)	0.0175 (5)
C7	0.6085 (2)	0.16549 (13)	0.45255 (18)	0.0192 (5)
C8	0.4962 (2)	0.13947 (14)	0.20002 (18)	0.0267 (6)
H8A	0.5810	0.1377	0.2122	0.040*
H8B	0.4648	0.1858	0.1625	0.040*
H8C	0.4602	0.0946	0.1614	0.040*
C9	0.3395 (2)	0.14003 (13)	0.28773 (18)	0.0230 (5)
H9A	0.3039	0.0935	0.2532	0.034*
H9B	0.3028	0.1847	0.2489	0.034*
H9C	0.3278	0.1419	0.3539	0.034*
C10	0.6869 (2)	0.20035 (13)	0.53710 (19)	0.0249 (6)
C11	0.5110 (2)	0.27850 (13)	0.34497 (19)	0.0213 (5)
H11	0.4545	0.2902	0.2832	0.026*
C12	0.5662 (2)	0.34009 (13)	0.40569 (18)	0.0199 (5)
H12	0.6218	0.3286	0.4680	0.024*
C13	0.5445 (2)	0.41560 (13)	0.38046 (18)	0.0187 (5)
H13	0.4878	0.4274	0.3189	0.022*
C14	0.6023 (2)	0.47710 (12)	0.44156 (18)	0.0177 (5)
C15	0.6857 (2)	0.46640 (13)	0.53460 (17)	0.0200 (5)
H15	0.7053	0.4160	0.5585	0.024*
C16	0.7392 (2)	0.52632 (13)	0.59169 (18)	0.0215 (5)
H16	0.7949	0.5161	0.6543	0.026*
C17	0.6354 (2)	0.61639 (13)	0.47287 (18)	0.0183 (5)
C18	0.6071 (2)	0.69282 (13)	0.44352 (19)	0.0239 (6)
H18	0.6452	0.7333	0.4858	0.029*
C19	0.5259 (2)	0.70876 (14)	0.3550 (2)	0.0255 (6)
H19	0.5076	0.7604	0.3361	0.031*
C20	0.4687 (2)	0.64998 (14)	0.2914 (2)	0.0248 (6)
H20	0.4127	0.6616	0.2294	0.030*
C21	0.4943 (2)	0.57559 (13)	0.31923 (19)	0.0225 (5)
H21	0.4549	0.5361	0.2759	0.027*
C22	0.5773 (2)	0.55588 (12)	0.41013 (18)	0.0180 (5)
C23	0.7869 (2)	0.66005 (14)	0.62744 (19)	0.0263 (6)
H23A	0.8249	0.6392	0.6948	0.032*
H23B	0.7347	0.7021	0.6342	0.032*
C24	0.8801 (2)	0.69102 (15)	0.5837 (2)	0.0309 (6)
H24A	0.8408	0.7117	0.5165	0.037*
H24B	0.9203	0.7340	0.6258	0.037*
C25	0.9718 (2)	0.63364 (16)	0.5750 (2)	0.0317 (6)
H25A	0.9313	0.5881	0.5394	0.038*
H25B	1.0173	0.6563	0.5337	0.038*
C26	1.0561 (2)	0.60831 (17)	0.6735 (2)	0.0338 (7)
H26A	1.0124	0.5794	0.7114	0.041*
H26B	1.0897	0.6540	0.7131	0.041*
C27	1.1554 (3)	0.55869 (17)	0.6611 (2)	0.0365 (7)
H27A	1.1216	0.5113	0.6259	0.044*
H27B	1.1944	0.5861	0.6181	0.044*
C28	1.2470 (3)	0.53727 (16)	0.7578 (2)	0.0355 (7)
H28A	1.3021	0.5004	0.7429	0.043*
H28B	1.2080	0.5116	0.8020	0.043*
C29	1.3162 (3)	0.60544 (16)	0.8131 (2)	0.0332 (6)
H29A	1.3485	0.6341	0.7665	0.040*
H29B	1.2620	0.6398	0.8336	0.040*
C31	1.4901 (3)	0.65227 (17)	0.9520 (2)	0.0425 (8)
H31A	1.5312	0.6713	0.9052	0.051*
H31B	1.4378	0.6934	0.9614	0.051*
C30	1.4160 (3)	0.58430 (16)	0.9049 (2)	0.0361 (7)
H30A	1.3833	0.5606	0.9548	0.043*
H30B	1.4663	0.5460	0.8860	0.043*
C32	1.5798 (3)	0.63604 (19)	1.0515 (2)	0.0452 (8)
H32A	1.5399	0.6195	1.0996	0.068*
H32B	1.6248	0.6824	1.0760	0.068*
H32C	1.6327	0.5957	1.0432	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0277 (10)	0.0096 (8)	0.0197 (9)	0.0001 (6)	−0.0012 (7)	−0.0001 (6)
N1	0.0443 (15)	0.0245 (12)	0.0293 (13)	−0.0011 (10)	−0.0051 (11)	0.0059 (10)
N2	0.0457 (15)	0.0170 (11)	0.0317 (13)	0.0001 (9)	0.0146 (11)	0.0010 (9)
N3	0.0457 (16)	0.0217 (12)	0.0380 (15)	0.0050 (10)	−0.0103 (12)	−0.0070 (10)
N4	0.0267 (11)	0.0128 (10)	0.0205 (11)	−0.0012 (8)	0.0049 (9)	−0.0039 (8)
C1	0.0289 (14)	0.0136 (12)	0.0266 (14)	0.0002 (9)	0.0029 (11)	0.0042 (10)
C2	0.0237 (13)	0.0129 (11)	0.0190 (12)	−0.0001 (9)	0.0023 (10)	0.0007 (9)
C3	0.0248 (13)	0.0152 (12)	0.0199 (13)	0.0024 (9)	0.0056 (10)	0.0042 (9)
C4	0.0235 (13)	0.0141 (11)	0.0181 (12)	−0.0015 (9)	0.0032 (10)	−0.0002 (9)
C5	0.0275 (13)	0.0083 (10)	0.0167 (12)	0.0012 (9)	−0.0010 (10)	0.0020 (8)
C6	0.0194 (12)	0.0144 (11)	0.0173 (12)	0.0011 (9)	0.0034 (9)	−0.0009 (9)
C7	0.0226 (13)	0.0143 (11)	0.0179 (12)	−0.0013 (9)	0.0018 (10)	−0.0018 (9)
C8	0.0398 (16)	0.0187 (12)	0.0200 (13)	−0.0002 (11)	0.0065 (12)	−0.0005 (10)
C9	0.0264 (13)	0.0154 (11)	0.0210 (13)	−0.0028 (9)	−0.0023 (10)	0.0016 (9)
C10	0.0292 (14)	0.0142 (12)	0.0253 (14)	0.0031 (10)	−0.0010 (11)	−0.0006 (10)
C11	0.0253 (13)	0.0147 (12)	0.0209 (13)	−0.0010 (9)	0.0021 (10)	−0.0004 (9)
C12	0.0227 (13)	0.0149 (11)	0.0201 (12)	0.0003 (9)	0.0035 (10)	0.0010 (9)
C13	0.0212 (13)	0.0129 (11)	0.0199 (12)	0.0008 (9)	0.0029 (10)	−0.0002 (9)
C14	0.0205 (12)	0.0119 (11)	0.0214 (12)	−0.0003 (8)	0.0073 (10)	−0.0004 (9)
C15	0.0249 (13)	0.0133 (11)	0.0203 (13)	0.0001 (9)	0.0041 (10)	0.0005 (9)
C16	0.0259 (14)	0.0164 (12)	0.0196 (13)	0.0002 (9)	0.0029 (10)	0.0011 (9)
C17	0.0213 (13)	0.0143 (11)	0.0198 (12)	0.0001 (9)	0.0069 (10)	−0.0009 (9)
C18	0.0314 (14)	0.0123 (12)	0.0281 (14)	−0.0011 (9)	0.0088 (12)	−0.0025 (10)
C19	0.0313 (15)	0.0124 (12)	0.0317 (15)	0.0006 (10)	0.0079 (12)	0.0012 (10)
C20	0.0269 (14)	0.0178 (12)	0.0254 (14)	0.0007 (10)	0.0012 (11)	0.0040 (10)
C21	0.0269 (14)	0.0138 (11)	0.0244 (14)	−0.0012 (9)	0.0037 (11)	0.0017 (9)
C22	0.0212 (13)	0.0126 (11)	0.0208 (12)	−0.0005 (9)	0.0071 (10)	0.0002 (9)
C23	0.0356 (15)	0.0162 (12)	0.0231 (14)	−0.0037 (10)	0.0025 (12)	−0.0071 (9)
C24	0.0364 (16)	0.0238 (14)	0.0285 (15)	−0.0103 (11)	0.0036 (12)	−0.0050 (11)
C25	0.0349 (16)	0.0325 (15)	0.0281 (15)	−0.0089 (12)	0.0099 (12)	−0.0054 (11)
C26	0.0338 (16)	0.0384 (16)	0.0301 (16)	−0.0025 (12)	0.0109 (13)	−0.0061 (12)
C27	0.0380 (17)	0.0374 (17)	0.0365 (17)	−0.0031 (13)	0.0146 (14)	−0.0077 (13)
C28	0.0400 (17)	0.0345 (16)	0.0359 (17)	0.0010 (13)	0.0173 (14)	−0.0021 (13)
C29	0.0370 (17)	0.0347 (16)	0.0302 (15)	0.0017 (12)	0.0137 (13)	0.0011 (12)
C31	0.047 (2)	0.0341 (17)	0.0436 (19)	0.0057 (13)	0.0088 (16)	−0.0045 (14)
C30	0.0364 (17)	0.0313 (16)	0.0420 (18)	0.0040 (12)	0.0139 (14)	0.0012 (13)
C32	0.044 (2)	0.049 (2)	0.0425 (19)	0.0006 (15)	0.0113 (16)	−0.0039 (15)

Geometric parameters (Å, º)

O1—C6	1.341 (3)	C18—H18	0.9500
O1—C5	1.477 (3)	C19—C20	1.402 (3)
N1—C1	1.151 (3)	C19—H19	0.9500
N2—C3	1.152 (3)	C20—C21	1.370 (3)
N3—C10	1.145 (3)	C20—H20	0.9500
N4—C16	1.347 (3)	C21—C22	1.408 (3)
N4—C17	1.384 (3)	C21—H21	0.9500
N4—C23	1.481 (3)	C23—C24	1.526 (4)
C1—C2	1.415 (3)	C23—H23A	0.9900
C2—C6	1.391 (3)	C23—H23B	0.9900
C2—C3	1.423 (3)	C24—C25	1.521 (4)
C4—C11	1.381 (3)	C24—H24A	0.9900
C4—C7	1.406 (3)	C24—H24B	0.9900
C4—C5	1.521 (3)	C25—C26	1.517 (4)
C5—C8	1.514 (3)	C25—H25A	0.9900
C5—C9	1.516 (3)	C25—H25B	0.9900
C6—C7	1.413 (3)	C26—C27	1.526 (4)
C7—C10	1.415 (3)	C26—H26A	0.9900
C8—H8A	0.9800	C26—H26B	0.9900
C8—H8B	0.9800	C27—C28	1.518 (4)
C8—H8C	0.9800	C27—H27A	0.9900
C9—H9A	0.9800	C27—H27B	0.9900
C9—H9B	0.9800	C28—C29	1.529 (4)
C9—H9C	0.9800	C28—H28A	0.9900
C11—C12	1.412 (3)	C28—H28B	0.9900
C11—H11	0.9500	C29—C30	1.521 (4)
C12—C13	1.375 (3)	C29—H29A	0.9900
C12—H12	0.9500	C29—H29B	0.9900
C13—C14	1.423 (3)	C31—C32	1.514 (4)
C13—H13	0.9500	C31—C30	1.516 (4)
C14—C15	1.401 (3)	C31—H31A	0.9900
C14—C22	1.454 (3)	C31—H31B	0.9900
C15—C16	1.361 (3)	C30—H30A	0.9900
C15—H15	0.9500	C30—H30B	0.9900
C16—H16	0.9500	C32—H32A	0.9800
C17—C18	1.413 (3)	C32—H32B	0.9800
C17—C22	1.422 (3)	C32—H32C	0.9800
C18—C19	1.360 (3)
C6—O1—C5	109.45 (16)	C20—C21—C22	122.0 (2)
C16—N4—C17	119.94 (19)	C20—C21—H21	119.0
C16—N4—C23	118.4 (2)	C22—C21—H21	119.0
C17—N4—C23	121.45 (19)	C21—C22—C17	117.5 (2)
N1—C1—C2	178.3 (3)	C21—C22—C14	122.3 (2)
C6—C2—C1	122.0 (2)	C17—C22—C14	120.2 (2)
C6—C2—C3	120.4 (2)	N4—C23—C24	111.3 (2)
C1—C2—C3	117.5 (2)	N4—C23—H23A	109.4
N2—C3—C2	178.2 (3)	C24—C23—H23A	109.4
C11—C4—C7	132.8 (2)	N4—C23—H23B	109.4
C11—C4—C5	120.8 (2)	C24—C23—H23B	109.4
C7—C4—C5	106.40 (19)	H23A—C23—H23B	108.0
O1—C5—C8	106.84 (19)	C25—C24—C23	115.4 (2)
O1—C5—C9	106.86 (18)	C25—C24—H24A	108.4
C8—C5—C9	113.4 (2)	C23—C24—H24A	108.4
O1—C5—C4	103.82 (17)	C25—C24—H24B	108.4
C8—C5—C4	113.2 (2)	C23—C24—H24B	108.4
C9—C5—C4	111.9 (2)	H24A—C24—H24B	107.5
O1—C6—C2	117.5 (2)	C26—C25—C24	115.0 (2)
O1—C6—C7	111.19 (19)	C26—C25—H25A	108.5
C2—C6—C7	131.3 (2)	C24—C25—H25A	108.5
C4—C7—C6	109.1 (2)	C26—C25—H25B	108.5
C4—C7—C10	126.9 (2)	C24—C25—H25B	108.5
C6—C7—C10	124.0 (2)	H25A—C25—H25B	107.5
C5—C8—H8A	109.5	C25—C26—C27	113.2 (2)
C5—C8—H8B	109.5	C25—C26—H26A	108.9
H8A—C8—H8B	109.5	C27—C26—H26A	108.9
C5—C8—H8C	109.5	C25—C26—H26B	108.9
H8A—C8—H8C	109.5	C27—C26—H26B	108.9
H8B—C8—H8C	109.5	H26A—C26—H26B	107.8
C5—C9—H9A	109.5	C28—C27—C26	114.9 (2)
C5—C9—H9B	109.5	C28—C27—H27A	108.6
H9A—C9—H9B	109.5	C26—C27—H27A	108.6
C5—C9—H9C	109.5	C28—C27—H27B	108.6
H9A—C9—H9C	109.5	C26—C27—H27B	108.6
H9B—C9—H9C	109.5	H27A—C27—H27B	107.5
N3—C10—C7	178.6 (3)	C27—C28—C29	113.6 (2)
C4—C11—C12	124.6 (2)	C27—C28—H28A	108.9
C4—C11—H11	117.7	C29—C28—H28A	108.9
C12—C11—H11	117.7	C27—C28—H28B	108.9
C13—C12—C11	124.2 (2)	C29—C28—H28B	108.9
C13—C12—H12	117.9	H28A—C28—H28B	107.7
C11—C12—H12	117.9	C30—C29—C28	114.3 (2)
C12—C13—C14	123.6 (2)	C30—C29—H29A	108.7
C12—C13—H13	118.2	C28—C29—H29A	108.7
C14—C13—H13	118.2	C30—C29—H29B	108.7
C15—C14—C13	123.0 (2)	C28—C29—H29B	108.7
C15—C14—C22	115.8 (2)	H29A—C29—H29B	107.6
C13—C14—C22	121.2 (2)	C32—C31—C30	114.7 (3)
C16—C15—C14	121.7 (2)	C32—C31—H31A	108.6
C16—C15—H15	119.1	C30—C31—H31A	108.6
C14—C15—H15	119.1	C32—C31—H31B	108.6
N4—C16—C15	123.0 (2)	C30—C31—H31B	108.6
N4—C16—H16	118.5	H31A—C31—H31B	107.6
C15—C16—H16	118.5	C31—C30—C29	112.9 (2)
N4—C17—C18	120.8 (2)	C31—C30—H30A	109.0
N4—C17—C22	119.4 (2)	C29—C30—H30A	109.0
C18—C17—C22	119.8 (2)	C31—C30—H30B	109.0
C19—C18—C17	120.4 (2)	C29—C30—H30B	109.0
C19—C18—H18	119.8	H30A—C30—H30B	107.8
C17—C18—H18	119.8	C31—C32—H32A	109.5
C18—C19—C20	120.8 (2)	C31—C32—H32B	109.5
C18—C19—H19	119.6	H32A—C32—H32B	109.5
C20—C19—H19	119.6	C31—C32—H32C	109.5
C21—C20—C19	119.5 (2)	H32A—C32—H32C	109.5
C21—C20—H20	120.2	H32B—C32—H32C	109.5
C19—C20—H20	120.2
C6—O1—C5—C8	121.1 (2)	C23—N4—C16—C15	−175.0 (2)
C6—O1—C5—C9	−117.2 (2)	C14—C15—C16—N4	−0.2 (4)
C6—O1—C5—C4	1.3 (2)	C16—N4—C17—C18	177.6 (2)
C11—C4—C5—O1	−180.0 (2)	C23—N4—C17—C18	−7.2 (3)
C7—C4—C5—O1	−0.9 (3)	C16—N4—C17—C22	−0.7 (3)
C11—C4—C5—C8	64.6 (3)	C23—N4—C17—C22	174.6 (2)
C7—C4—C5—C8	−116.4 (2)	N4—C17—C18—C19	−179.0 (2)
C11—C4—C5—C9	−65.1 (3)	C22—C17—C18—C19	−0.8 (4)
C7—C4—C5—C9	114.0 (2)	C17—C18—C19—C20	0.0 (4)
C5—O1—C6—C2	178.2 (2)	C18—C19—C20—C21	0.6 (4)
C5—O1—C6—C7	−1.2 (3)	C19—C20—C21—C22	−0.4 (4)
C1—C2—C6—O1	−174.4 (2)	C20—C21—C22—C17	−0.5 (4)
C3—C2—C6—O1	2.6 (4)	C20—C21—C22—C14	178.1 (2)
C1—C2—C6—C7	4.8 (4)	N4—C17—C22—C21	179.3 (2)
C3—C2—C6—C7	−178.1 (3)	C18—C17—C22—C21	1.1 (3)
C11—C4—C7—C6	179.2 (3)	N4—C17—C22—C14	0.7 (3)
C5—C4—C7—C6	0.3 (3)	C18—C17—C22—C14	−177.5 (2)
C11—C4—C7—C10	−2.0 (5)	C15—C14—C22—C21	−179.0 (2)
C5—C4—C7—C10	179.2 (3)	C13—C14—C22—C21	0.9 (4)
O1—C6—C7—C4	0.5 (3)	C15—C14—C22—C17	−0.5 (3)
C2—C6—C7—C4	−178.8 (3)	C13—C14—C22—C17	179.4 (2)
O1—C6—C7—C10	−178.3 (2)	C16—N4—C23—C24	102.6 (3)
C2—C6—C7—C10	2.4 (4)	C17—N4—C23—C24	−72.8 (3)
C7—C4—C11—C12	1.0 (5)	N4—C23—C24—C25	−62.8 (3)
C5—C4—C11—C12	179.8 (2)	C23—C24—C25—C26	−69.8 (3)
C4—C11—C12—C13	179.0 (3)	C24—C25—C26—C27	−172.8 (2)
C11—C12—C13—C14	−178.8 (2)	C25—C26—C27—C28	175.4 (2)
C12—C13—C14—C15	−1.3 (4)	C26—C27—C28—C29	−65.2 (3)
C12—C13—C14—C22	178.9 (2)	C27—C28—C29—C30	−174.5 (2)
C13—C14—C15—C16	−179.7 (2)	C32—C31—C30—C29	171.9 (3)
C22—C14—C15—C16	0.2 (4)	C28—C29—C30—C31	174.3 (3)
C17—N4—C16—C15	0.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···N3^i	0.98	2.45	3.367 (3)	156
C21—H21···N1^i	0.95	2.53	3.424 (3)	158

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

(II) 2-{3-cyano-4-[5-(1-decyl-1,4-dihydroquinolin-4-ylidene)penta-1,3-dienyl]-5,5- dimethyl-2,5-dihydrofuran-2-ylidene}malononitrile

Crystal data

C34H38N4O	F(000) = 1112
Mr = 518.68	Dx = 1.143 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3141 reflections
a = 12.5261 (7) Å	θ = 3.3–27.9°
b = 9.8849 (5) Å	µ = 0.07 mm^−1
c = 24.3711 (13) Å	T = 97 K
β = 92.211 (3)°	Block, green
V = 3015.4 (3) Å^3	0.26 × 0.24 × 0.10 mm
Z = 4

Data collection

Bruker Nonius APEXII CCD area-detector diffractometer	2887 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.083
Graphite monochromator	θmax = 25.0°, θmin = 3.2°
Detector resolution: 8.333 pixels mm^-1	h = −14→13
ϕ and ω scans	k = −11→11
18727 measured reflections	l = −28→24
5267 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0715P)^2] where P = (Fo^2 + 2Fc^2)/3
5267 reflections	(Δ/σ)max = 0.009
370 parameters	Δρmax = 0.39 e Å^−3
24 restraints	Δρmin = −0.34 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.82801 (14)	−0.17716 (17)	0.22223 (7)	0.0266 (5)
N1	1.0270 (2)	−0.3194 (3)	0.30598 (10)	0.0412 (7)
N2	1.0646 (2)	−0.4810 (3)	0.13747 (10)	0.0547 (8)
N3	0.90150 (19)	−0.3019 (3)	0.03842 (10)	0.0371 (6)
N4	0.21965 (17)	0.5556 (2)	−0.00711 (9)	0.0289 (6)
C1	1.0008 (2)	−0.3233 (3)	0.26051 (12)	0.0295 (7)
C2	0.9669 (2)	−0.3276 (3)	0.20428 (10)	0.0260 (6)
C3	1.0215 (2)	−0.4117 (3)	0.16790 (12)	0.0357 (7)
C4	0.7560 (2)	−0.1253 (3)	0.13410 (10)	0.0237 (6)
C5	0.7432 (2)	−0.0938 (3)	0.19433 (10)	0.0248 (6)
C6	0.8820 (2)	−0.2474 (3)	0.18462 (10)	0.0232 (6)
C7	0.8397 (2)	−0.2223 (3)	0.13184 (10)	0.0227 (6)
C8	0.7697 (2)	0.0513 (3)	0.21009 (11)	0.0314 (7)
H8A	0.7699	0.0606	0.2501	0.047*
H8B	0.7159	0.1120	0.1933	0.047*
H8C	0.8403	0.0748	0.1970	0.047*
C9	0.6377 (2)	−0.1424 (3)	0.21562 (11)	0.0306 (7)
H9A	0.6270	−0.2377	0.2058	0.046*
H9B	0.5793	−0.0882	0.1992	0.046*
H9C	0.6385	−0.1327	0.2557	0.046*
C10	0.8776 (2)	−0.2704 (3)	0.08150 (12)	0.0266 (7)
C11	0.7026 (2)	−0.0691 (3)	0.09009 (11)	0.0265 (7)
H11	0.7210	−0.1019	0.0550	0.032*
C12	0.6231 (2)	0.0320 (3)	0.09039 (11)	0.0267 (7)
H12	0.5972	0.0591	0.1248	0.032*
C13	0.5811 (2)	0.0932 (3)	0.04440 (11)	0.0265 (6)
H13	0.6041	0.0630	0.0098	0.032*
C14	0.5055 (2)	0.1986 (3)	0.04512 (11)	0.0256 (6)
H14	0.4783	0.2241	0.0795	0.031*
C15	0.4693 (2)	0.2659 (3)	−0.00037 (11)	0.0244 (6)
H15	0.4994	0.2420	−0.0342	0.029*
C16	0.3899 (2)	0.3696 (3)	−0.00195 (10)	0.0231 (6)
C17	0.3274 (2)	0.3970 (3)	0.04291 (11)	0.0309 (7)
H17	0.3430	0.3529	0.0769	0.037*
C18	0.2441 (2)	0.4862 (3)	0.03878 (11)	0.0317 (7)
H18	0.2017	0.4995	0.0698	0.038*
C19	0.2811 (2)	0.5413 (3)	−0.05266 (10)	0.0250 (6)
C20	0.2569 (2)	0.6160 (3)	−0.10066 (10)	0.0291 (7)
H20	0.1973	0.6754	−0.1023	0.035*
C21	0.3196 (2)	0.6026 (3)	−0.14486 (11)	0.0323 (7)
H21	0.3035	0.6539	−0.1771	0.039*
C22	0.4068 (2)	0.5152 (3)	−0.14363 (11)	0.0319 (7)
H22	0.4503	0.5083	−0.1746	0.038*
C23	0.4297 (2)	0.4397 (3)	−0.09792 (10)	0.0269 (7)
H23	0.4889	0.3797	−0.0977	0.032*
C24	0.3672 (2)	0.4484 (3)	−0.05059 (10)	0.0236 (6)
C25	0.1219 (2)	0.6402 (3)	−0.00832 (12)	0.0373 (8)
H25A	0.0739	0.6073	0.0201	0.045*
H25B	0.0840	0.6294	−0.0445	0.045*
C26	0.1445 (2)	0.7890 (3)	0.00141 (12)	0.0399 (8)
H26A	0.0762	0.8394	−0.0013	0.048*
H26B	0.1900	0.8226	−0.0280	0.048*
C27	0.1996 (3)	0.8187 (3)	0.05686 (12)	0.0455 (9)
H27A	0.2738	0.7841	0.0564	0.055*
H27B	0.1624	0.7680	0.0855	0.055*
C28	0.2034 (3)	0.9676 (4)	0.07311 (14)	0.0599 (10)
H28A	0.2226	1.0236	0.0413	0.072*
H28B	0.2580	0.9819	0.1030	0.072*
C29A	0.0924 (4)	1.0091 (5)	0.0925 (2)	0.0429 (13)	0.683 (4)
H29A	0.0731	0.9518	0.1239	0.051*	0.683 (4)
H29B	0.0382	0.9950	0.0624	0.051*	0.683 (4)
C30A	0.0929 (4)	1.1605 (5)	0.11014 (19)	0.0516 (15)	0.683 (4)
H30A	0.1166	1.2154	0.0789	0.062*	0.683 (4)
H30B	0.0186	1.1874	0.1173	0.062*	0.683 (4)
C31A	0.1603 (4)	1.1945 (5)	0.15850 (18)	0.0570 (16)	0.683 (4)
H31A	0.2323	1.1568	0.1531	0.068*	0.683 (4)
H31B	0.1676	1.2942	0.1599	0.068*	0.683 (4)
C32A	0.1279 (4)	1.1517 (6)	0.2090 (2)	0.0574 (16)	0.683 (4)
H32A	0.1265	1.0516	0.2089	0.069*	0.683 (4)
H32B	0.0537	1.1832	0.2134	0.069*	0.683 (4)
C33A	0.1953 (6)	1.1982 (10)	0.2589 (2)	0.107 (3)*	0.683 (4)
H33A	0.2689	1.1637	0.2551	0.128*	0.683 (4)
H33B	0.1991	1.2982	0.2581	0.128*	0.683 (4)
C34A	0.1589 (6)	1.1571 (8)	0.3131 (3)	0.113 (3)*	0.683 (4)
H34A	0.0890	1.1977	0.3193	0.170*	0.683 (4)
H34B	0.2106	1.1878	0.3417	0.170*	0.683 (4)
H34C	0.1530	1.0583	0.3145	0.170*	0.683 (4)
C29B	0.1197 (12)	1.0701 (17)	0.0784 (5)	0.071 (5)*	0.317 (4)
H29C	0.0701	1.0684	0.0458	0.085*	0.317 (4)
H29D	0.1519	1.1614	0.0815	0.085*	0.317 (4)
C30B	0.0607 (13)	1.0375 (19)	0.1292 (6)	0.106 (6)*	0.317 (4)
H30C	−0.0011	1.0997	0.1304	0.127*	0.317 (4)
H30D	0.0316	0.9449	0.1248	0.127*	0.317 (4)
C31B	0.1139 (14)	1.043 (2)	0.1795 (5)	0.140*	0.317 (4)
H31C	0.1322	0.9473	0.1864	0.168*	0.317 (4)
H31D	0.1822	1.0867	0.1704	0.168*	0.317 (4)
C32B	0.0982 (12)	1.0911 (18)	0.2314 (6)	0.130 (8)*	0.317 (4)
H32C	0.0561	1.0215	0.2502	0.156*	0.317 (4)
H32D	0.0516	1.1716	0.2272	0.156*	0.317 (4)
C33B	0.1879 (11)	1.1300 (11)	0.2704 (6)	0.077 (5)*	0.317 (4)
H33C	0.2554	1.0974	0.2552	0.092*	0.317 (4)
H33D	0.1784	1.0813	0.3054	0.092*	0.317 (4)
C34B	0.2010 (9)	1.2816 (10)	0.2836 (5)	0.057 (3)*	0.317 (4)
H34D	0.2311	1.3280	0.2522	0.085*	0.317 (4)
H34E	0.2492	1.2926	0.3159	0.085*	0.317 (4)
H34F	0.1311	1.3206	0.2911	0.085*	0.317 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0307 (11)	0.0274 (10)	0.0216 (10)	0.0093 (8)	−0.0007 (8)	0.0011 (8)
N1	0.0349 (16)	0.0584 (18)	0.0301 (15)	0.0052 (13)	−0.0001 (12)	0.0082 (14)
N2	0.065 (2)	0.065 (2)	0.0349 (17)	0.0321 (16)	0.0123 (15)	0.0118 (15)
N3	0.0299 (15)	0.0519 (17)	0.0293 (15)	0.0082 (12)	−0.0009 (12)	−0.0009 (13)
N4	0.0262 (14)	0.0329 (14)	0.0275 (14)	0.0092 (11)	0.0014 (10)	0.0044 (11)
C1	0.0215 (16)	0.0386 (18)	0.0287 (18)	0.0046 (13)	0.0029 (13)	0.0105 (15)
C2	0.0229 (16)	0.0331 (16)	0.0219 (15)	0.0050 (12)	0.0009 (12)	0.0050 (13)
C3	0.0371 (19)	0.0445 (19)	0.0257 (17)	0.0131 (15)	0.0035 (14)	0.0111 (15)
C4	0.0267 (16)	0.0222 (15)	0.0221 (15)	−0.0008 (12)	−0.0004 (12)	−0.0007 (12)
C5	0.0256 (16)	0.0255 (15)	0.0229 (15)	0.0081 (12)	−0.0041 (12)	0.0007 (12)
C6	0.0243 (16)	0.0225 (14)	0.0230 (15)	−0.0006 (12)	0.0039 (12)	0.0007 (12)
C7	0.0238 (15)	0.0245 (15)	0.0199 (15)	0.0031 (12)	0.0000 (11)	0.0012 (12)
C8	0.0392 (19)	0.0250 (16)	0.0292 (16)	0.0042 (13)	−0.0066 (13)	−0.0018 (13)
C9	0.0315 (17)	0.0327 (17)	0.0276 (16)	0.0042 (13)	0.0003 (13)	−0.0001 (13)
C10	0.0231 (16)	0.0320 (17)	0.0244 (17)	0.0035 (12)	−0.0034 (12)	0.0018 (13)
C11	0.0273 (16)	0.0261 (16)	0.0258 (16)	0.0024 (12)	−0.0021 (12)	−0.0028 (13)
C12	0.0289 (17)	0.0282 (16)	0.0226 (16)	0.0011 (12)	−0.0024 (12)	−0.0015 (13)
C13	0.0285 (17)	0.0284 (16)	0.0222 (15)	0.0033 (12)	−0.0055 (12)	−0.0020 (13)
C14	0.0266 (16)	0.0276 (16)	0.0224 (15)	0.0022 (12)	−0.0012 (12)	−0.0027 (12)
C15	0.0249 (16)	0.0288 (16)	0.0192 (15)	0.0017 (12)	−0.0018 (12)	−0.0025 (12)
C16	0.0248 (16)	0.0251 (15)	0.0191 (15)	0.0001 (12)	−0.0025 (12)	0.0002 (12)
C17	0.0336 (18)	0.0363 (17)	0.0226 (16)	0.0073 (14)	−0.0009 (13)	0.0056 (13)
C18	0.0352 (18)	0.0356 (18)	0.0248 (17)	0.0068 (14)	0.0069 (13)	0.0020 (14)
C19	0.0253 (16)	0.0267 (16)	0.0229 (16)	0.0023 (12)	−0.0019 (12)	0.0013 (12)
C20	0.0312 (17)	0.0306 (17)	0.0249 (16)	0.0066 (13)	−0.0072 (13)	0.0019 (13)
C21	0.046 (2)	0.0265 (16)	0.0234 (16)	−0.0001 (14)	−0.0060 (14)	0.0042 (13)
C22	0.0402 (19)	0.0332 (17)	0.0224 (16)	−0.0006 (14)	0.0037 (13)	0.0017 (14)
C23	0.0279 (17)	0.0312 (16)	0.0215 (16)	0.0036 (12)	−0.0003 (12)	−0.0005 (13)
C24	0.0230 (16)	0.0265 (15)	0.0209 (15)	0.0000 (12)	−0.0041 (12)	−0.0009 (12)
C25	0.0287 (18)	0.0411 (19)	0.0423 (19)	0.0158 (14)	0.0059 (14)	0.0070 (15)
C26	0.0353 (19)	0.043 (2)	0.042 (2)	0.0166 (14)	0.0069 (15)	0.0057 (15)
C27	0.053 (2)	0.044 (2)	0.040 (2)	0.0109 (16)	0.0091 (16)	0.0024 (16)
C28	0.073 (3)	0.057 (2)	0.050 (2)	0.019 (2)	0.0030 (19)	−0.0057 (19)
C29A	0.056 (4)	0.037 (3)	0.036 (3)	0.007 (3)	0.011 (3)	0.000 (3)
C30A	0.064 (4)	0.041 (3)	0.050 (3)	0.016 (3)	−0.005 (3)	−0.016 (3)
C31A	0.059 (4)	0.056 (4)	0.055 (4)	0.018 (3)	−0.014 (3)	−0.023 (3)
C32A	0.046 (3)	0.075 (4)	0.050 (4)	−0.002 (3)	−0.011 (3)	−0.011 (3)

Geometric parameters (Å, º)

O1—C6	1.352 (3)	C25—C26	1.515 (4)
O1—C5	1.488 (3)	C25—H25A	0.9900
N1—C1	1.144 (3)	C25—H25B	0.9900
N2—C3	1.158 (3)	C26—C27	1.522 (4)
N3—C10	1.146 (3)	C26—H26A	0.9900
N4—C18	1.337 (3)	C26—H26B	0.9900
N4—C19	1.382 (3)	C27—C28	1.524 (4)
N4—C25	1.482 (3)	C27—H27A	0.9900
C1—C2	1.420 (4)	C27—H27B	0.9900
C2—C6	1.396 (3)	C28—C29B	1.467 (15)
C2—C3	1.412 (4)	C28—C29A	1.541 (6)
C4—C11	1.360 (3)	C28—H28A	0.9900
C4—C7	1.423 (3)	C28—H28B	0.9900
C4—C5	1.515 (3)	C29A—C30A	1.556 (7)
C5—C9	1.516 (4)	C29A—H29A	0.9900
C5—C8	1.518 (3)	C29A—H29B	0.9900
C6—C7	1.394 (3)	C30A—C31A	1.462 (5)
C7—C10	1.415 (4)	C30A—H30A	0.9900
C8—H8A	0.9800	C30A—H30B	0.9900
C8—H8B	0.9800	C31A—C32A	1.377 (6)
C8—H8C	0.9800	C31A—H31A	0.9900
C9—H9A	0.9800	C31A—H31B	0.9900
C9—H9B	0.9800	C32A—C33A	1.525 (7)
C9—H9C	0.9800	C32A—H32A	0.9900
C11—C12	1.412 (4)	C32A—H32B	0.9900
C11—H11	0.9500	C33A—C34A	1.472 (7)
C12—C13	1.361 (3)	C33A—H33A	0.9900
C12—H12	0.9500	C33A—H33B	0.9900
C13—C14	1.409 (3)	C34A—H34A	0.9800
C13—H13	0.9500	C34A—H34B	0.9800
C14—C15	1.356 (3)	C34A—H34C	0.9800
C14—H14	0.9500	C29B—C30B	1.501 (18)
C15—C16	1.427 (3)	C29B—H29C	0.9900
C15—H15	0.9500	C29B—H29D	0.9900
C16—C17	1.396 (4)	C30B—C31B	1.373 (8)
C16—C24	1.438 (3)	C30B—H30C	0.9900
C17—C18	1.367 (4)	C30B—H30D	0.9900
C17—H17	0.9500	C31B—C32B	1.371 (9)
C18—H18	0.9500	C31B—H31C	0.9900
C19—C20	1.407 (3)	C31B—H31D	0.9900
C19—C24	1.415 (4)	C32B—C33B	1.494 (8)
C20—C21	1.364 (4)	C32B—H32C	0.9900
C20—H20	0.9500	C32B—H32D	0.9900
C21—C22	1.392 (4)	C33B—C34B	1.539 (8)
C21—H21	0.9500	C33B—H33C	0.9900
C22—C23	1.362 (3)	C33B—H33D	0.9900
C22—H22	0.9500	C34B—H34D	0.9800
C23—C24	1.421 (3)	C34B—H34E	0.9800
C23—H23	0.9500	C34B—H34F	0.9800
C6—O1—C5	109.97 (18)	C25—C26—H26A	108.8
C18—N4—C19	120.2 (2)	C27—C26—H26A	108.8
C18—N4—C25	117.9 (2)	C25—C26—H26B	108.8
C19—N4—C25	121.8 (2)	C27—C26—H26B	108.8
N1—C1—C2	179.2 (3)	H26A—C26—H26B	107.7
C6—C2—C3	120.0 (2)	C26—C27—C28	115.2 (3)
C6—C2—C1	120.7 (2)	C26—C27—H27A	108.5
C3—C2—C1	119.3 (2)	C28—C27—H27A	108.5
N2—C3—C2	178.7 (3)	C26—C27—H27B	108.5
C11—C4—C7	125.8 (2)	C28—C27—H27B	108.5
C11—C4—C5	127.8 (2)	H27A—C27—H27B	107.5
C7—C4—C5	106.4 (2)	C29B—C28—C27	132.4 (7)
O1—C5—C4	103.20 (19)	C27—C28—C29A	108.5 (3)
O1—C5—C9	106.5 (2)	C29B—C28—H28A	83.1
C4—C5—C9	113.2 (2)	C27—C28—H28A	110.0
O1—C5—C8	105.2 (2)	C29A—C28—H28A	110.0
C4—C5—C8	114.1 (2)	C29B—C28—H28B	108.2
C9—C5—C8	113.4 (2)	C27—C28—H28B	110.0
O1—C6—C7	110.6 (2)	C29A—C28—H28B	110.0
O1—C6—C2	116.9 (2)	H28A—C28—H28B	108.4
C7—C6—C2	132.4 (2)	C28—C29A—C30A	110.3 (4)
C6—C7—C10	127.7 (2)	C28—C29A—H29A	109.6
C6—C7—C4	109.8 (2)	C30A—C29A—H29A	109.6
C10—C7—C4	122.2 (2)	C28—C29A—H29B	109.6
C5—C8—H8A	109.5	C30A—C29A—H29B	109.6
C5—C8—H8B	109.5	H29A—C29A—H29B	108.1
H8A—C8—H8B	109.5	C31A—C30A—C29A	116.1 (4)
C5—C8—H8C	109.5	C31A—C30A—H30A	108.3
H8A—C8—H8C	109.5	C29A—C30A—H30A	108.3
H8B—C8—H8C	109.5	C31A—C30A—H30B	108.3
C5—C9—H9A	109.5	C29A—C30A—H30B	108.3
C5—C9—H9B	109.5	H30A—C30A—H30B	107.4
H9A—C9—H9B	109.5	C32A—C31A—C30A	118.0 (5)
C5—C9—H9C	109.5	C32A—C31A—H31A	107.8
H9A—C9—H9C	109.5	C30A—C31A—H31A	107.8
H9B—C9—H9C	109.5	C32A—C31A—H31B	107.8
N3—C10—C7	173.8 (3)	C30A—C31A—H31B	107.8
C4—C11—C12	127.6 (3)	H31A—C31A—H31B	107.1
C4—C11—H11	116.2	C31A—C32A—C33A	116.6 (5)
C12—C11—H11	116.2	C31A—C32A—H32A	108.2
C13—C12—C11	124.1 (3)	C33A—C32A—H32A	108.2
C13—C12—H12	117.9	C31A—C32A—H32B	108.2
C11—C12—H12	117.9	C33A—C32A—H32B	108.2
C12—C13—C14	123.9 (3)	H32A—C32A—H32B	107.3
C12—C13—H13	118.1	C34A—C33A—C32A	116.9 (6)
C14—C13—H13	118.1	C34A—C33A—H33A	108.1
C15—C14—C13	123.8 (3)	C32A—C33A—H33A	108.1
C15—C14—H14	118.1	C34A—C33A—H33B	108.1
C13—C14—H14	118.1	C32A—C33A—H33B	108.1
C14—C15—C16	125.8 (3)	H33A—C33A—H33B	107.3
C14—C15—H15	117.1	C28—C29B—C30B	107.5 (12)
C16—C15—H15	117.1	C28—C29B—H29C	110.2
C17—C16—C15	122.0 (2)	C30B—C29B—H29C	110.2
C17—C16—C24	116.2 (2)	C28—C29B—H29D	110.2
C15—C16—C24	121.8 (2)	C30B—C29B—H29D	110.2
C18—C17—C16	121.2 (3)	H29C—C29B—H29D	108.5
C18—C17—H17	119.4	C31B—C30B—C29B	119.4 (14)
C16—C17—H17	119.4	C31B—C30B—H30C	107.5
N4—C18—C17	122.8 (3)	C29B—C30B—H30C	107.5
N4—C18—H18	118.6	C31B—C30B—H30D	107.5
C17—C18—H18	118.6	C29B—C30B—H30D	107.5
N4—C19—C20	120.3 (2)	H30C—C30B—H30D	107.0
N4—C19—C24	119.0 (2)	C32B—C31B—C30B	139.2 (16)
C20—C19—C24	120.7 (2)	C32B—C31B—H31C	102.3
C21—C20—C19	119.6 (3)	C30B—C31B—H31C	102.3
C21—C20—H20	120.2	C32B—C31B—H31D	102.3
C19—C20—H20	120.2	C30B—C31B—H31D	102.3
C20—C21—C22	121.3 (3)	H31C—C31B—H31D	104.9
C20—C21—H21	119.4	C31B—C32B—C33B	123.0 (13)
C22—C21—H21	119.4	C31B—C32B—H32C	106.6
C23—C22—C21	119.8 (3)	C33B—C32B—H32C	106.6
C23—C22—H22	120.1	C31B—C32B—H32D	106.6
C21—C22—H22	120.1	C33B—C32B—H32D	106.6
C22—C23—C24	121.7 (3)	H32C—C32B—H32D	106.5
C22—C23—H23	119.1	C32B—C33B—C34B	117.1 (10)
C24—C23—H23	119.1	C32B—C33B—H33C	108.0
C19—C24—C23	116.9 (2)	C34B—C33B—H33C	108.0
C19—C24—C16	120.5 (2)	C32B—C33B—H33D	108.0
C23—C24—C16	122.6 (2)	C34B—C33B—H33D	108.0
N4—C25—C26	113.3 (2)	H33C—C33B—H33D	107.3
N4—C25—H25A	108.9	C33B—C34B—H34D	109.5
C26—C25—H25A	108.9	C33B—C34B—H34E	109.5
N4—C25—H25B	108.9	H34D—C34B—H34E	109.5
C26—C25—H25B	108.9	C33B—C34B—H34F	109.5
H25A—C25—H25B	107.7	H34D—C34B—H34F	109.5
C25—C26—C27	113.7 (2)	H34E—C34B—H34F	109.5
C6—O1—C5—C4	−0.4 (3)	C25—N4—C19—C20	5.1 (4)
C6—O1—C5—C9	119.0 (2)	C18—N4—C19—C24	2.5 (4)
C6—O1—C5—C8	−120.3 (2)	C25—N4—C19—C24	−173.6 (2)
C11—C4—C5—O1	−175.5 (2)	N4—C19—C20—C21	178.7 (3)
C7—C4—C5—O1	1.9 (3)	C24—C19—C20—C21	−2.6 (4)
C11—C4—C5—C9	69.8 (3)	C19—C20—C21—C22	0.6 (4)
C7—C4—C5—C9	−112.8 (2)	C20—C21—C22—C23	1.0 (4)
C11—C4—C5—C8	−61.9 (4)	C21—C22—C23—C24	−0.7 (4)
C7—C4—C5—C8	115.5 (2)	N4—C19—C24—C23	−178.5 (2)
C5—O1—C6—C7	−1.4 (3)	C20—C19—C24—C23	2.8 (4)
C5—O1—C6—C2	178.0 (2)	N4—C19—C24—C16	0.4 (4)
C3—C2—C6—O1	175.1 (2)	C20—C19—C24—C16	−178.3 (2)
C1—C2—C6—O1	−6.4 (4)	C22—C23—C24—C19	−1.2 (4)
C3—C2—C6—C7	−5.7 (5)	C22—C23—C24—C16	180.0 (2)
C1—C2—C6—C7	172.8 (3)	C17—C16—C24—C19	−4.0 (4)
O1—C6—C7—C10	176.2 (2)	C15—C16—C24—C19	173.8 (2)
C2—C6—C7—C10	−3.1 (5)	C17—C16—C24—C23	174.8 (2)
O1—C6—C7—C4	2.7 (3)	C15—C16—C24—C23	−7.4 (4)
C2—C6—C7—C4	−176.5 (3)	C18—N4—C25—C26	100.4 (3)
C11—C4—C7—C6	174.6 (3)	C19—N4—C25—C26	−83.4 (3)
C5—C4—C7—C6	−2.8 (3)	N4—C25—C26—C27	−60.5 (3)
C11—C4—C7—C10	0.7 (4)	C25—C26—C27—C28	−168.1 (3)
C5—C4—C7—C10	−176.7 (2)	C26—C27—C28—C29B	55.7 (9)
C7—C4—C11—C12	−176.6 (3)	C26—C27—C28—C29A	76.9 (4)
C5—C4—C11—C12	0.4 (5)	C29B—C28—C29A—C30A	−33.0 (12)
C4—C11—C12—C13	172.8 (3)	C27—C28—C29A—C30A	179.4 (3)
C11—C12—C13—C14	−176.8 (3)	C28—C29A—C30A—C31A	−66.0 (6)
C12—C13—C14—C15	175.2 (3)	C29A—C30A—C31A—C32A	−71.4 (7)
C13—C14—C15—C16	177.4 (3)	C30A—C31A—C32A—C33A	−175.4 (6)
C14—C15—C16—C17	−11.2 (4)	C31A—C32A—C33A—C34A	177.8 (7)
C14—C15—C16—C24	171.1 (3)	C27—C28—C29B—C30B	72.9 (12)
C15—C16—C17—C18	−172.8 (3)	C29A—C28—C29B—C30B	29.4 (9)
C24—C16—C17—C18	5.0 (4)	C28—C29B—C30B—C31B	64 (2)
C19—N4—C18—C17	−1.6 (4)	C29B—C30B—C31B—C32B	136 (3)
C25—N4—C18—C17	174.7 (3)	C30B—C31B—C32B—C33B	−154 (2)
C16—C17—C18—N4	−2.4 (4)	C31B—C32B—C33B—C34B	111 (2)
C18—N4—C19—C20	−178.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···N2^i	0.95	2.43	3.371 (4)	169
C21—H21···O1^ii	0.95	2.49	3.328 (3)	146
C12—H12···N1^iii	0.95	2.63	3.527 (4)	158
C10—N3···Cg2^iv	1.15 (1)	3.13 (1)	3.481 (3)	98 (2)

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