2-(3-Cyano-4-methyl-5,5-diphenyl-5H-furan-2-yl­idene)malono­nitrile

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

doi:10.1107/S1600536813020849

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 9| September 2013| Pages o1365-o1366

doi:10.1107/S1600536813020849

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2-(3-Cyano-4-methyl-5,5-diphenyl-5H-furan-2-ylidene)malononitrile

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

^aCallaghan Innovation Research Limited, PO Box 31-310, Lower Hutt, New Zealand, and ^bIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
^*Correspondence e-mail: graeme.gainsford@callaghaninnovation.govt.nz

(Received 20 July 2013; accepted 26 July 2013; online 3 August 2013)

The title compound, C₂₁H₁₃N₃O, crystallizes with two independent molecules with similar conformations per asymmetric unit. The dihydrofuran rings are essentially planar with maximum deviations of 0.017 (1) and 0.006 (1) Å for the O atoms. The dihedral angles between the dihydrofuran ring and the attached phenyl rings are 79.90 (6) and 82.07 (6)° in one molecule and 79.36 (6) and 72.26 (6)° in the other. In the crystal, the molecules are linked by weak C—H⋯π and C—H⋯N interactions similar to those in other closely related crystals. The replacement of appended methyl by phenyl groups has not significantly affected the dihydrofuran ring structure or the crystal packing interactions.

Related literature

For general background to NLO chromophores, see: Smith et al. (2006 , 2010 ); Carey et al. (2002 ); Kay et al. (2004 ). For details of the synthesis, see: Anderson (2009 ). For related structures, see: Anderson (2009); Gainsford et al. (2011 ); Li et al. (2005 ); Liao et al. (2005 ). For geometric analysis of structures, see: Spek (2009 ). For a description of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

C₂₁H₁₃N₃O
M_r = 323.34
Triclinic, $[P \overline 1]$
a = 9.2308 (3) Å
b = 12.5991 (4) Å
c = 14.3043 (4) Å
α = 89.954 (2)°
β = 89.052 (2)°
γ = 79.233 (2)°
V = 1634.07 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 123 K
0.36 × 0.32 × 0.29 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.651, T_max = 0.746
45305 measured reflections
9930 independent reflections
7329 reflections with I > 2σ(I)
R_int = 0.042

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.119
S = 1.04
9930 reflections
453 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C10–C15 phenyl ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20′—H20′⋯Cg1ⁱ	0.95	2.69	3.4041 (14)	133
C9—H9B⋯N3′	0.98	2.70	3.4560 (14)	134
Symmetry code: (i) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813020849/rz5081sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813020849/rz5081Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813020849/rz5081Isup3.cml

checkCIF report

Comment top

Organic non-linear optical (NLO) chromophores consist of donor and acceptor units connecting through π-conjugation. To realise a strong NLO response, chromophores need to be in uniform alignment. Unfortunately organic chromophores have a tendency to aggregate rather than align due to their highly polar nature (Smith et al., 2006). These push-pull chromophores can also exist as two rotomeric (cis and trans) forms (Kay et al., 2004). As a result, these chromophores are difficult to crystallize, therefore they may not be able to be used in devices that require crystals such as terahertz wave emitters (Carey et al., 2002). Consequently it is of interest to design and synthesize molecules which will be much less prone to aggregation and isomerization. It has been found that through changing the shape of the chromophore molecules, aggregation can be minimized. The most successful strategy has been to add bulky pendant groups onto the donor end (Smith et al., 2010). We have reported our previous attempts with two benzyloxyphenyl groups (Gainsford et al., 2011; Anderson, 2009) and report here the structure of a related acceptor unit with two phenyl groups.

The asymmetric unit of the title compound (I) contains two independent, nearly identical, 2-(3-cyano-4-methyl-5,5-diphenyl-5H-furan-2-ylidene)malononitrile molecules (Fig. 1). The second molecule (1') has identical labels with an appended prime (e.g. C10 and C10'); the r.m.s. bond and angle fits are 0.003 Å and 0.48° (Spek, 2009). The five-membered dihydrofuran rings (atoms C4-C7/O1, hereafter plane 1) are planar (maximum deviation 0.017 (1) Å for O1) with the appended cyano groups almost coplanar (maximum deviation 0.093 (1) Å for N1). The 5,5-dimethyl adduct (Li et al., 2005; CSD refcode PANLUM), in which plane 1 was constrained to a crystallographic mirror plane, has identical ring dimensions with the exception of the C4–C5 bond which is just significantly longer here (by 0.013 (4) Å). This marginally longer distance seems the exception and is not observed in related molecules [Allen (2002); CSD version 5.34 with May 2013 updates: e.g. KAJCII and KATCEE, 1.518 and 1.536, 1.537 Å respectively (Liao et al., 2005); YAHKUP 1.512 Å (Gainsford et al., 2011)].

The only significant conformational differences between the two molecules concern the interplanar angles between the phenyl rings and plane 1, corresponding to the different torsion angles (C4–C5–C10–C15 = -21.21 (15)°; O1–C5–C16–C17 = -30.62 (13)°; C4'–C5'–C10'–C15' = -30.22 (14)°; O1'–C5'–C16'–C17' = -21.91 (15)°). The plane 1 angle to phenyl plane (C10–C15) is 79.90 (6) and 82.07 (6)° for molecules 1 and 1' while the other phenyl plane (C16–C21) makes interplane angle of 79.36 (6) and 72.26 (6)° for molecules 1 and 1'.

Lattice binding is provided mainly by one non-classical C–H···π interaction (Table 1, Figure 2 where Cg1 is the centroid of the C10–C15 ring), the dominant binding interaction type in related compound YAHKUP (Gainsford et al., 2011). As in PANLUM, a weak methylC–H···N(cyano) interaction is observed. Other C–H···N(cyano), C–H···π and cyano···cyano very weak interactions even closer to van der Waal's contact distances are also present. Overall, the effect of the phenyl for methyl replacement on C5 has given insignificant molecular structural and cystal packing alignment affects.

Related literature top

For general background to NLO chromophores, see: Smith et al. (2006, 2010); Carey et al. (2002); Kay et al. (2004). For details of the synthesis, see: Anderson (2009). For related structures, see: Anderson (2009); Gainsford et al. (2011); Li et al. (2005); Liao et al. (2005). For geometric analysis of structures, see: Spek (2009). For a description of the Cambridge Structural Database, see: Allen (2002).

Experimental top

The title compound was prepared by the condensation of 1-hydroxy-1,1-diphenylpropan-2-one with 4 equivalents of malononitrile over 10 days as described in Anderson (2009). A small portion was recrystallized in dichloromethane and acetone (1:1) mixture to give colourless crystals. M.p. 223 °C. Found: C, 77.70; H, 3.91; N, 13.06, C₂₁H₁₃N₃O requires C, 78.00; H, 4.05; N, 13.00%. Found: M⁺ m/z 323.1059 C₂₁H₁₃N₃O requires: M+ m/z 323.1056 (Δ 0.9 p.p.m.). ¹H NMR– (300 MHz, CDCl₃) δ (p.p.m.): 2.41 (s, 3H), 7.18 (d, J 9.6 Hz, 4H), 7.51–7.47 (m, 6H). ¹³C NMR– (75 MHz, CDCl₃) δ (p.p.m.): 16.2 (CH₃), 59.5 (C_Q), 105.6 (C_Q), 106.4 (C_Q), 109.0 (C_Q), 110.2 (C_Q), 110.7 (C_Q), 127.3 (CH), 129.5 (CH), 130.6 (CH), 134.9 (C_Q), 175.1 (C_Q), 180.2 (C_Q).

Computing details top

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 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Content of the asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level. The partially obscured atom C15 is not labelled.
	Fig. 2. Packing diagram of the title compound with one C–H···π and C(methyl)–H···N(cyano) interaction shown as dashed blue lines. H atoms not involved in intermolecular contacts are excluded except on methyl C9. Cg1 is the centroid of the phenyl ring (C10–C15) at symmetry 1-x, 1-y, -z. Symmetry code: (i) -1+x, y, z.

2-(3-Cyano-4-methyl-5,5-diphenyl-5H-furan-2-ylidene)malononitrile top

Crystal data top

C₂₁H₁₃N₃O	Z = 4
M_r = 323.34	F(000) = 672
Triclinic, P1	D_x = 1.314 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2308 (3) Å	Cell parameters from 9027 reflections
b = 12.5991 (4) Å	θ = 2.2–30.5°
c = 14.3043 (4) Å	µ = 0.08 mm⁻¹
α = 89.954 (2)°	T = 123 K
β = 89.052 (2)°	Block, colourless
γ = 79.233 (2)°	0.36 × 0.32 × 0.29 mm
V = 1634.07 (9) Å³

Data collection top

Bruker APEXII CCD diffractometer	9930 independent reflections
Radiation source: fine-focus sealed tube	7329 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.042
Detector resolution: 8.333 pixels mm^-1	θ_max = 30.7°, θ_min = 1.4°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −18→18
T_min = 0.651, T_max = 0.746	l = −20→20
45305 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0512P)² + 0.3811P] where P = (F_o² + 2F_c²)/3
9930 reflections	(Δ/σ)_max < 0.001
453 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₂₁H₁₃N₃O	γ = 79.233 (2)°
M_r = 323.34	V = 1634.07 (9) Å³
Triclinic, P1	Z = 4
a = 9.2308 (3) Å	Mo Kα radiation
b = 12.5991 (4) Å	µ = 0.08 mm⁻¹
c = 14.3043 (4) Å	T = 123 K
α = 89.954 (2)°	0.36 × 0.32 × 0.29 mm
β = 89.052 (2)°

Data collection top

Bruker APEXII CCD diffractometer	9930 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	7329 reflections with I > 2σ(I)
T_min = 0.651, T_max = 0.746	R_int = 0.042
45305 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.04	Δρ_max = 0.35 e Å⁻³
9930 reflections	Δρ_min = −0.24 e Å⁻³
453 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.34806 (9)	0.80434 (6)	0.09747 (5)	0.01913 (17)
N1	0.71127 (14)	0.64480 (10)	−0.12562 (9)	0.0387 (3)
N2	0.41086 (13)	0.95957 (10)	−0.09834 (8)	0.0315 (3)
N3	0.68541 (13)	0.46791 (10)	0.06030 (8)	0.0320 (3)
C1	0.62087 (14)	0.70061 (10)	−0.08395 (9)	0.0255 (3)
C2	0.50822 (13)	0.77028 (10)	−0.03197 (8)	0.0204 (2)
C3	0.45366 (13)	0.87575 (10)	−0.06807 (8)	0.0228 (2)
C4	0.40415 (12)	0.64052 (9)	0.17749 (8)	0.0194 (2)
C5	0.30203 (12)	0.74917 (9)	0.18178 (8)	0.0176 (2)
C6	0.45279 (12)	0.73785 (9)	0.04999 (8)	0.0183 (2)
C7	0.49044 (12)	0.63614 (9)	0.10052 (8)	0.0193 (2)
C8	0.60060 (13)	0.54476 (10)	0.07557 (8)	0.0225 (2)
C9	0.40783 (15)	0.55820 (10)	0.25144 (9)	0.0269 (3)
H9A	0.4637	0.4889	0.2288	0.032*
H9B	0.3069	0.5502	0.2677	0.032*
H9C	0.4553	0.5808	0.3069	0.032*
C10	0.14038 (12)	0.74436 (9)	0.16821 (8)	0.0188 (2)
C11	0.03222 (13)	0.83316 (10)	0.19229 (8)	0.0225 (2)
H11	0.0589	0.8940	0.2219	0.027*
C12	−0.11448 (14)	0.83266 (11)	0.17303 (9)	0.0278 (3)
H12	−0.1884	0.8930	0.1899	0.033*
C13	−0.15301 (14)	0.74430 (12)	0.12926 (9)	0.0301 (3)
H13	−0.2535	0.7441	0.1162	0.036*
C14	−0.04624 (15)	0.65645 (11)	0.10437 (9)	0.0288 (3)
H14	−0.0733	0.5963	0.0738	0.035*
C15	0.10062 (14)	0.65600 (10)	0.12400 (9)	0.0238 (2)
H15	0.1740	0.5953	0.1072	0.029*
C16	0.33659 (12)	0.80840 (9)	0.26874 (8)	0.0186 (2)
C17	0.45540 (13)	0.86160 (10)	0.26897 (9)	0.0226 (2)
H17	0.5119	0.8654	0.2134	0.027*
C18	0.49144 (15)	0.90922 (11)	0.35082 (9)	0.0287 (3)
H18	0.5728	0.9456	0.3512	0.034*
C19	0.40914 (17)	0.90379 (12)	0.43177 (9)	0.0337 (3)
H19	0.4334	0.9371	0.4875	0.040*
C20	0.29189 (17)	0.85014 (12)	0.43188 (9)	0.0329 (3)
H20	0.2352	0.8468	0.4875	0.040*
C21	0.25681 (15)	0.80120 (10)	0.35100 (8)	0.0255 (3)
H21	0.1778	0.7625	0.3517	0.031*
O1'	0.98981 (9)	0.20107 (6)	0.40488 (5)	0.01929 (17)
N1'	1.26942 (15)	0.36533 (11)	0.61930 (9)	0.0397 (3)
N2'	1.13037 (14)	0.05064 (10)	0.60095 (8)	0.0346 (3)
N3'	1.16038 (13)	0.53580 (9)	0.43102 (8)	0.0302 (2)
C1'	1.20774 (14)	0.30913 (11)	0.57926 (9)	0.0265 (3)
C2'	1.13161 (13)	0.23860 (10)	0.53017 (8)	0.0214 (2)
C3'	1.12990 (14)	0.13375 (10)	0.56895 (8)	0.0236 (2)
C4'	0.97057 (12)	0.35981 (9)	0.31831 (8)	0.0192 (2)
C5'	0.92300 (12)	0.25132 (9)	0.31831 (8)	0.0181 (2)
C6'	1.06105 (12)	0.26850 (9)	0.44854 (8)	0.0183 (2)
C7'	1.05045 (12)	0.36764 (9)	0.39479 (8)	0.0194 (2)
C8'	1.11373 (13)	0.45944 (10)	0.41679 (8)	0.0220 (2)
C9'	0.93503 (15)	0.43960 (10)	0.24239 (9)	0.0262 (3)
H9'A	0.9634	0.5077	0.2607	0.031*
H9'B	0.8289	0.4520	0.2309	0.031*
H9'C	0.9893	0.4120	0.1853	0.031*
C10'	0.75678 (12)	0.26066 (9)	0.33075 (8)	0.0187 (2)
C11'	0.68589 (13)	0.18118 (10)	0.29681 (9)	0.0231 (2)
H11'	0.7401	0.1214	0.2630	0.028*
C12'	0.53511 (14)	0.18933 (11)	0.31243 (9)	0.0276 (3)
H12'	0.4859	0.1359	0.2879	0.033*
C13'	0.45660 (14)	0.27472 (11)	0.36351 (10)	0.0290 (3)
H13'	0.3537	0.2798	0.3741	0.035*
C14'	0.52747 (14)	0.35269 (11)	0.39920 (10)	0.0291 (3)
H14'	0.4737	0.4106	0.4353	0.035*
C15'	0.67724 (14)	0.34638 (10)	0.38225 (9)	0.0241 (2)
H15'	0.7256	0.4007	0.4059	0.029*
C16'	0.99343 (13)	0.18644 (9)	0.23453 (8)	0.0189 (2)
C17'	1.13164 (13)	0.12020 (9)	0.24063 (9)	0.0217 (2)
H17'	1.1791	0.1096	0.2992	0.026*
C18'	1.19993 (14)	0.06974 (10)	0.16117 (9)	0.0262 (3)
H18'	1.2949	0.0254	0.1654	0.031*
C19'	1.13090 (16)	0.08335 (10)	0.07570 (9)	0.0288 (3)
H19'	1.1776	0.0478	0.0216	0.035*
C20'	0.99357 (15)	0.14899 (11)	0.06954 (9)	0.0287 (3)
H20'	0.9458	0.1584	0.0110	0.034*
C21'	0.92545 (14)	0.20087 (10)	0.14786 (8)	0.0252 (3)
H21'	0.8317	0.2467	0.1428	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0182 (4)	0.0211 (4)	0.0176 (4)	−0.0025 (3)	0.0024 (3)	0.0021 (3)
N1	0.0364 (7)	0.0400 (7)	0.0369 (7)	−0.0012 (6)	0.0125 (5)	−0.0044 (6)
N2	0.0309 (6)	0.0339 (6)	0.0282 (6)	−0.0025 (5)	0.0041 (5)	0.0049 (5)
N3	0.0288 (6)	0.0323 (6)	0.0317 (6)	0.0029 (5)	−0.0057 (5)	−0.0042 (5)
C1	0.0244 (6)	0.0287 (6)	0.0235 (6)	−0.0057 (5)	0.0027 (5)	0.0005 (5)
C2	0.0182 (5)	0.0246 (6)	0.0184 (5)	−0.0042 (4)	0.0005 (4)	−0.0005 (4)
C3	0.0206 (6)	0.0305 (6)	0.0177 (5)	−0.0060 (5)	0.0025 (4)	−0.0003 (5)
C4	0.0180 (5)	0.0202 (5)	0.0208 (5)	−0.0057 (4)	−0.0035 (4)	0.0002 (4)
C5	0.0172 (5)	0.0196 (5)	0.0160 (5)	−0.0039 (4)	0.0017 (4)	0.0020 (4)
C6	0.0153 (5)	0.0216 (5)	0.0184 (5)	−0.0045 (4)	−0.0021 (4)	−0.0018 (4)
C7	0.0171 (5)	0.0206 (5)	0.0204 (5)	−0.0039 (4)	−0.0027 (4)	−0.0016 (4)
C8	0.0193 (5)	0.0258 (6)	0.0225 (6)	−0.0045 (5)	−0.0035 (4)	−0.0022 (5)
C9	0.0306 (7)	0.0238 (6)	0.0258 (6)	−0.0040 (5)	−0.0005 (5)	0.0060 (5)
C10	0.0170 (5)	0.0241 (5)	0.0161 (5)	−0.0055 (4)	−0.0003 (4)	0.0021 (4)
C11	0.0203 (5)	0.0264 (6)	0.0211 (5)	−0.0049 (5)	0.0002 (4)	−0.0015 (5)
C12	0.0188 (6)	0.0365 (7)	0.0265 (6)	−0.0013 (5)	0.0000 (5)	0.0007 (5)
C13	0.0187 (6)	0.0440 (8)	0.0297 (6)	−0.0110 (5)	−0.0043 (5)	0.0040 (6)
C14	0.0281 (6)	0.0318 (7)	0.0301 (6)	−0.0146 (5)	−0.0055 (5)	0.0011 (5)
C15	0.0234 (6)	0.0238 (6)	0.0254 (6)	−0.0070 (5)	−0.0015 (5)	0.0000 (5)
C16	0.0180 (5)	0.0197 (5)	0.0180 (5)	−0.0032 (4)	−0.0026 (4)	0.0010 (4)
C17	0.0188 (5)	0.0234 (6)	0.0259 (6)	−0.0047 (4)	−0.0024 (5)	0.0033 (5)
C18	0.0287 (6)	0.0274 (6)	0.0330 (7)	−0.0121 (5)	−0.0109 (5)	0.0032 (5)
C19	0.0466 (8)	0.0355 (7)	0.0231 (6)	−0.0175 (6)	−0.0107 (6)	−0.0007 (5)
C20	0.0451 (8)	0.0385 (7)	0.0185 (6)	−0.0164 (6)	0.0006 (6)	0.0005 (5)
C21	0.0287 (6)	0.0306 (6)	0.0204 (5)	−0.0135 (5)	−0.0011 (5)	0.0015 (5)
O1'	0.0198 (4)	0.0208 (4)	0.0176 (4)	−0.0045 (3)	−0.0035 (3)	0.0023 (3)
N1'	0.0412 (7)	0.0389 (7)	0.0397 (7)	−0.0079 (6)	−0.0131 (6)	−0.0056 (6)
N2'	0.0397 (7)	0.0325 (6)	0.0303 (6)	−0.0033 (5)	−0.0062 (5)	0.0042 (5)
N3'	0.0302 (6)	0.0310 (6)	0.0312 (6)	−0.0109 (5)	0.0057 (5)	−0.0038 (5)
C1'	0.0250 (6)	0.0289 (6)	0.0243 (6)	−0.0013 (5)	−0.0044 (5)	−0.0013 (5)
C2'	0.0192 (5)	0.0246 (6)	0.0195 (5)	−0.0020 (4)	−0.0017 (4)	−0.0006 (4)
C3'	0.0229 (6)	0.0276 (6)	0.0184 (5)	−0.0002 (5)	−0.0034 (5)	−0.0010 (5)
C4'	0.0154 (5)	0.0209 (5)	0.0203 (5)	−0.0016 (4)	0.0033 (4)	0.0007 (4)
C5'	0.0175 (5)	0.0201 (5)	0.0158 (5)	−0.0011 (4)	−0.0022 (4)	0.0023 (4)
C6'	0.0141 (5)	0.0214 (5)	0.0188 (5)	−0.0019 (4)	0.0020 (4)	−0.0018 (4)
C7'	0.0161 (5)	0.0213 (5)	0.0208 (5)	−0.0036 (4)	0.0030 (4)	−0.0005 (4)
C8'	0.0188 (5)	0.0251 (6)	0.0219 (6)	−0.0042 (5)	0.0032 (4)	−0.0009 (5)
C9'	0.0293 (6)	0.0250 (6)	0.0241 (6)	−0.0046 (5)	−0.0004 (5)	0.0061 (5)
C10'	0.0167 (5)	0.0215 (5)	0.0172 (5)	−0.0015 (4)	−0.0001 (4)	0.0031 (4)
C11'	0.0214 (6)	0.0240 (6)	0.0234 (6)	−0.0030 (5)	0.0003 (5)	−0.0010 (5)
C12'	0.0221 (6)	0.0299 (6)	0.0325 (7)	−0.0087 (5)	−0.0021 (5)	0.0027 (5)
C13'	0.0177 (6)	0.0339 (7)	0.0344 (7)	−0.0025 (5)	0.0028 (5)	0.0059 (6)
C14'	0.0225 (6)	0.0284 (6)	0.0335 (7)	0.0019 (5)	0.0060 (5)	0.0001 (5)
C15'	0.0215 (6)	0.0234 (6)	0.0268 (6)	−0.0029 (5)	0.0013 (5)	−0.0013 (5)
C16'	0.0185 (5)	0.0196 (5)	0.0187 (5)	−0.0037 (4)	0.0012 (4)	0.0004 (4)
C17'	0.0196 (5)	0.0208 (5)	0.0244 (6)	−0.0029 (4)	0.0004 (4)	0.0020 (5)
C18'	0.0235 (6)	0.0215 (6)	0.0313 (6)	0.0008 (5)	0.0060 (5)	0.0021 (5)
C19'	0.0347 (7)	0.0257 (6)	0.0245 (6)	−0.0023 (5)	0.0103 (5)	−0.0019 (5)
C20'	0.0331 (7)	0.0337 (7)	0.0183 (5)	−0.0035 (6)	0.0014 (5)	0.0000 (5)
C21'	0.0220 (6)	0.0308 (6)	0.0208 (6)	0.0002 (5)	−0.0012 (5)	0.0022 (5)

Geometric parameters (Å, º) top

O1—C6	1.3320 (14)	O1'—C6'	1.3295 (14)
O1—C5	1.4866 (13)	O1'—C5'	1.4808 (12)
N1—C1	1.1450 (17)	N1'—C1'	1.1469 (18)
N2—C3	1.1437 (16)	N2'—C3'	1.1417 (17)
N3—C8	1.1443 (16)	N3'—C8'	1.1448 (16)
C1—C2	1.4280 (18)	C1'—C2'	1.4239 (18)
C2—C6	1.3642 (16)	C2'—C6'	1.3647 (15)
C2—C3	1.4295 (16)	C2'—C3'	1.4351 (17)
C4—C7	1.3432 (17)	C4'—C7'	1.3432 (16)
C4—C9	1.4772 (16)	C4'—C9'	1.4779 (15)
C4—C5	1.5107 (16)	C4'—C5'	1.5118 (16)
C5—C16	1.5197 (16)	C5'—C16'	1.5180 (16)
C5—C10	1.5202 (16)	C5'—C10'	1.5243 (15)
C6—C7	1.4580 (15)	C6'—C7'	1.4547 (15)
C7—C8	1.4277 (17)	C7'—C8'	1.4273 (17)
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
C10—C15	1.3912 (17)	C10'—C11'	1.3866 (17)
C10—C11	1.3926 (17)	C10'—C15'	1.3911 (17)
C11—C12	1.3875 (17)	C11'—C12'	1.3907 (17)
C11—H11	0.9500	C11'—H11'	0.9500
C12—C13	1.384 (2)	C12'—C13'	1.3816 (19)
C12—H12	0.9500	C12'—H12'	0.9500
C13—C14	1.380 (2)	C13'—C14'	1.380 (2)
C13—H13	0.9500	C13'—H13'	0.9500
C14—C15	1.3879 (17)	C14'—C15'	1.3872 (18)
C14—H14	0.9500	C14'—H14'	0.9500
C15—H15	0.9500	C15'—H15'	0.9500
C16—C17	1.3881 (16)	C16'—C17'	1.3919 (16)
C16—C21	1.3898 (17)	C16'—C21'	1.3952 (16)
C17—C18	1.3894 (18)	C17'—C18'	1.3861 (18)
C17—H17	0.9500	C17'—H17'	0.9500
C18—C19	1.383 (2)	C18'—C19'	1.3837 (19)
C18—H18	0.9500	C18'—H18'	0.9500
C19—C20	1.379 (2)	C19'—C20'	1.3822 (19)
C19—H19	0.9500	C19'—H19'	0.9500
C20—C21	1.3826 (18)	C20'—C21'	1.3792 (18)
C20—H20	0.9500	C20'—H20'	0.9500
C21—H21	0.9500	C21'—H21'	0.9500

C6—O1—C5	110.17 (8)	C6'—O1'—C5'	110.25 (8)
N1—C1—C2	179.94 (19)	N1'—C1'—C2'	179.47 (14)
C6—C2—C1	121.39 (11)	C6'—C2'—C1'	121.78 (11)
C6—C2—C3	120.28 (11)	C6'—C2'—C3'	120.02 (11)
C1—C2—C3	118.33 (11)	C1'—C2'—C3'	118.20 (10)
N2—C3—C2	178.90 (14)	N2'—C3'—C2'	178.76 (14)
C7—C4—C9	127.97 (11)	C7'—C4'—C9'	127.80 (11)
C7—C4—C5	109.10 (10)	C7'—C4'—C5'	109.09 (10)
C9—C4—C5	122.86 (11)	C9'—C4'—C5'	123.09 (10)
O1—C5—C4	102.37 (9)	O1'—C5'—C4'	102.35 (9)
O1—C5—C16	109.19 (9)	O1'—C5'—C16'	109.11 (8)
C4—C5—C16	108.53 (9)	C4'—C5'—C16'	108.89 (9)
O1—C5—C10	105.72 (8)	O1'—C5'—C10'	106.34 (8)
C4—C5—C10	114.22 (10)	C4'—C5'—C10'	112.82 (9)
C16—C5—C10	115.82 (10)	C16'—C5'—C10'	116.33 (10)
O1—C6—C2	120.36 (10)	O1'—C6'—C2'	120.27 (10)
O1—C6—C7	109.26 (10)	O1'—C6'—C7'	109.49 (9)
C2—C6—C7	130.38 (11)	C2'—C6'—C7'	130.22 (11)
C4—C7—C8	123.65 (11)	C4'—C7'—C8'	124.09 (11)
C4—C7—C6	109.02 (10)	C4'—C7'—C6'	108.81 (10)
C8—C7—C6	127.34 (11)	C8'—C7'—C6'	127.10 (10)
N3—C8—C7	175.48 (14)	N3'—C8'—C7'	176.62 (13)
C4—C9—H9A	109.5	C4'—C9'—H9'A	109.5
C4—C9—H9B	109.5	C4'—C9'—H9'B	109.5
H9A—C9—H9B	109.5	H9'A—C9'—H9'B	109.5
C4—C9—H9C	109.5	C4'—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
C15—C10—C11	119.65 (11)	C11'—C10'—C15'	119.72 (11)
C15—C10—C5	120.37 (11)	C11'—C10'—C5'	120.81 (10)
C11—C10—C5	119.70 (11)	C15'—C10'—C5'	119.32 (11)
C12—C11—C10	119.95 (12)	C10'—C11'—C12'	119.71 (12)
C12—C11—H11	120.0	C10'—C11'—H11'	120.1
C10—C11—H11	120.0	C12'—C11'—H11'	120.1
C13—C12—C11	119.97 (12)	C13'—C12'—C11'	120.31 (12)
C13—C12—H12	120.0	C13'—C12'—H12'	119.8
C11—C12—H12	120.0	C11'—C12'—H12'	119.8
C14—C13—C12	120.39 (12)	C14'—C13'—C12'	120.11 (12)
C14—C13—H13	119.8	C14'—C13'—H13'	119.9
C12—C13—H13	119.8	C12'—C13'—H13'	119.9
C13—C14—C15	119.99 (12)	C13'—C14'—C15'	119.93 (12)
C13—C14—H14	120.0	C13'—C14'—H14'	120.0
C15—C14—H14	120.0	C15'—C14'—H14'	120.0
C14—C15—C10	120.03 (12)	C14'—C15'—C10'	120.18 (12)
C14—C15—H15	120.0	C14'—C15'—H15'	119.9
C10—C15—H15	120.0	C10'—C15'—H15'	119.9
C17—C16—C21	119.62 (11)	C17'—C16'—C21'	119.14 (11)
C17—C16—C5	120.49 (11)	C17'—C16'—C5'	120.97 (10)
C21—C16—C5	119.64 (10)	C21'—C16'—C5'	119.62 (10)
C16—C17—C18	119.77 (12)	C18'—C17'—C16'	119.95 (11)
C16—C17—H17	120.1	C18'—C17'—H17'	120.0
C18—C17—H17	120.1	C16'—C17'—H17'	120.0
C19—C18—C17	120.14 (12)	C19'—C18'—C17'	120.54 (11)
C19—C18—H18	119.9	C19'—C18'—H18'	119.7
C17—C18—H18	119.9	C17'—C18'—H18'	119.7
C20—C19—C18	120.17 (13)	C20'—C19'—C18'	119.58 (12)
C20—C19—H19	119.9	C20'—C19'—H19'	120.2
C18—C19—H19	119.9	C18'—C19'—H19'	120.2
C19—C20—C21	119.97 (13)	C21'—C20'—C19'	120.41 (12)
C19—C20—H20	120.0	C21'—C20'—H20'	119.8
C21—C20—H20	120.0	C19'—C20'—H20'	119.8
C20—C21—C16	120.30 (12)	C20'—C21'—C16'	120.36 (11)
C20—C21—H21	119.9	C20'—C21'—H21'	119.8
C16—C21—H21	119.9	C16'—C21'—H21'	119.8

C6—O1—C5—C4	2.74 (11)	C6'—O1'—C5'—C4'	1.01 (11)
C6—O1—C5—C16	117.63 (10)	C6'—O1'—C5'—C16'	116.26 (10)
C6—O1—C5—C10	−117.13 (10)	C6'—O1'—C5'—C10'	−117.54 (10)
C7—C4—C5—O1	−1.50 (12)	C7'—C4'—C5'—O1'	−0.64 (12)
C9—C4—C5—O1	175.57 (10)	C9'—C4'—C5'—O1'	177.60 (10)
C7—C4—C5—C16	−116.87 (11)	C7'—C4'—C5'—C16'	−116.05 (10)
C9—C4—C5—C16	60.21 (14)	C9'—C4'—C5'—C16'	62.19 (13)
C7—C4—C5—C10	112.25 (11)	C7'—C4'—C5'—C10'	113.21 (11)
C9—C4—C5—C10	−70.67 (14)	C9'—C4'—C5'—C10'	−68.54 (14)
C5—O1—C6—C2	177.73 (10)	C5'—O1'—C6'—C2'	−179.83 (10)
C5—O1—C6—C7	−2.95 (12)	C5'—O1'—C6'—C7'	−1.00 (12)
C1—C2—C6—O1	179.78 (11)	C1'—C2'—C6'—O1'	−179.38 (11)
C3—C2—C6—O1	−0.45 (17)	C3'—C2'—C6'—O1'	0.38 (17)
C1—C2—C6—C7	0.6 (2)	C1'—C2'—C6'—C7'	2.1 (2)
C3—C2—C6—C7	−179.61 (11)	C3'—C2'—C6'—C7'	−178.17 (12)
C9—C4—C7—C8	2.6 (2)	C9'—C4'—C7'—C8'	1.5 (2)
C5—C4—C7—C8	179.51 (11)	C5'—C4'—C7'—C8'	179.64 (11)
C9—C4—C7—C6	−177.01 (11)	C9'—C4'—C7'—C6'	−178.04 (11)
C5—C4—C7—C6	−0.12 (13)	C5'—C4'—C7'—C6'	0.10 (13)
O1—C6—C7—C4	1.95 (13)	O1'—C6'—C7'—C4'	0.57 (13)
C2—C6—C7—C4	−178.82 (12)	C2'—C6'—C7'—C4'	179.24 (12)
O1—C6—C7—C8	−177.67 (11)	O1'—C6'—C7'—C8'	−178.96 (11)
C2—C6—C7—C8	1.6 (2)	C2'—C6'—C7'—C8'	−0.3 (2)
O1—C5—C10—C15	90.54 (12)	O1'—C5'—C10'—C11'	−94.48 (12)
C4—C5—C10—C15	−21.21 (15)	C4'—C5'—C10'—C11'	154.11 (10)
C16—C5—C10—C15	−148.43 (10)	C16'—C5'—C10'—C11'	27.23 (14)
O1—C5—C10—C11	−83.48 (12)	O1'—C5'—C10'—C15'	81.20 (12)
C4—C5—C10—C11	164.77 (10)	C4'—C5'—C10'—C15'	−30.22 (14)
C16—C5—C10—C11	37.56 (14)	C16'—C5'—C10'—C15'	−157.09 (10)
C15—C10—C11—C12	0.68 (17)	C15'—C10'—C11'—C12'	1.69 (17)
C5—C10—C11—C12	174.74 (11)	C5'—C10'—C11'—C12'	177.34 (10)
C10—C11—C12—C13	−0.52 (18)	C10'—C11'—C12'—C13'	−1.61 (18)
C11—C12—C13—C14	−0.1 (2)	C11'—C12'—C13'—C14'	0.16 (19)
C12—C13—C14—C15	0.6 (2)	C12'—C13'—C14'—C15'	1.22 (19)
C13—C14—C15—C10	−0.41 (19)	C13'—C14'—C15'—C10'	−1.13 (19)
C11—C10—C15—C14	−0.22 (17)	C11'—C10'—C15'—C14'	−0.33 (17)
C5—C10—C15—C14	−174.24 (11)	C5'—C10'—C15'—C14'	−176.05 (11)
O1—C5—C16—C17	−30.62 (13)	O1'—C5'—C16'—C17'	−21.91 (15)
C4—C5—C16—C17	80.23 (12)	C4'—C5'—C16'—C17'	89.06 (12)
C10—C5—C16—C17	−149.77 (10)	C10'—C5'—C16'—C17'	−142.14 (11)
O1—C5—C16—C21	155.10 (10)	O1'—C5'—C16'—C21'	164.16 (10)
C4—C5—C16—C21	−94.05 (12)	C4'—C5'—C16'—C21'	−84.88 (13)
C10—C5—C16—C21	35.95 (15)	C10'—C5'—C16'—C21'	43.92 (15)
C21—C16—C17—C18	−1.44 (17)	C21'—C16'—C17'—C18'	0.08 (18)
C5—C16—C17—C18	−175.72 (10)	C5'—C16'—C17'—C18'	−173.88 (11)
C16—C17—C18—C19	−0.09 (19)	C16'—C17'—C18'—C19'	−0.94 (19)
C17—C18—C19—C20	0.7 (2)	C17'—C18'—C19'—C20'	0.8 (2)
C18—C19—C20—C21	0.3 (2)	C18'—C19'—C20'—C21'	0.1 (2)
C19—C20—C21—C16	−1.8 (2)	C19'—C20'—C21'—C16'	−1.0 (2)
C17—C16—C21—C20	2.41 (18)	C17'—C16'—C21'—C20'	0.86 (19)
C5—C16—C21—C20	176.74 (11)	C5'—C16'—C21'—C20'	174.90 (12)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C10–C15 phenyl ring

D—H···A	D—H	H···A	D···A	D—H···A
C20′—H20′···Cg1ⁱ	0.95	2.69	3.4041 (14)	133
C9—H9B···N3′	0.98	2.70	3.4560 (14)	134

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C10–C15 phenyl ring

D—H···A	D—H	H···A	D···A	D—H···A
C20'—H20'···Cg1ⁱ	0.95	2.69	3.4041 (14)	133
C9—H9B···N3'	0.98	2.70	3.4560 (14)	134

Symmetry code: (i) −x+1, −y+1, −z.

Acknowledgements

This work was supported by a New Zealand Foundation for Research Science and Technology grant (contract No. C08X0704). We thank Dr C. Fitchett of the University of Canterbury, New Zealand, for his assistance.

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Volume 69| Part 9| September 2013| Pages o1365-o1366

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