Conformational polymorphs of 22-cyano-N-methyl-5-phenylpent-2-en-4-ynamide

Although the two polymorphic modifications, (I) and (II), of the title compound, C₁₃H₁₀N₂O, crystallize in the same space group (P2₁/c), their asymmetric units have Z' values of 1 and 2, respectively. These are conformational polymorphs, since the mol­ecules in phases (I) and (II) adopt different rotations of the phenyl ring with respect the central 2-cyano­carboxy­amino­prop-2-enyl fragment. Calculations of crystal packing using Cerius² [Molecular Simulations (1999). 9685 Scranton Road, San Diego, CA 92121, USA] have shown that (I) is more stable than (II), by 1.3 kcal mol^-1 for the crystallographically determined structures and by 1.56 kcal mol^-1 for the optimized structures (1 kcal mol^-1 = 4.184 kJ mol^-1). This difference is mainly attributed to the different strengths of the hydrogen bonding in the two forms.

S1. Comment

Derivatives of 2-cyanoacrylic acid with unsaturated substitutents in the 3-position are of great interest because of their potential bioactivity and versatility in the synthesis of polymeric and heterocyxlic compounds. For example, such compounds can undergo polymerization under very mild conditions (Gololobov & Gruber, 1997; Denchev & Kabaivanov, 1993). In addition, our previous structural studies show that topochemical reactions can occur in some of these derivatives, namely in 2-cyano-(2E)-pentadien-2,4-oic acid and its ethyl ester (Borbulevych et al., 1998). As a part of our further structural investigation of this class of compounds (Borbulevych et al., 1998, 1999; Golding et al., 1999; Khrustalev et al., 1996), we present here our results on two polymorphic modifications, (I) and (II), of the title compound, (1). \sch

Although the two polymorphic modifications crystallize in the same space group, namely P2₁/c, there are two independent molecules, A and B, in the asymmetric unit of form (II), whereas there is only one for form (I). Most bond lengths in (I) and (II) are equal to within three standard uncertainties (Tables 1 and 4). It should be mentioned that in (IIA), the N2—C13 bond is somewhat elongated [1.466 (3) Å], and the O1—C1 bond length of 1.213 (3) Å is shortened, compared with those in (I) and (IIB). On the other hand, the C═O bond is equal to that found in the analogous phenyl-substituted compound, (2) (Borbulevych et al., 1999). The variation in this bond length is attributed to the difference of the hydrogen bonds in compounds (1) and (2) (see below).

The 2-cyanocarboxyaminoprop-2-enylic fragment (N2/C1/O1/C2/C3/C6/N1) in (I) and (II) is rather flattened, despite the presence of shortened intramolecular contacts (Tables 2 and 5). The maximum deviations from the least-squares mean plane passing through all non-H atoms of this fragment are observed for O1 in each case, and equal 0.1430 (8), 0.066 (2) and -0.131 (2) Å for (I), (IIA) and (IIB), respectively.

The main differences between the geometry of the molecules in (I) and (II) are attributed to the degree of rotation of the phenyl ring with the respect to the 2-cyanocarboxyaminoprop-2-enylic fragment. In (I) and (IIB), the C7—C12 ring is considerably twisted, with interplanar angles between these fragments of 34.94 (4) and 43.0 (1)°, respectively. However, in (IIA), the phenyl ring is almost coplanar with the above-mentioned fragment, as shown by the corresponding dihedral angle of 8.9 (1)°. Moreover, where only one IR band (at 1581 cm^-1), corresponding to the vibrations of the conjugated fragment PhC≡CCH═C, appears in the IR spectra of (I), two such bands (at 1566 and 1583 cm^-1) are seen for (II). We attribute this observation to the presence of two molecules having different rotations of the phenyl ring.

In (I), the molecules are linked into infinite chains through intermolecular hydrogen bonds (Table 3), and similar chains are seen for (II) (Table 6). However, in (II), each chain consists exclusively of molecules of type A or type B. Therefore, molecules of (I) and (II) are not linked into centrosymmetric dimers by intermolecular hydrogen bonding, in contrast with derivatives of 2-cyanopentadien-2,4-oic acid (Borbulevych et al., 1998; Golding et al., 1999). A similar hydrogen-bonding network was observed in (2) (Borbulevych et al., 1999).

In order to allow comparison between the polymorphic forms (I) and (II), calculations of the crystal lattice energies for their crystallographic and optimized structures were carried out using the Dreiding 2.21 force field (Mayo et al., 1990). According to these calculations (see Experimental) the X-ray structure of (I) is more stable than that of (II) by 1.3 kcal mol^-1. We attribute this difference mainly to differences in the contribution made by the hydrogen bonding (Table 7). Optimization of the structures of (I) and (II) gives rise to similar results, (I) being more stable than (II) by 1.56 kcal mol^-1. In this case, the van der Waals energy contributions are equal, but for (I), the hydrogen-bonding and Coulombic contributions are lower by 1.03 and 0.53 kcal mol^-1, respectively. Thus, we conclude that the difference in the lattice energies arises from differences in the energies associated with hydrogen bonding, which appears to be somewhat stronger in (I).

Related literature

For related literature, see: Borbulevych et al. (1998, 1999); Denchev & Kabaivanov (1993); Golding et al. (1999); Gololobov & Gruber (1997); Khrustalev et al. (1996); Mayo et al. (1990); Molecular (1999); Rappé & Goddard (1991); Shchegolikhin & Lazareva (1997).

S2. Experimental

Compound (1) was synthesized by the Knoevenagel condensation method. A clear solution of N-methyl cyanoacetamide (0.98 g, 0.01 mol) and phenylpropiolic aldehyde (1.44 g, 0.01 mol) in N-methylpyrrolidone (NMP, 3 ml) was stirred with aluminium oxide (5 g) as catalyst until the exothermic reaction had ceased and the reaction mixture had solidified. AUTHOR: Please check the wording above. After being left to stand overnight at room temperature, further NMP (5 ml) was added. The precipitate was filtered off and washed with NMP (5 ml). AUTHOR: It is not clear what is happening below. Does the following procedure result in more of the same material? The filtrate was poured into water and the precipitate was separated and crystallized from toluene (yield 67%). Spectroscopic analysis: ¹H NMR (400.26 MHz, acetone, δ, p.p.m): 2.90 (d, J = 4.8 Hz, 3H, CH₃), 7.47–7.62 (m, 7H, CH + NH + 5H_arom). Crystals of the polymorphic forms (I) and (II) were obtained by isothermal evaporation from CCl₄ and n-C₆H₁₄ solutions, respectively. The melting point of (I) is 381 K and the melting point of (II) is 384 K. IR spectra were recorded on a Perkin-Elmer 1725 F T—IR spectrometer with a modified sample holder (Shchegolikhin & Lazareva, 1997). Optimization of the crystal structures of (I) and (II) and calculation of the lattice energies were carried out using Cerius² (Molecular Simulations, 1999), taking into account their monoclinic cell setting (i.e. the angles α and γ were constrained) using the `Smart Minimizer' option of the Cerius² package. Using this option, optimization begins with a steepest descent method, followed by a quasi-Newton method and finishing with a truncated Newton method. Atom-atom potentials were estimated using the Dreiding 2.21 forcefield (Mayo et al., 1990) and atomic charges were estimated using the charge equilibration method (Rappé & Goddard, 1991). All molecules in the crystal were treated as rigid entities. In this case, the total lattice energy is the sum of three contributions, namely van der Waals, Coulombic and hydrogen-bonding.

S3. Refinement

For polymorph (I), all H atoms were refined freely. For polymorph (II), H atoms were treated as riding, with C—H = 0.93–0.96 Å, N—H = 0.86 Å and U_iso(H) = 1.2U_eq of the parent atom. Query.

Computing details

Data collection: SMART (Bruker, 1998) for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: SMART for (I); CAD-4 Software for (II). Data reduction: SAINT (Bruker, 1998) for (I); CAD-4 Software for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A molecular view of (1) in polymorphic form (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A molecular view of (1) in polymorphic form (II). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

(I) 2-cyano-5-phenyl-pent-2-en-4-ynoic acid N-methylamide form (I)

Crystal data

C13H10N2O	Dx = 1.312 Mg m^−3
Mr = 210.23	Melting point: 381 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.9794 (18) Å	Cell parameters from 540 reflections
b = 8.9951 (13) Å	θ = 2–24°
c = 10.0786 (16) Å	µ = 0.09 mm^−1
β = 101.557 (3)°	T = 110 K
V = 1064.0 (3) Å^3	Square prism, yellow
Z = 4	0.5 × 0.4 × 0.3 mm
F(000) = 440

Data collection

Bruker SMART CCD area-detector diffractometer	2991 independent reflections
Radiation source: fine-focus sealed tube	2195 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 30.1°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −16→8
Tmin = 0.958, Tmax = 0.975	k = −12→12
8003 measured reflections	l = −13→14

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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F^2) = 0.116	All H-atom parameters refined
S = 0.97	w = 1/[σ^2(Fo^2) + (0.077P)^2] where P = (Fo^2 + 2Fc^2)/3
2991 reflections	(Δ/σ)max = 0.001
185 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.20 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
O1	0.45358 (7)	0.25582 (10)	0.31185 (8)	0.0277 (2)
N1	0.69725 (10)	0.13868 (14)	0.72697 (11)	0.0377 (3)
N2	0.45292 (8)	0.29913 (10)	0.53215 (9)	0.0203 (2)
H2	0.4751 (13)	0.2680 (17)	0.6192 (17)	0.035 (4)*
C1	0.49430 (9)	0.23537 (12)	0.43267 (11)	0.0196 (2)
C2	0.59765 (9)	0.13833 (11)	0.47501 (10)	0.0196 (2)
C3	0.63525 (9)	0.05662 (12)	0.38099 (12)	0.0230 (2)
H3	0.5905 (13)	0.0602 (18)	0.2920 (17)	0.038 (4)*
C4	0.73229 (9)	−0.03567 (12)	0.40165 (11)	0.0232 (2)
C5	0.81166 (9)	−0.11817 (12)	0.40337 (11)	0.0222 (2)
C6	0.65475 (10)	0.13724 (13)	0.61427 (12)	0.0247 (2)
C7	0.89937 (9)	−0.22331 (12)	0.39560 (11)	0.0207 (2)
C8	1.00752 (10)	−0.21557 (13)	0.47945 (12)	0.0239 (2)
H8	1.0228 (12)	−0.1395 (16)	0.5478 (15)	0.026 (3)*
C9	1.09029 (10)	−0.31896 (14)	0.46542 (12)	0.0274 (3)
H9	1.1645 (13)	−0.3144 (16)	0.5249 (15)	0.030 (4)*
C10	1.06531 (10)	−0.43096 (14)	0.36945 (13)	0.0286 (3)
H10	1.1218 (12)	−0.5026 (17)	0.3544 (15)	0.028 (4)*
C11	0.95755 (11)	−0.44116 (13)	0.28754 (12)	0.0276 (3)
H11	0.9390 (12)	−0.5184 (17)	0.2246 (16)	0.033 (4)*
C12	0.87504 (10)	−0.33771 (13)	0.29904 (11)	0.0240 (2)
H12	0.7981 (13)	−0.3457 (17)	0.2460 (15)	0.031 (4)*
C13	0.35410 (10)	0.39571 (14)	0.50063 (12)	0.0242 (2)
H13A	0.2841 (16)	0.341 (2)	0.4605 (19)	0.052 (5)*
H13B	0.3414 (13)	0.4378 (18)	0.5882 (17)	0.041 (4)*
H13C	0.3675 (13)	0.4750 (19)	0.4387 (17)	0.041 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0281 (4)	0.0365 (5)	0.0180 (4)	0.0089 (4)	0.0033 (3)	0.0015 (3)
N1	0.0360 (6)	0.0466 (7)	0.0274 (5)	0.0149 (5)	−0.0009 (4)	−0.0019 (5)
N2	0.0211 (4)	0.0212 (4)	0.0190 (4)	0.0020 (3)	0.0047 (3)	0.0013 (3)
C1	0.0205 (5)	0.0191 (5)	0.0195 (5)	0.0003 (4)	0.0047 (4)	0.0014 (4)
C2	0.0196 (5)	0.0180 (5)	0.0213 (5)	−0.0001 (4)	0.0041 (4)	0.0020 (4)
C3	0.0227 (5)	0.0218 (5)	0.0247 (5)	−0.0001 (4)	0.0053 (4)	0.0003 (4)
C4	0.0252 (5)	0.0202 (5)	0.0253 (5)	−0.0006 (4)	0.0075 (4)	−0.0023 (4)
C5	0.0234 (5)	0.0192 (5)	0.0248 (5)	−0.0033 (4)	0.0070 (4)	−0.0010 (4)
C6	0.0235 (5)	0.0251 (5)	0.0255 (5)	0.0064 (4)	0.0049 (4)	0.0009 (4)
C7	0.0224 (5)	0.0180 (5)	0.0229 (5)	−0.0001 (4)	0.0078 (4)	0.0023 (4)
C8	0.0249 (5)	0.0227 (5)	0.0241 (5)	−0.0027 (4)	0.0049 (4)	0.0013 (4)
C9	0.0216 (5)	0.0308 (6)	0.0295 (6)	0.0015 (4)	0.0043 (4)	0.0071 (5)
C10	0.0282 (6)	0.0281 (6)	0.0319 (6)	0.0080 (5)	0.0116 (5)	0.0050 (5)
C11	0.0338 (6)	0.0251 (6)	0.0256 (5)	0.0017 (5)	0.0096 (5)	−0.0029 (5)
C12	0.0239 (5)	0.0246 (5)	0.0237 (5)	−0.0002 (4)	0.0051 (4)	−0.0011 (4)
C13	0.0236 (5)	0.0234 (5)	0.0269 (5)	0.0046 (4)	0.0080 (4)	0.0021 (4)

Geometric parameters (Å, º)

O1—C1	1.2315 (13)	C9—C10	1.3871 (18)
N1—C6	1.1480 (16)	C10—C11	1.3889 (18)
N2—C1	1.3338 (14)	C11—C12	1.3792 (16)
N2—C13	1.4513 (14)	N2—H2	0.908 (16)
C1—C2	1.5050 (15)	C3—H3	0.949 (17)
C2—C3	1.3462 (15)	C8—H8	0.962 (15)
C2—C6	1.4329 (15)	C9—H9	0.969 (16)
C3—C4	1.4096 (15)	C10—H10	0.968 (15)
C4—C5	1.2035 (15)	C11—H11	0.937 (16)
C5—C7	1.4274 (15)	C12—H12	0.971 (15)
C7—C8	1.3996 (16)	C13—H13A	0.984 (19)
C7—C12	1.4062 (16)	C13—H13B	0.999 (16)
C8—C9	1.3872 (17)	C13—H13C	0.982 (17)
O1···H3	2.44 (2)	C6···H2	2.46 (2)
C1—N2—C13	120.17 (10)	C13—N2—H2	117.6 (10)
O1—C1—N2	123.08 (10)	C2—C3—H3	116.2 (10)
O1—C1—C2	120.49 (10)	C4—C3—H3	116.9 (10)
N2—C1—C2	116.41 (9)	C9—C8—H8	120.8 (9)
C3—C2—C6	121.63 (10)	C7—C8—H8	119.2 (9)
C3—C2—C1	119.30 (10)	C10—C9—H9	120.4 (9)
C6—C2—C1	119.07 (9)	C8—C9—H9	119.6 (9)
C2—C3—C4	126.87 (11)	C9—C10—H10	122.2 (9)
C5—C4—C3	172.33 (12)	C11—C10—H10	117.3 (9)
C4—C5—C7	174.77 (11)	C12—C11—H11	118.7 (9)
N1—C6—C2	177.63 (13)	C10—C11—H11	121.2 (9)
C8—C7—C12	119.52 (10)	C11—C12—H12	121.4 (9)
C8—C7—C5	122.44 (10)	C7—C12—H12	118.5 (9)
C12—C7—C5	118.04 (10)	N2—C13—H13A	112.6 (11)
C9—C8—C7	119.95 (11)	N2—C13—H13B	107.2 (9)
C10—C9—C8	119.95 (11)	N2—C13—H13C	110.1 (9)
C9—C10—C11	120.49 (11)	H13A—C13—H13B	106.4 (14)
C12—C11—C10	120.12 (11)	H13A—C13—H13C	109.5 (14)
C11—C12—C7	119.95 (11)	H13B—C13—H13C	111.0 (13)
C1—N2—H2	120.9 (10)
C13—N2—C1—O1	1.16 (17)	C12—C7—C8—C9	1.01 (16)
C13—N2—C1—C2	179.39 (9)	C5—C7—C8—C9	−178.60 (10)
O1—C1—C2—C3	−9.75 (16)	C7—C8—C9—C10	−0.79 (17)
N2—C1—C2—C3	171.98 (10)	C8—C9—C10—C11	−0.42 (18)
O1—C1—C2—C6	169.20 (11)	C9—C10—C11—C12	1.42 (18)
N2—C1—C2—C6	−9.08 (15)	C10—C11—C12—C7	−1.19 (18)
C6—C2—C3—C4	−1.32 (18)	C8—C7—C12—C11	−0.02 (17)
C1—C2—C3—C4	177.60 (10)	C5—C7—C12—C11	179.61 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.91 (2)	2.02 (2)	2.860 (1)	153 (1)

Symmetry code: (i) x, −y+1/2, z+1/2.

(II) 2-cyano-5-phenyl-pent-2-en-4-ynoic acid N-methylamide form (II)

Crystal data

C13H10N2O	Dx = 1.244 Mg m^−3
Mr = 210.23	Melting point: 384 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.652 (12) Å	Cell parameters from 24 reflections
b = 9.728 (7) Å	θ = 10–11°
c = 10.269 (5) Å	µ = 0.08 mm^−1
β = 97.29 (4)°	T = 293 K
V = 2245 (2) Å^3	Needle, yellow
Z = 8	0.5 × 0.2 × 0.2 mm
F(000) = 880

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.079
Radiation source: fine-focus sealed tube	θmax = 27.0°, θmin = 1.8°
Graphite monochromator	h = −28→0
θ/2θ scans	k = 0→12
4929 measured reflections	l = −12→13
4810 independent reflections	2 standard reflections every 90 reflections
2134 reflections with I > 2σ(I)	intensity decay: 3.4%

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)] = 0.052	Hydrogen site location: difference Fourier map
wR(F^2) = 0.169	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.091P)^2] where P = (Fo^2 + 2Fc^2)/3
4810 reflections	(Δ/σ)max = 0.001
291 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.22 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
O1	0.51989 (9)	0.1326 (2)	0.65637 (18)	0.0714 (6)
N1	0.40660 (13)	0.5274 (3)	0.5243 (3)	0.0824 (8)
N2	0.52030 (9)	0.3542 (2)	0.72239 (19)	0.0545 (6)
H2	0.5022	0.4320	0.7122	0.065*
C1	0.50077 (11)	0.2491 (3)	0.6456 (2)	0.0490 (6)
C2	0.45142 (11)	0.2854 (3)	0.5377 (2)	0.0476 (6)
C3	0.43153 (11)	0.1924 (3)	0.4453 (2)	0.0555 (7)
H3	0.4479	0.1046	0.4507	0.067*
C4	0.38672 (12)	0.2227 (3)	0.3404 (2)	0.0536 (7)
C5	0.34816 (12)	0.2549 (3)	0.2550 (2)	0.0519 (7)
C6	0.42675 (12)	0.4201 (3)	0.5295 (2)	0.0558 (7)
C7	0.30001 (11)	0.2962 (3)	0.1603 (2)	0.0462 (6)
C8	0.27396 (13)	0.4228 (3)	0.1721 (3)	0.0664 (8)
H8	0.2894	0.4825	0.2387	0.080*
C9	0.22506 (14)	0.4615 (4)	0.0858 (3)	0.0778 (9)
H9	0.2074	0.5468	0.0946	0.093*
C10	0.20243 (13)	0.3740 (4)	−0.0132 (3)	0.0694 (9)
H10	0.1689	0.3994	−0.0701	0.083*
C11	0.22856 (13)	0.2512 (3)	−0.0285 (3)	0.0632 (8)
H11	0.2138	0.1939	−0.0975	0.076*
C12	0.27716 (12)	0.2101 (3)	0.0581 (2)	0.0546 (7)
H12	0.2946	0.1248	0.0479	0.066*
C13	0.57174 (12)	0.3410 (3)	0.8237 (3)	0.0679 (8)
H13A	0.5790	0.2455	0.8432	0.102*
H13B	0.5637	0.3880	0.9018	0.102*
H13C	0.6061	0.3807	0.7926	0.102*
O1'	1.01898 (9)	0.7563 (2)	0.68323 (15)	0.0689 (6)
N1'	0.89839 (14)	0.6122 (4)	0.3035 (3)	0.1193 (14)
N2'	1.01957 (9)	0.7867 (2)	0.46670 (17)	0.0479 (5)
H2'	1.0037	0.7650	0.3889	0.058*
C1'	0.99860 (11)	0.7301 (3)	0.5693 (2)	0.0446 (6)
C2'	0.94784 (10)	0.6320 (3)	0.5402 (2)	0.0455 (6)
C3'	0.92944 (12)	0.5580 (3)	0.6369 (2)	0.0576 (7)
H3'	0.9508	0.5691	0.7197	0.069*
C4'	0.88133 (13)	0.4649 (3)	0.6277 (3)	0.0581 (7)
C5'	0.84124 (13)	0.3868 (3)	0.6332 (3)	0.0554 (7)
C6'	0.91935 (13)	0.6196 (3)	0.4093 (3)	0.0668 (8)
C7'	0.79511 (11)	0.2901 (3)	0.6496 (2)	0.0478 (6)
C8'	0.73735 (12)	0.3048 (3)	0.5861 (3)	0.0588 (7)
H8'	0.7283	0.3764	0.5269	0.071*
C9'	0.69395 (13)	0.2145 (3)	0.6104 (3)	0.0719 (9)
H9'	0.6554	0.2252	0.5684	0.086*
C10'	0.70703 (14)	0.1083 (3)	0.6964 (3)	0.0733 (9)
H10'	0.6772	0.0480	0.7139	0.088*
C11'	0.76401 (14)	0.0903 (3)	0.7570 (3)	0.0699 (8)
H11'	0.7730	0.0158	0.8129	0.084*
C12'	0.80749 (12)	0.1811 (3)	0.7356 (3)	0.0570 (7)
H12'	0.8458	0.1699	0.7790	0.068*
C13'	1.06840 (12)	0.8841 (3)	0.4823 (3)	0.0603 (7)
H13D	1.0622	0.9495	0.5493	0.091*
H13E	1.0702	0.9314	0.4009	0.091*
H13F	1.1051	0.8360	0.5072	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0835 (14)	0.0633 (13)	0.0603 (12)	0.0207 (11)	−0.0185 (10)	−0.0021 (10)
N1	0.100 (2)	0.0637 (18)	0.0753 (18)	0.0127 (16)	−0.0191 (15)	0.0025 (15)
N2	0.0523 (13)	0.0602 (14)	0.0472 (12)	0.0020 (11)	−0.0079 (9)	0.0056 (11)
C1	0.0486 (14)	0.0600 (18)	0.0372 (12)	0.0031 (13)	0.0012 (10)	0.0035 (13)
C2	0.0491 (14)	0.0542 (16)	0.0384 (12)	0.0015 (13)	0.0015 (10)	0.0068 (12)
C3	0.0577 (16)	0.0655 (18)	0.0417 (13)	0.0068 (14)	0.0001 (12)	0.0023 (13)
C4	0.0570 (16)	0.0620 (17)	0.0410 (13)	−0.0002 (14)	0.0029 (12)	−0.0055 (13)
C5	0.0538 (15)	0.0637 (18)	0.0374 (12)	0.0016 (13)	0.0034 (12)	0.0001 (12)
C6	0.0575 (17)	0.0609 (19)	0.0457 (14)	−0.0014 (15)	−0.0059 (12)	0.0058 (14)
C7	0.0517 (14)	0.0537 (16)	0.0332 (12)	−0.0066 (13)	0.0053 (10)	0.0003 (11)
C8	0.082 (2)	0.067 (2)	0.0463 (15)	0.0068 (17)	−0.0049 (14)	−0.0102 (14)
C9	0.085 (2)	0.076 (2)	0.0685 (19)	0.0271 (18)	−0.0049 (17)	0.0016 (18)
C10	0.0617 (19)	0.094 (3)	0.0497 (16)	0.0131 (18)	−0.0034 (13)	0.0090 (17)
C11	0.0592 (17)	0.085 (2)	0.0429 (14)	−0.0154 (16)	−0.0048 (12)	−0.0057 (15)
C12	0.0585 (16)	0.0569 (17)	0.0477 (14)	−0.0055 (14)	0.0040 (12)	−0.0053 (13)
C13	0.0569 (17)	0.086 (2)	0.0557 (16)	−0.0011 (16)	−0.0146 (13)	−0.0020 (15)
O1'	0.0752 (13)	0.1020 (16)	0.0283 (8)	−0.0310 (11)	0.0014 (8)	−0.0067 (9)
N1'	0.115 (3)	0.183 (4)	0.0527 (16)	−0.072 (2)	−0.0178 (16)	0.000 (2)
N2'	0.0511 (12)	0.0631 (14)	0.0287 (9)	−0.0101 (11)	0.0017 (8)	−0.0056 (10)
C1'	0.0490 (14)	0.0551 (16)	0.0294 (11)	−0.0039 (12)	0.0033 (10)	−0.0067 (11)
C2'	0.0435 (13)	0.0585 (16)	0.0335 (12)	−0.0036 (12)	0.0013 (10)	−0.0055 (12)
C3'	0.0564 (16)	0.0710 (19)	0.0436 (14)	−0.0109 (15)	−0.0010 (12)	0.0047 (14)
C4'	0.0615 (18)	0.0609 (18)	0.0516 (15)	−0.0017 (16)	0.0055 (13)	0.0070 (13)
C5'	0.0578 (17)	0.0577 (17)	0.0514 (15)	0.0018 (15)	0.0097 (12)	0.0058 (13)
C6'	0.0627 (18)	0.089 (2)	0.0461 (15)	−0.0277 (16)	−0.0028 (13)	−0.0014 (15)
C7'	0.0516 (15)	0.0491 (15)	0.0432 (13)	0.0015 (12)	0.0088 (11)	−0.0003 (12)
C8'	0.0647 (18)	0.0573 (17)	0.0514 (15)	0.0020 (15)	−0.0036 (13)	0.0037 (13)
C9'	0.0526 (17)	0.086 (2)	0.074 (2)	−0.0091 (17)	−0.0054 (14)	−0.0035 (19)
C10'	0.070 (2)	0.072 (2)	0.081 (2)	−0.0176 (17)	0.0198 (17)	0.0017 (18)
C11'	0.075 (2)	0.069 (2)	0.0672 (18)	−0.0007 (17)	0.0146 (16)	0.0179 (16)
C12'	0.0596 (17)	0.0593 (17)	0.0515 (15)	0.0030 (14)	0.0046 (12)	0.0060 (13)
C13'	0.0591 (17)	0.073 (2)	0.0506 (14)	−0.0145 (15)	0.0117 (13)	−0.0041 (14)

Geometric parameters (Å, º)

O1—C1	1.213 (3)	C7'—C12'	1.385 (4)
N1—C6	1.138 (4)	C7'—C8'	1.393 (4)
N2—C1	1.332 (3)	C8'—C9'	1.365 (4)
N2—C13	1.466 (3)	C9'—C10'	1.366 (4)
C1—C2	1.513 (3)	C10'—C11'	1.371 (4)
C2—C3	1.346 (4)	C11'—C12'	1.362 (4)
C2—C6	1.423 (4)	N2—H2	0.8600
C3—C4	1.414 (4)	C3—H3	0.9300
C4—C5	1.199 (3)	C8—H8	0.9300
C5—C7	1.424 (4)	C9—H9	0.9300
C7—C8	1.378 (4)	C10—H10	0.9300
C7—C12	1.391 (3)	C11—H11	0.9300
C8—C9	1.381 (4)	C12—H12	0.9300
C9—C10	1.375 (4)	C13—H13A	0.9600
C10—C11	1.351 (4)	C13—H13B	0.9600
C11—C12	1.383 (4)	C13—H13C	0.9600
O1'—C1'	1.228 (3)	N2'—H2'	0.8600
N1'—C6'	1.131 (3)	C3'—H3'	0.9300
N2'—C1'	1.329 (3)	C8'—H8'	0.9300
N2'—C13'	1.450 (3)	C9'—H9'	0.9300
C1'—C2'	1.495 (3)	C10'—H10'	0.9300
C2'—C3'	1.335 (3)	C11'—H11'	0.9300
C2'—C6'	1.420 (3)	C12'—H12'	0.9300
C3'—C4'	1.411 (4)	C13'—H13D	0.9600
C4'—C5'	1.191 (4)	C13'—H13E	0.9600
C5'—C7'	1.432 (4)	C13'—H13F	0.9600
C6···H2	2.38	C6'···H2'	2.41
O1'···H3'	2.45
C1—N2—C13	121.8 (2)	C13—N2—H2	119.1
O1—C1—N2	125.1 (2)	C2—C3—H3	118.6
O1—C1—C2	120.4 (2)	C4—C3—H3	118.6
N2—C1—C2	114.5 (2)	C7—C8—H8	119.8
C3—C2—C6	118.9 (2)	C9—C8—H8	119.8
C3—C2—C1	120.7 (2)	C10—C9—H9	120.0
C6—C2—C1	120.4 (2)	C8—C9—H9	120.0
C2—C3—C4	122.7 (3)	C11—C10—H10	119.8
C5—C4—C3	176.4 (3)	C9—C10—H10	119.8
C4—C5—C7	176.1 (3)	C10—C11—H11	119.8
N1—C6—C2	179.1 (3)	C12—C11—H11	119.8
C8—C7—C12	118.9 (2)	C11—C12—H12	120.0
C8—C7—C5	119.4 (2)	C7—C12—H12	120.0
C12—C7—C5	121.7 (2)	N2—C13—H13A	109.5
C7—C8—C9	120.3 (3)	N2—C13—H13B	109.5
C10—C9—C8	120.0 (3)	N2—C13—H13C	109.5
C11—C10—C9	120.4 (3)	H13A—C13—H13B	109.5
C10—C11—C12	120.4 (3)	H13A—C13—H13C	109.5
C11—C12—C7	120.0 (3)	H13B—C13—H13C	109.5
C1'—N2'—C13'	121.8 (2)	C1'—N2'—H2'	119.1
O1'—C1'—N2'	122.7 (2)	C13'—N2'—H2'	119.1
O1'—C1'—C2'	120.7 (2)	C2'—C3'—H3'	116.3
N2'—C1'—C2'	116.7 (2)	C4'—C3'—H3'	116.3
C3'—C2'—C6'	120.7 (2)	C9'—C8'—H8'	119.9
C3'—C2'—C1'	120.0 (2)	C7'—C8'—H8'	119.9
C6'—C2'—C1'	119.3 (2)	C8'—C9'—H9'	119.9
C2'—C3'—C4'	127.5 (2)	C10'—C9'—H9'	119.9
C5'—C4'—C3'	173.5 (3)	C9'—C10'—H10'	119.8
C4'—C5'—C7'	175.7 (3)	C11'—C10'—H10'	119.8
N1'—C6'—C2'	177.4 (3)	C12'—C11'—H11'	119.9
C12'—C7'—C8'	118.6 (3)	C10'—C11'—H11'	119.9
C12'—C7'—C5'	119.1 (2)	C11'—C12'—H12'	119.7
C8'—C7'—C5'	122.2 (2)	C7'—C12'—H12'	119.7
C9'—C8'—C7'	120.2 (3)	N2'—C13'—H13D	109.5
C8'—C9'—C10'	120.2 (3)	N2'—C13'—H13E	109.5
C9'—C10'—C11'	120.3 (3)	N2'—C13'—H13F	109.5
C12'—C11'—C10'	120.1 (3)	H13D—C13'—H13E	109.5
C11'—C12'—C7'	120.5 (3)	H13D—C13'—H13F	109.5
C1—N2—H2	119.1	H13E—C13'—H13F	109.5
C13—N2—C1—O1	5.3 (4)	C13'—N2'—C1'—O1'	0.1 (4)
C13—N2—C1—C2	−174.0 (2)	C13'—N2'—C1'—C2'	179.6 (2)
O1—C1—C2—C3	−5.8 (4)	O1'—C1'—C2'—C3'	−9.1 (4)
N2—C1—C2—C3	173.5 (2)	N2'—C1'—C2'—C3'	171.5 (2)
O1—C1—C2—C6	176.5 (3)	O1'—C1'—C2'—C6'	170.4 (3)
N2—C1—C2—C6	−4.2 (3)	N2'—C1'—C2'—C6'	−9.1 (4)
C6—C2—C3—C4	−0.4 (4)	C6'—C2'—C3'—C4'	−1.8 (5)
C1—C2—C3—C4	−178.2 (2)	C1'—C2'—C3'—C4'	177.7 (3)
C12—C7—C8—C9	1.6 (4)	C12'—C7'—C8'—C9'	1.1 (4)
C5—C7—C8—C9	−176.3 (3)	C5'—C7'—C8'—C9'	−176.2 (3)
C7—C8—C9—C10	−0.5 (5)	C7'—C8'—C9'—C10'	−0.6 (5)
C8—C9—C10—C11	−1.4 (5)	C8'—C9'—C10'—C11'	−1.2 (5)
C9—C10—C11—C12	2.2 (5)	C9'—C10'—C11'—C12'	2.4 (5)
C10—C11—C12—C7	−1.0 (4)	C10'—C11'—C12'—C7'	−1.9 (4)
C8—C7—C12—C11	−0.9 (4)	C8'—C7'—C12'—C11'	0.2 (4)
C5—C7—C12—C11	176.9 (2)	C5'—C7'—C12'—C11'	177.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.86	2.46	3.163 (4)	139
N2′—H2′···O1′^ii	0.86	2.19	2.939 (3)	145

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