1-(2-Pyridyl)ethan-1-one 8-quinolylhydrazone and 1-(1H-pyrrol-2-yl)ethan-1-one 8-quinolylhydrazone

The structures of the title compounds, C₁₆H₁₄N₄, (I), and C₁₅H₁₄N₄, (II), respectively, have been determined, and their molecular packing arrangements compared. Both are essentially flat mol­ecules, with respective dihedral angles between the quinoline and heterocyclic rings of 19.0 (1) and 8.5 (2)°. The pyridyl derivative, (I), packs in a P2₁/c unit cell, while in the pyrrolyl compound, (II), the mol­ecules pack in Pca2₁ and form a crinkled ribbon arrangement through the association of pyrrole NH groups with the quinoline N atoms.

S1. Comment

The Fischer indole synthesis, discovered in 1883 by Emil Fischer, occurs when phenylhydrazine is heated in acidic solution with an aldehyde or ketone (Clayden et al., 2001). The first step involves the formation of the phenylhydrazone, which is itself stable and can be isolated. The next three steps involve cyclization and the loss of ammonia to produce the aromatic indole. Substituents on the aldehyde or ketone are important because 4-methyl-2-phenyl-2H-phthalazin-1-one is produced by reacting phenylhydrazine with, respectively, 2-acetylbenzoic acid (Rowe & Peters, 1931), 2-acetylbenzonitrile (Helberger & von Rebay, 1937), or 3-(2-carboxyphenyl)-3-oxopropionic acid (Roser, 1885) in an analogous reaction to the indole synthesis. We have recently been studying the potential of 8-hydrazinoquinoline and produced 4-methyl-2-(8-quinolyl)phthalazin-1-one in a reaction containing 2-acetylbenzoic acid (Lynch & McClenaghan, 2002a).

The title compounds, (I) and (II), were synthesized by refluxing 8-hydrazinoquinoline dihydrochloride hydrate (Lynch & McClenaghan, 2002b) with the relevant 2-acetylheterocyclic compound (Fig. 1). The structure of an analogous product, (E)-2-acetylthiophene-8-quinonylhydrazone, has been reported (Lynch & McClenaghan, 2001a) and was found to be planar [dihedral angle between quinoline and thiophene rings 2.6 (2)°]. Each of these products can undergo additional cyclization to the corresponding pyrrolo[3,2-h]quinoline [see, for example, Lynch et al. (2001), Lynch & McClenaghan (2002c)] (Fig. 1).

Such molecules have potential as metal binding agents, although we have yet to study this possibility. In the quinonylhydrazone form, molecules such as (I) and (II) have one strong hydrogen-bond donor and two strong hydrogen-bond acceptors, as well as any similar atoms on the attached R group. The structure of the thienyl derivative showed that an intramolecular association to the adjacent quinoline N atom influenced the position of the hydrazone NH group. The subsequent arrangement (and steric hindrance) of the thienyl `tail' thus prevented any further intermolecular associations to the sp² N atom of the hydrazone.

As part of an overall study of the structural aspects of both of the quinonylhydrazones and the pyrrolo[3,2-h]quinolines we decided to study the structures of quinonylhydrazone analogues with varying numbers of hydrogen-bond acceptor and donor atoms within the R group. Here, we compare two structures, one with a single hydrogen-bond acceptor (pyridine) in the R group, (I), and one with a single hydrogen-bond donor (pyrrole), (II), with both hydrogen-bond components contained within heterocyclic rings. \sch

The structure of compound (I) (Fig. 2) is very similar to that of the thienyl derivative, being an essentially flat molecule [dihedral angle between quinoline and pyridine rings 19.0 (1)°] and having essentially the same trans-conformation for the two ring systems. Similarities extend to the packing of both compounds, in that both exist in centrosymmetric space groups; P2₁/c for (I) (Fig. 3) and Pbca for the thienyl derivative. In addition to the (hydrazone)N—H···N(quinoline) association, in (I), there is also an intramolecular C—H···N close contact from one of the methyl H atoms to the pyridine N atom. Two possible intermolecular close contacts (not listed in Table 1) are both from different quinoline H atoms to the quinoline N atom [H4···N1 2.74 Å and 135°] and pyridine N atom [H2···N15 2.69 Å and 135°].

Compound (II) is also essentially flat (Fig. 4) [dihedral angle 8.5 (2)°] and exists in the previously mentioned trans-conformation. However, the additional strong hydrogen-bond donor atom, and its requirement to be involved in a formal hydrogen bond when there are hydrogen-bond acceptors available for association, significantly influences the solid-state packing of (II). The subsequent N—H···N interaction between the pyrrole NH group and the quinoline N atom creates a crinkled ribbon arrangement that propagates along the a axis (Fig. 5), with the overall packing being noncentrosymmetric. The dihedral angle between associated pyrrole and quinoline rings is 83 (1)°.

The production and control of noncentrosymmetric space groups by hydrogen-bonding interactions is still an area of crystal engineering that is little understood, but it is worth pursuing because of the resultant nonlinear optical properties that any noncentrosymmetric material may possess. For this reason, we have decided to investigate further the solid-state structure and properties of quinonylhydrazone analogues, such as (II), that contain additional hydrogen-bond donor elements in the R group.

The table caption should be 'Hydrogen bonding amd contact geometry' for Tables 1 and 2.

S2. Experimental

The title compounds were obtained from Key Organics Ltd. and crystals were grown from ethanol solutions.

S3. Refinement

H atoms on N atoms were located in difference syntheses and had both positional and displacement parameters refined. All other H atoms were included at calculated positions and refined as riding models, with C—H set to 0.95 (Ar—H) and 0.98 Å (CH₃). High R_int values of 0.095 and 0.111 for (I) and (II), respectively, were the result of poor diffraction and weak high-angle data. The number of Friedel pairs for compound (II) is 1166. Is this sentence still needed if the data were merged?

Computing details

For both compounds, data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Nonius, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON94 (Spek, 1994) and PLATON97 (Spek, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A reaction schematic for the synthesis and use of 8-quinonylhydrozone analogues. Fig. 2. The molecular configuration and atom-numbering scheme for (I), with 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii. Fig. 3. The molecular packing for (I). Fig. 4. The molecular configuration and atom numbering scheme for (II), with 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii. Fig. 5. The molecular packing for (II). Hydrogen-bonding associations are indicated by dotted lines [symmetry code: (i) x + 1/2, 1 - y, z].

(I) 1-(2-Pyridyl)ethan-1-one (8-quinolyl)hydrazone

Crystal data

C16H14N4	F(000) = 552
Mr = 262.31	Dx = 1.336 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 13136 reflections
a = 10.1678 (4) Å	θ = 2.9–27.5°
b = 11.2970 (6) Å	µ = 0.08 mm^−1
c = 11.3566 (6) Å	T = 150 K
β = 90.284 (3)°	Needle, yellow
V = 1304.47 (11) Å^3	0.20 × 0.08 × 0.07 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	2987 independent reflections
Radiation source: Nonius FR591 rotating anode	1709 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.095
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −14→14
Tmin = 0.984, Tmax = 0.994	l = −14→14
17166 measured 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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0853P)^2] where P = (Fo^2 + 2Fc^2)/3
2987 reflections	(Δ/σ)max < 0.001
186 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

Geometry. Mean plane data ex SHELXL97 for molecule (I) ############################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

5.8864 (0.0064) x + 9.2083 (0.0051) y + 0.2055 (0.0083) z = 4.7515 (0.0054)

* 0.0051 (0.0012) N1 * -0.0076 (0.0013) C2 * 0.0021 (0.0013) C3 * 0.0051 (0.0013) C4 * -0.0070 (0.0012) C10 * 0.0023 (0.0012) C9

Rms deviation of fitted atoms = 0.0053

4.8575 (0.0063) x + 9.3561 (0.0047) y - 3.3547 (0.0088) z = 3.1097 (0.0066)

Angle to previous plane (with approximate e.s.d.) = 19.00 (0.08)

* 0.0008 (0.0012) N15 * 0.0009 (0.0012) C16 * -0.0001 (0.0013) C17 * -0.0023 (0.0013) C18 * 0.0040 (0.0013) C19 * -0.0033 (0.0013) C20

Rms deviation of fitted atoms = 0.0024

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.53216 (14)	0.16635 (14)	0.44951 (14)	0.0330 (4)
C2	0.44153 (19)	0.22151 (17)	0.51220 (19)	0.0378 (5)
H2	0.3746	0.2634	0.4710	0.047*
C3	0.4380 (2)	0.22205 (18)	0.63475 (19)	0.0417 (6)
H3	0.3712	0.2643	0.6751	0.052*
C4	0.5315 (2)	0.16125 (18)	0.69621 (18)	0.0397 (5)
H4	0.5304	0.1612	0.7799	0.050*
C5	0.7295 (2)	0.03098 (19)	0.69042 (17)	0.0395 (5)
H5	0.7328	0.0253	0.7738	0.049*
C6	0.8216 (2)	−0.02637 (18)	0.62345 (17)	0.0394 (5)
H6	0.8884	−0.0714	0.6614	0.049*
C7	0.81919 (19)	−0.01984 (17)	0.50142 (17)	0.0336 (5)
H7	0.8847	−0.0597	0.4572	0.042*
C8	0.72347 (17)	0.04345 (16)	0.44404 (16)	0.0280 (5)
C9	0.62621 (17)	0.10454 (16)	0.51098 (15)	0.0273 (4)
C10	0.62999 (18)	0.09834 (16)	0.63535 (16)	0.0323 (5)
N11	0.71540 (16)	0.05302 (15)	0.32222 (13)	0.0312 (4)
H11	0.642 (2)	0.089 (2)	0.2893 (19)	0.059 (7)*
N12	0.79755 (14)	−0.01433 (13)	0.25621 (13)	0.0299 (4)
C13	0.77639 (17)	−0.02003 (16)	0.14457 (16)	0.0275 (4)
C14	0.66589 (18)	0.04056 (18)	0.08165 (17)	0.0357 (5)
H141	0.5821	0.0168	0.1167	0.045*
H142	0.6668	0.0182	−0.0017	0.045*
H143	0.6764	0.1265	0.0887	0.045*
N15	0.84202 (15)	−0.11715 (14)	−0.03470 (13)	0.0319 (4)
C16	0.87285 (17)	−0.09272 (15)	0.07802 (16)	0.0276 (4)
C17	0.98815 (18)	−0.13360 (17)	0.13125 (17)	0.0323 (5)
H17	1.0073	−0.1148	0.2111	0.040*
C18	1.07367 (18)	−0.20149 (17)	0.06643 (18)	0.0368 (5)
H18	1.1525	−0.2306	0.1012	0.046*
C19	1.04407 (19)	−0.22697 (17)	−0.04939 (17)	0.0344 (5)
H19	1.1020	−0.2729	−0.0963	0.043*
C20	0.92811 (19)	−0.18383 (17)	−0.09480 (17)	0.0353 (5)
H20	0.9073	−0.2025	−0.1743	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0277 (8)	0.0289 (9)	0.0423 (10)	−0.0020 (7)	0.0031 (8)	−0.0009 (8)
C2	0.0295 (11)	0.0312 (12)	0.0528 (14)	−0.0018 (9)	0.0048 (10)	−0.0010 (10)
C3	0.0357 (12)	0.0339 (12)	0.0558 (14)	−0.0059 (9)	0.0178 (11)	−0.0057 (10)
C4	0.0469 (13)	0.0382 (13)	0.0342 (11)	−0.0146 (10)	0.0135 (10)	−0.0046 (9)
C5	0.0479 (13)	0.0426 (13)	0.0279 (11)	−0.0120 (10)	−0.0039 (10)	0.0037 (9)
C6	0.0405 (12)	0.0360 (12)	0.0416 (12)	−0.0019 (9)	−0.0094 (10)	0.0064 (10)
C7	0.0338 (11)	0.0314 (11)	0.0355 (11)	−0.0005 (9)	−0.0022 (9)	−0.0035 (9)
C8	0.0267 (10)	0.0219 (10)	0.0354 (11)	−0.0025 (8)	−0.0005 (8)	−0.0009 (8)
C9	0.0277 (10)	0.0225 (10)	0.0319 (10)	−0.0053 (8)	0.0007 (8)	−0.0012 (8)
C10	0.0340 (11)	0.0271 (11)	0.0359 (11)	−0.0110 (9)	0.0049 (9)	−0.0009 (9)
N11	0.0291 (9)	0.0344 (10)	0.0301 (9)	0.0050 (7)	0.0003 (8)	−0.0035 (7)
N12	0.0266 (8)	0.0260 (9)	0.0371 (10)	0.0013 (7)	0.0030 (8)	−0.0032 (7)
C13	0.0258 (10)	0.0259 (10)	0.0308 (11)	−0.0030 (8)	−0.0005 (8)	−0.0005 (8)
C14	0.0305 (10)	0.0375 (12)	0.0392 (11)	0.0062 (9)	0.0019 (9)	0.0000 (9)
N15	0.0342 (9)	0.0322 (9)	0.0294 (9)	0.0016 (7)	0.0019 (7)	0.0020 (7)
C16	0.0256 (9)	0.0226 (10)	0.0347 (10)	−0.0023 (8)	0.0015 (8)	0.0021 (8)
C17	0.0307 (10)	0.0316 (11)	0.0344 (10)	0.0016 (8)	−0.0024 (9)	−0.0014 (9)
C18	0.0274 (10)	0.0313 (12)	0.0517 (13)	0.0047 (8)	−0.0026 (10)	−0.0009 (10)
C19	0.0353 (11)	0.0270 (11)	0.0410 (12)	0.0009 (8)	0.0068 (10)	−0.0035 (9)
C20	0.0412 (12)	0.0328 (12)	0.0320 (11)	0.0013 (9)	0.0054 (10)	−0.0011 (9)

Geometric parameters (Å, º)

N1—C2	1.323 (2)	N11—N12	1.358 (2)
N1—C9	1.372 (2)	N11—H11	0.93 (2)
C2—C3	1.392 (3)	N12—C13	1.287 (2)
C2—H2	0.95	C13—C16	1.488 (2)
C3—C4	1.362 (3)	C13—C14	1.494 (3)
C3—H3	0.95	C14—H141	0.98
C4—C10	1.412 (3)	C14—H142	0.98
C4—H4	0.95	C14—H143	0.98
C5—C6	1.372 (3)	N15—C20	1.344 (2)
C5—C10	1.410 (3)	N15—C16	1.345 (2)
C5—H5	0.95	C16—C17	1.395 (3)
C6—C7	1.388 (3)	C17—C18	1.376 (3)
C6—H6	0.95	C17—H17	0.95
C7—C8	1.370 (3)	C18—C19	1.378 (3)
C7—H7	0.95	C18—H18	0.95
C8—N11	1.390 (2)	C19—C20	1.374 (3)
C8—C9	1.428 (2)	C19—H19	0.95
C9—C10	1.414 (3)	C20—H20	0.95
C2—N1—C9	116.83 (16)	N12—N11—H11	121.2 (14)
N1—C2—C3	124.13 (19)	C8—N11—H11	118.6 (14)
N1—C2—H2	117.9	C13—N12—N11	118.14 (15)
C3—C2—H2	117.9	N12—C13—C16	114.88 (16)
C4—C3—C2	119.26 (17)	N12—C13—C14	124.75 (16)
C4—C3—H3	120.4	C16—C13—C14	120.38 (15)
C2—C3—H3	120.4	C13—C14—H141	109.5
C3—C4—C10	119.85 (18)	C13—C14—H142	109.5
C3—C4—H4	120.1	H141—C14—H142	109.5
C10—C4—H4	120.1	C13—C14—H143	109.5
C6—C5—C10	119.95 (18)	H141—C14—H143	109.5
C6—C5—H5	120.0	H142—C14—H143	109.5
C10—C5—H5	120.0	C20—N15—C16	116.69 (16)
C5—C6—C7	121.3 (2)	N15—C16—C17	122.41 (16)
C5—C6—H6	119.3	N15—C16—C13	116.45 (16)
C7—C6—H6	119.3	C17—C16—C13	121.14 (16)
C8—C7—C6	120.78 (18)	C18—C17—C16	118.99 (18)
C8—C7—H7	119.6	C18—C17—H17	120.5
C6—C7—H7	119.6	C16—C17—H17	120.5
C7—C8—N11	123.54 (16)	C17—C18—C19	119.44 (18)
C7—C8—C9	119.42 (17)	C17—C18—H18	120.3
N11—C8—C9	117.04 (16)	C19—C18—H18	120.3
N1—C9—C10	123.27 (16)	C20—C19—C18	117.85 (17)
N1—C9—C8	117.25 (16)	C20—C19—H19	121.1
C10—C9—C8	119.47 (17)	C18—C19—H19	121.1
C5—C10—C4	124.32 (18)	N15—C20—C19	124.63 (18)
C5—C10—C9	119.05 (16)	N15—C20—H20	117.7
C4—C10—C9	116.63 (18)	C19—C20—H20	117.7
N12—N11—C8	118.19 (16)
C9—N1—C2—C3	1.3 (3)	N1—C9—C10—C4	−0.8 (3)
N1—C2—C3—C4	−1.0 (3)	C8—C9—C10—C4	179.65 (16)
C2—C3—C4—C10	−0.3 (3)	C7—C8—N11—N12	7.6 (3)
C10—C5—C6—C7	−0.1 (3)	C9—C8—N11—N12	−172.94 (15)
C5—C6—C7—C8	−0.7 (3)	C8—N11—N12—C13	169.08 (16)
C6—C7—C8—N11	−179.76 (18)	N11—N12—C13—C16	178.32 (14)
C6—C7—C8—C9	0.8 (3)	N11—N12—C13—C14	−1.2 (3)
C2—N1—C9—C10	−0.3 (3)	C20—N15—C16—C17	0.1 (3)
C2—N1—C9—C8	179.21 (16)	C20—N15—C16—C13	−179.30 (15)
C7—C8—C9—N1	−179.78 (16)	N12—C13—C16—N15	169.20 (16)
N11—C8—C9—N1	0.7 (2)	C14—C13—C16—N15	−11.3 (2)
C7—C8—C9—C10	−0.2 (3)	N12—C13—C16—C17	−10.3 (2)
N11—C8—C9—C10	−179.72 (16)	C14—C13—C16—C17	169.26 (17)
C6—C5—C10—C4	−179.50 (18)	N15—C16—C17—C18	−0.1 (3)
C6—C5—C10—C9	0.6 (3)	C13—C16—C17—C18	179.37 (16)
C3—C4—C10—C5	−178.78 (18)	C16—C17—C18—C19	0.4 (3)
C3—C4—C10—C9	1.1 (3)	C17—C18—C19—C20	−0.7 (3)
N1—C9—C10—C5	179.04 (17)	C16—N15—C20—C19	−0.6 (3)
C8—C9—C10—C5	−0.5 (3)	C18—C19—C20—N15	0.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···N1	0.93 (2)	2.31 (2)	2.688 (2)	104 (3)
C14—H142···N15	0.98	2.38	2.855 (2)	109

(II) 1-(1H-Pyrrol-2-yl)ethan-1-one (8-quinolyl)hydrazone

Crystal data

C15H14N4	F(000) = 528
Mr = 250.30	Dx = 1.322 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2c-2ac	Cell parameters from 4172 reflections
a = 10.690 (2) Å	θ = 2.9–27.5°
b = 5.5066 (11) Å	µ = 0.08 mm^−1
c = 21.363 (4) Å	T = 150 K
V = 1257.5 (4) Å^3	Plate, yellow
Z = 4	0.32 × 0.24 × 0.01 mm

Data collection

Nonius KappaCCD area-detector diffractometer	1445 independent reflections
Radiation source: Nonius FR591 rotating anode	876 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.111
Detector resolution: 9.091 pixels mm^-1	θmax = 27.4°, θmin = 3.7°
ϕ and ω scans	h = −13→13
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −7→7
Tmin = 0.974, Tmax = 0.999	l = −27→23
7258 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0497P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max < 0.001
1445 reflections	Δρmax = 0.23 e Å^−3
181 parameters	Δρmin = −0.33 e Å^−3
1 restraint	Absolute structure: (Flack, 1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (5)

Special details

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

Geometry. Mean plane data ex SHELXL97 for molecule (II) #############################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

8.3706 (0.0093) x + 3.3753 (0.0060) y + 2.2524 (0.0297) z = 10.5584 (0.0229)

* -0.0044 (0.0023) N1 * 0.0040 (0.0026) C2 * 0.0006 (0.0027) C3 * -0.0044 (0.0026) C4 * 0.0037 (0.0024) C10 * 0.0005 (0.0024) C9

Rms deviation of fitted atoms = 0.0034

8.1553 (0.0137) x + 3.5541 (0.0083) y - 0.8007 (0.0423) z = 8.6944 (0.0292)

Angle to previous plane (with approximate e.s.d.) = 8.48 (0.22)

* -0.0033 (0.0024) N15 * 0.0018 (0.0023) C16 * 0.0003 (0.0022) C17 * -0.0022 (0.0024) C18 * 0.0034 (0.0025) C19

Rms deviation of fitted atoms = 0.0025

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.6874 (3)	0.9214 (6)	0.75041 (14)	0.0258 (8)
C2	0.6150 (3)	1.0857 (7)	0.7770 (2)	0.0302 (10)
H2	0.5761	1.2024	0.7506	0.038*
C3	0.5915 (3)	1.0997 (8)	0.84171 (19)	0.0295 (11)
H3	0.5381	1.2215	0.8583	0.037*
C4	0.6474 (3)	0.9341 (7)	0.8800 (2)	0.0296 (10)
H4	0.6324	0.9394	0.9238	0.037*
C5	0.7882 (3)	0.5783 (7)	0.89170 (18)	0.0275 (10)
H5	0.7764	0.5756	0.9358	0.034*
C6	0.8640 (3)	0.4112 (7)	0.86422 (17)	0.0271 (10)
H6	0.9048	0.2932	0.8894	0.034*
C7	0.8829 (3)	0.4105 (7)	0.79905 (17)	0.0265 (10)
H7	0.9362	0.2921	0.7808	0.033*
C8	0.8250 (3)	0.5794 (7)	0.76150 (18)	0.0228 (9)
C9	0.7444 (3)	0.7558 (6)	0.78886 (18)	0.0222 (10)
C10	0.7269 (3)	0.7559 (7)	0.85514 (17)	0.0235 (10)
N11	0.8423 (3)	0.5871 (7)	0.69708 (15)	0.0290 (9)
H11	0.808 (3)	0.720 (7)	0.6776 (16)	0.012 (9)*
N12	0.9213 (3)	0.4212 (7)	0.67012 (15)	0.0260 (8)
C13	0.9336 (3)	0.4290 (8)	0.60966 (17)	0.0217 (10)
C14	0.8683 (4)	0.6031 (8)	0.56800 (19)	0.0288 (10)
H141	0.8908	0.7694	0.5799	0.036*
H142	0.7777	0.5814	0.5720	0.036*
H143	0.8934	0.5737	0.5245	0.036*
N15	1.0855 (3)	0.0943 (7)	0.62013 (17)	0.0272 (9)
H15	1.094 (4)	0.103 (8)	0.659 (2)	0.041 (15)*
C16	1.0158 (3)	0.2474 (7)	0.58325 (17)	0.0227 (9)
C17	1.0391 (3)	0.1795 (7)	0.52143 (19)	0.0301 (9)
H17	1.0040	0.2519	0.4851	0.038*
C18	1.1241 (3)	−0.0160 (8)	0.5226 (2)	0.0354 (10)
H18	1.1564	−0.0995	0.4872	0.044*
C19	1.1519 (3)	−0.0642 (8)	0.5843 (2)	0.0322 (11)
H19	1.2073	−0.1861	0.5991	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0245 (17)	0.030 (2)	0.023 (2)	0.0018 (15)	−0.0032 (13)	−0.0006 (18)
C2	0.026 (2)	0.031 (3)	0.034 (3)	0.0036 (19)	−0.0048 (19)	−0.007 (2)
C3	0.028 (2)	0.036 (3)	0.024 (3)	0.0042 (18)	0.0030 (17)	−0.009 (2)
C4	0.027 (2)	0.041 (3)	0.021 (2)	−0.0045 (19)	0.0059 (17)	−0.013 (2)
C5	0.032 (2)	0.039 (3)	0.011 (2)	−0.0049 (19)	0.0016 (16)	−0.003 (2)
C6	0.030 (2)	0.033 (3)	0.018 (2)	−0.0001 (18)	0.0023 (16)	0.004 (2)
C7	0.0246 (19)	0.031 (3)	0.024 (3)	−0.0016 (18)	0.0027 (18)	−0.004 (2)
C8	0.0242 (19)	0.030 (3)	0.014 (2)	0.0012 (18)	0.0008 (16)	0.000 (2)
C9	0.0178 (17)	0.029 (2)	0.020 (2)	−0.0013 (17)	0.0011 (16)	−0.0041 (18)
C10	0.0187 (17)	0.032 (3)	0.019 (2)	−0.0041 (17)	0.0021 (15)	−0.0063 (18)
N11	0.036 (2)	0.034 (2)	0.017 (2)	0.0102 (17)	0.0016 (15)	0.002 (2)
N12	0.0220 (17)	0.037 (2)	0.019 (2)	0.0037 (15)	0.0023 (13)	−0.0046 (18)
C13	0.0213 (19)	0.027 (3)	0.017 (3)	−0.0037 (16)	−0.0035 (16)	0.001 (2)
C14	0.026 (2)	0.042 (3)	0.019 (2)	0.0037 (19)	−0.0003 (17)	0.003 (2)
N15	0.0271 (19)	0.038 (2)	0.017 (2)	0.0057 (15)	−0.0016 (15)	−0.0059 (19)
C16	0.0212 (19)	0.030 (2)	0.017 (2)	−0.0036 (18)	−0.0002 (16)	0.000 (2)
C17	0.027 (2)	0.045 (3)	0.018 (2)	−0.0067 (17)	0.0010 (18)	−0.001 (2)
C18	0.035 (2)	0.043 (3)	0.028 (2)	−0.0058 (19)	0.009 (2)	−0.013 (2)
C19	0.026 (2)	0.035 (3)	0.035 (3)	0.0033 (18)	0.0021 (19)	−0.006 (2)

Geometric parameters (Å, º)

N1—C2	1.319 (5)	N11—N12	1.371 (4)
N1—C9	1.371 (4)	N11—H11	0.92 (4)
C2—C3	1.408 (6)	N12—C13	1.299 (5)
C2—H2	0.95	C13—C16	1.446 (5)
C3—C4	1.363 (6)	C13—C14	1.483 (6)
C3—H3	0.95	C14—H141	0.98
C4—C10	1.402 (5)	C14—H142	0.98
C4—H4	0.95	C14—H143	0.98
C5—C6	1.359 (5)	N15—C19	1.361 (5)
C5—C10	1.413 (5)	N15—C16	1.374 (5)
C5—H5	0.95	N15—H15	0.83 (5)
C6—C7	1.407 (5)	C16—C17	1.395 (5)
C6—H6	0.95	C17—C18	1.409 (5)
C7—C8	1.376 (5)	C17—H17	0.95
C7—H7	0.95	C18—C19	1.376 (6)
C8—N11	1.389 (5)	C18—H18	0.95
C8—C9	1.424 (5)	C19—H19	0.95
C9—C10	1.428 (4)
C2—N1—C9	117.4 (3)	N12—N11—C8	118.6 (3)
N1—C2—C3	124.4 (4)	N12—N11—H11	126 (2)
N1—C2—H2	117.8	C8—N11—H11	115 (2)
C3—C2—H2	117.8	C13—N12—N11	117.3 (3)
C4—C3—C2	118.4 (4)	N12—C13—C16	115.3 (4)
C4—C3—H3	120.8	N12—C13—C14	124.8 (4)
C2—C3—H3	120.8	C16—C13—C14	119.9 (3)
C3—C4—C10	120.4 (4)	C13—C14—H141	109.5
C3—C4—H4	119.8	C13—C14—H142	109.5
C10—C4—H4	119.8	H141—C14—H142	109.5
C6—C5—C10	120.4 (3)	C13—C14—H143	109.5
C6—C5—H5	119.8	H141—C14—H143	109.5
C10—C5—H5	119.8	H142—C14—H143	109.5
C5—C6—C7	121.0 (4)	C19—N15—C16	110.7 (4)
C5—C6—H6	119.5	C19—N15—H15	122 (3)
C7—C6—H6	119.5	C16—N15—H15	127 (3)
C8—C7—C6	120.7 (4)	N15—C16—C17	106.3 (3)
C8—C7—H7	119.6	N15—C16—C13	122.0 (3)
C6—C7—H7	119.6	C17—C16—C13	131.6 (3)
C7—C8—N11	122.6 (4)	C16—C17—C18	107.6 (4)
C7—C8—C9	119.6 (3)	C16—C17—H17	126.2
N11—C8—C9	117.8 (4)	C18—C17—H17	126.2
N1—C9—C8	118.5 (3)	C19—C18—C17	107.7 (4)
N1—C9—C10	122.4 (3)	C19—C18—H18	126.1
C8—C9—C10	119.1 (3)	C17—C18—H18	126.1
C4—C10—C5	123.8 (4)	N15—C19—C18	107.6 (4)
C4—C10—C9	117.1 (4)	N15—C19—H19	126.2
C5—C10—C9	119.1 (3)	C18—C19—H19	126.2
C9—N1—C2—C3	−0.8 (6)	N1—C9—C10—C5	179.6 (3)
N1—C2—C3—C4	0.4 (6)	C8—C9—C10—C5	−1.2 (5)
C2—C3—C4—C10	0.5 (6)	C7—C8—N11—N12	−0.7 (5)
C10—C5—C6—C7	−0.2 (6)	C9—C8—N11—N12	178.9 (3)
C5—C6—C7—C8	0.0 (6)	C8—N11—N12—C13	178.5 (4)
C6—C7—C8—N11	179.2 (4)	N11—N12—C13—C16	−178.8 (3)
C6—C7—C8—C9	−0.4 (6)	N11—N12—C13—C14	−0.2 (6)
C2—N1—C9—C8	−178.8 (3)	C19—N15—C16—C17	0.5 (4)
C2—N1—C9—C10	0.5 (5)	C19—N15—C16—C13	178.1 (3)
C7—C8—C9—N1	−179.7 (3)	N12—C13—C16—N15	−6.4 (5)
N11—C8—C9—N1	0.7 (5)	C14—C13—C16—N15	175.0 (4)
C7—C8—C9—C10	1.0 (5)	N12—C13—C16—C17	170.5 (4)
N11—C8—C9—C10	−178.6 (3)	C14—C13—C16—C17	−8.1 (6)
C3—C4—C10—C5	180.0 (4)	N15—C16—C17—C18	−0.2 (4)
C3—C4—C10—C9	−0.8 (5)	C13—C16—C17—C18	−177.4 (4)
C6—C5—C10—C4	−180.0 (3)	C16—C17—C18—C19	−0.2 (4)
C6—C5—C10—C9	0.8 (6)	C16—N15—C19—C18	−0.7 (5)
N1—C9—C10—C4	0.3 (5)	C17—C18—C19—N15	0.6 (5)
C8—C9—C10—C4	179.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11···N1	0.92 (4)	2.30 (3)	2.726 (4)	107 (3)
N15—H15···N1^i	0.83 (5)	2.20 (5)	2.990 (5)	159 (4)

Symmetry code: (i) x+1/2, −y+1, z.