A simple hydrogen-bonded chain in (3Z)-3-{1-[(5-phenyl-1H-pyrazol-3-yl)amino]ethyl­idene}-4,5-dihydro­furan-2(3H)-one, and a hydrogen-bonded ribbon of centrosymmetric rings in the self-assembled adduct (3Z)-3-{1-[(5-methyl-1H-pyrazol-3-yl)amino]ethyl­idene}-4,5-dihydro­furan-2(3H)-one–6-(2-hydroxy­ethyl)-2,5-dimethyl­pyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1)

(3Z)-3-{1-[(5-Phenyl-1H-pyrazol-3-yl)amino]ethyl­idene}-4,5-dihydro­furan-2(3H)-one, C₁₅H₁₅N₃O₂, (I), and the stoichiometric adduct (3Z)-3-{1-[(5-methyl-1H-pyrazol-3-yl)­amino]ethyl­idene}-4,5-dihydro­furan-2(3H)-one–6-(2-hydroxy­ethyl)-2,5-dimethyl­pyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1), C₁₀H₁₃N₃O₂·C₁₀H₁₃N₃O₂, (II), in which the two components have the same composition but different constitutions, are formed in the reactions of 2-acetyl-4-butyrolactone with 5-amino-3-phenyl-1H-pyrazole and 5-amino-3-methyl-1H-pyra­zole, respectively. In each compound, the furan­one component contains an intra­molecular N—H...O hydrogen bond. The mol­ecules of (I) are linked into a chain by a single inter­molecular N—H...O hydrogen bond, while in (II), a combination of one O—H...N hydrogen bond, within the selected asymmetric unit, and two N—H...O hydrogen bonds link the mol­ecular components into a ribbon containing alternating centrosymmetric R₄⁴(20) and R₆⁶(22) rings.

S1. Comment

The condensation reactions between substituted aminopyrazoles and dicarbonyl compounds provide a potentially very versatile route for the synthesis of new fused heterocyclic compounds with precisely defined regiochemistry (Portilla et al., 2008), and fused pyrazole derivatives are potentially valuable for drug and pesticide applications (Elguero, 1984,1996). Here, we report the structures of the two title compounds, (I) and (II) (Figs. 1 and 2), which result from the condensation reactions between 2-acetyl-4-butyrolactone and two 5-amino-1H-pyrazoles carrying different hydrocarbyl substituents at position 3 (see reaction scheme).

The reaction between equimolar quantities of the lactone and 5-amino-3-phenyl-1H-pyrazole provides (3Z)-3-{1-[(5-phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5-dihydrofuran-2(3H)-one, (I), which apparently results from a simple condensation involving only the 2-acetyl substituent in the lactone reagent, to form a product in which the lactone ring survives intact (see reaction scheme). By contrast, the corresponding reaction between the same lactone reagent and 5-amino-3-methyl-1H-pyrazole proceeds along two different reaction pathways. One of these pathways is entirely analogous to that which forms compound (I), leading to the product denoted (A) in the reaction scheme. The second pathway involves both carbonyl functions in the lactone component, which itself undergoes ring opening, so that this pathway is indeed a cyclocondensation reaction giving a fused heterocyclic system in the product denoted (B) in the reaction scheme. The product (II) which crystallizes from the reaction between 5-amino-3-methyl-1H-pyrazole and the lactone is a 1:1 hydrogen-bonded adduct formed by the primary products (A) and (B), which are, in fact, isomeric with one another despite their very different constitutions.

Within the molecule of compound (I), the C2—O2 and C3—C6 bonds (Table 1) are both long for their types [mean values (Allen et al., 1987) 1.201 and 1.340 Å, respectively, upper quartile values 1.206 and 1.348 Å, respectively] and the C2—C3 bond is short for its type (mean value 1.464 Å, lower quartile value 1.453 Å), while the N7—C6 bond is significantly shorter than the N7—C13 bond. These values provide evidence for electronic polarization in the vinylogous amide fragment of (I), indicating that the form (Ia) is a significant contributor to the overall electronic structure. A similar pattern of distances is found in component (A) of compound (II) (Table 3), but the deviations from the expected values are all somewhat smaller in (II), indicative of a lesser degree of electronic polarization in this component. A similar pattern is found also in the vinylogous amide fragment in component (B) of (II), indicating a contribution from the form (IIa). Consistent with this observation concerning component (B) of (II), the C12—C13 and C13—C13A bonds in (II) differ in length by almost 0.04 Å, while the corresponding differences in (I) and in component (A) of (II) are no more than half of this value. In addition, the C13A—N17A bond in (II) is rather longer than the corresponding bonds in the unfused pyrazole rings of both (I) and (II), indicating stronger bond fixation in the fused pyrazole ring than in either of the unfused pyrazole rings.

The molecules of (I) contain an intramolecular N—H···O hydrogen bond (Table 2, Fig. 1) forming an S(6) motif (Bernstein et al., 1995), and molecules related by the 2₁ screw axis along (1/2, y, 3/4) are linked into chains by a second N—H···O hydrogen bond to form an S(6)C(9)C¹₂(7) chain of rings running parallel to the [010] direction (Fig. 3). Two chains of this type, related to one another by inversion, pass through each unit cell, but there are no direction-specific interactions between adjacent chains. In particular, there are neither C—H···π(arene) hydrogen bonds nor aromatic π–π stacking interactions in the structure of (I).

Within the selected asymmetric unit of (II) (Fig. 2), the two components are linked by a fairly short and almost linear O—H···N hydrogen bond (Table 4), and there is also an intramolecular N—H···O hydrogen bond, analogous to that in (I). Two further N—H···O hydrogen bonds then link the bimolecular aggregates into a ribbon containing two types of centrosymmetric ring and running parallel to the [100] direction. Within the ribbon, R₄⁴(20) rings centred at (n + 1/2, 1/2, 1/2), where n represents an integer, alternate with R₆⁶(22) rings centred at (n, 1/2, 1/2) where n again represents an integer (Fig. 4).

S2. Experimental

For the synthesis of compound (I), a mixture of 2-acetyl-4-butyrolactone (1 mmol), 5-amino-3-phenyl-1H-pyrazole (1 mmol) and 4-toluenesulfonic acid (0.01 mmol) in ethanol (15 ml) was heated under reflux with magnetic stirring for 18 h. The mixture was cooled to ambient temperature and the solvent was removed under reduced pressure. The resulting solid product was recrystallized from dimethylformamide to yield (I) as colourless crystals (yield 63%, m.p. 595–596 K). Analysis: MS (70 eV) m/z (%) 269 (5, M⁺), 251 (35), 104 (25), 18 (100).

For the synthesis of compound (II), a mixture of 2-acetyl-4-butyrolactone (1 mmol), 5-amino-3-methyl-1H-pyrazole (1 mmol) and 4-toluenesulfonic acid (0.01 mmol) in ethanol (15 ml) was heated under reflux with magnetic stirring for 23 h. The reaction mixture was cooled to ambient temperature and the solvent was removed under reduced pressure. The resulting solid product was recrystallized from dimethylformamide to yield (II) as colourless crystals (yield 48%, m.p. 493–494 K). Analysis: MS (70 eV) m/z (%) 207 (6, M⁺), 189 (23), 152 (8), 86 (41), 43 (100).

S3. Refinement

All H atoms were located in difference maps. H atoms bonded to C or N atoms were then treated as riding in geometrically idealized positions, with C—H = 0.95 (aromatic or pyrazole), 0.98 (CH₃) or 0.99 Å (CH₂) and N—H = 0.88 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms bonded to C or N atoms. The H atom bonded to an O atom in compound (II) was permitted to ride at the position deduced from the difference maps, with U_iso(H) = 1.5U_eq(O), giving an O—H distance of 0.86 Å.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of compound (I), showing the atom-labelling scheme and the intramolecular hydrogen bond (dashed line). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The independent molecular components of compound (II), showing the atom-labelling scheme and the hydrogen bonds within the asymmetric unit (dashed line). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. Part of the crystal structure of compound (I), showing the formation of a hydrogen-bonded chain of rings running parallel to [010]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Dashed lines indicate hydrogen bonds. Atoms marked with an asterisk (*), a dollar sign ($) or an ampersand (&) are at the symmetry positions (1 - x, -1/2 + y, 3/2 - z), (1 - x, 1/2 + y, 3/2 - z) and (x, -1 + y, z), respectively.
	Fig. 4. A stereoview of part of the crystal structure of (II), showing the formation of a hydrogen-bonded ribbon parallel to [100]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Dashed lines indicate hydrogen bonds.

(I) (3Z)-3-{1-[(5-phenyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5- dihydrofuran-2(3H)-one

Crystal data

C15H15N3O2	F(000) = 568
Mr = 269.30	Dx = 1.385 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2536 reflections
a = 10.4969 (17) Å	θ = 3.3–26.1°
b = 9.8550 (9) Å	µ = 0.10 mm^−1
c = 12.6739 (16) Å	T = 120 K
β = 99.883 (9)°	Block, colourless
V = 1291.6 (3) Å^3	0.39 × 0.25 × 0.14 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2536 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1704 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 9.091 pixels mm^-1	θmax = 26.1°, θmin = 3.3°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→12
Tmin = 0.964, Tmax = 0.987	l = −15→15
19109 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0499P)^2 + 0.7664P] where P = (Fo^2 + 2Fc^2)/3
2536 reflections	(Δ/σ)max = 0.001
182 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	0.24565 (15)	0.99120 (16)	0.48162 (13)	0.0398 (4)
C2	0.3290 (2)	0.8906 (2)	0.51543 (18)	0.0321 (5)
C3	0.40566 (19)	0.8586 (2)	0.43747 (16)	0.0269 (5)
C4	0.3659 (2)	0.9450 (2)	0.34120 (18)	0.0363 (6)
H4A	0.3342	0.8894	0.2770	0.044*
H4B	0.4382	1.0029	0.3269	0.044*
C5	0.2574 (2)	1.0299 (2)	0.37378 (19)	0.0377 (6)
H5A	0.2780	1.1277	0.3710	0.045*
H5B	0.1751	1.0126	0.3244	0.045*
O2	0.33004 (15)	0.84051 (17)	0.60463 (12)	0.0397 (4)
C6	0.50234 (19)	0.7638 (2)	0.45348 (16)	0.0260 (5)
C61	0.5851 (2)	0.7370 (2)	0.37190 (17)	0.0320 (5)
H61A	0.6753	0.7580	0.4020	0.048*
H61B	0.5568	0.7941	0.3089	0.048*
H61C	0.5778	0.6412	0.3509	0.048*
N7	0.52487 (16)	0.69449 (18)	0.54559 (14)	0.0298 (4)
H7	0.4737	0.7167	0.5910	0.036*
N11	0.69552 (16)	0.45224 (18)	0.69836 (13)	0.0291 (4)
H11	0.7092	0.4029	0.7571	0.035*
N12	0.59966 (17)	0.54334 (18)	0.67646 (14)	0.0305 (4)
C13	0.61353 (19)	0.5946 (2)	0.58251 (16)	0.0267 (5)
C14	0.71760 (19)	0.5361 (2)	0.54421 (16)	0.0275 (5)
H14	0.7470	0.5555	0.4790	0.033*
C15	0.76826 (19)	0.4442 (2)	0.62139 (16)	0.0257 (5)
C51	0.87557 (19)	0.3499 (2)	0.62863 (16)	0.0267 (5)
C52	0.9272 (2)	0.3170 (2)	0.53853 (18)	0.0344 (6)
H52	0.8947	0.3597	0.4722	0.041*
C53	1.0251 (2)	0.2229 (2)	0.54399 (19)	0.0392 (6)
H53	1.0586	0.2004	0.4812	0.047*
C54	1.0744 (2)	0.1618 (2)	0.63896 (19)	0.0366 (6)
H54	1.1417	0.0966	0.6423	0.044*
C55	1.0261 (2)	0.1953 (2)	0.72947 (18)	0.0375 (6)
H55	1.0606	0.1540	0.7960	0.045*
C56	0.9278 (2)	0.2888 (2)	0.72418 (17)	0.0343 (5)
H56	0.8953	0.3116	0.7874	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0343 (9)	0.0378 (9)	0.0484 (10)	0.0083 (8)	0.0103 (7)	−0.0040 (8)
C2	0.0293 (12)	0.0279 (12)	0.0387 (14)	−0.0009 (10)	0.0046 (10)	−0.0060 (10)
C3	0.0265 (11)	0.0250 (11)	0.0298 (12)	−0.0024 (9)	0.0064 (9)	−0.0035 (9)
C4	0.0338 (12)	0.0352 (13)	0.0406 (13)	0.0022 (11)	0.0080 (10)	0.0015 (11)
C5	0.0306 (12)	0.0302 (13)	0.0513 (15)	0.0017 (10)	0.0037 (10)	−0.0027 (12)
O2	0.0406 (9)	0.0484 (10)	0.0325 (9)	0.0030 (8)	0.0133 (7)	−0.0049 (8)
C6	0.0259 (11)	0.0249 (11)	0.0275 (11)	−0.0052 (9)	0.0055 (8)	−0.0035 (9)
C61	0.0309 (11)	0.0339 (13)	0.0330 (12)	0.0033 (10)	0.0109 (9)	0.0033 (10)
N7	0.0311 (10)	0.0312 (10)	0.0287 (10)	0.0043 (8)	0.0100 (8)	−0.0024 (8)
N11	0.0326 (10)	0.0284 (10)	0.0269 (9)	0.0006 (8)	0.0071 (8)	0.0012 (8)
N12	0.0338 (10)	0.0301 (10)	0.0288 (10)	0.0004 (9)	0.0087 (8)	−0.0023 (8)
C13	0.0270 (11)	0.0260 (11)	0.0274 (11)	−0.0041 (9)	0.0052 (9)	−0.0037 (9)
C14	0.0264 (11)	0.0310 (12)	0.0256 (11)	−0.0005 (10)	0.0059 (9)	−0.0004 (9)
C15	0.0268 (11)	0.0252 (11)	0.0247 (11)	−0.0057 (9)	0.0038 (9)	−0.0030 (9)
C51	0.0250 (10)	0.0244 (11)	0.0303 (12)	−0.0032 (9)	0.0037 (9)	0.0005 (9)
C52	0.0312 (12)	0.0398 (14)	0.0324 (13)	0.0055 (11)	0.0060 (9)	0.0056 (10)
C53	0.0330 (12)	0.0467 (15)	0.0402 (13)	0.0070 (11)	0.0127 (10)	0.0025 (12)
C54	0.0267 (11)	0.0349 (13)	0.0474 (15)	0.0040 (10)	0.0042 (10)	0.0034 (11)
C55	0.0372 (13)	0.0360 (14)	0.0363 (13)	0.0039 (11)	−0.0021 (10)	0.0064 (11)
C56	0.0370 (12)	0.0358 (13)	0.0294 (12)	0.0011 (11)	0.0034 (10)	0.0001 (10)

Geometric parameters (Å, º)

O1—C2	1.343 (3)	N11—H11	0.8800
O1—C5	1.444 (3)	N12—C13	1.324 (3)
C2—O2	1.232 (3)	C13—C14	1.394 (3)
C2—C3	1.413 (3)	C14—C15	1.371 (3)
C3—C6	1.369 (3)	C15—N11	1.340 (2)
C3—C4	1.488 (3)	C14—H14	0.9500
C4—C5	1.527 (3)	C15—C51	1.451 (3)
C4—H4A	0.9900	C51—C56	1.379 (3)
C4—H4B	0.9900	C51—C52	1.384 (3)
C5—H5A	0.9900	C52—C53	1.377 (3)
C5—H5B	0.9900	C52—H52	0.9500
C6—N7	1.338 (3)	C53—C54	1.366 (3)
C6—C61	1.484 (3)	C53—H53	0.9500
C61—H61A	0.9800	C54—C55	1.372 (3)
C61—H61B	0.9800	C54—H54	0.9500
C61—H61C	0.9800	C55—C56	1.376 (3)
N7—C13	1.380 (3)	C55—H55	0.9500
N7—H7	0.8800	C56—H56	0.9500
N11—N12	1.341 (2)
C2—O1—C5	109.89 (17)	C15—N11—N12	112.93 (17)
O2—C2—O1	119.42 (19)	C15—N11—H11	123.5
O2—C2—C3	129.5 (2)	N12—N11—H11	123.5
O1—C2—C3	111.1 (2)	C13—N12—N11	104.32 (16)
C6—C3—C2	123.1 (2)	N12—C13—N7	113.91 (18)
C6—C3—C4	127.50 (18)	N12—C13—C14	111.62 (19)
C2—C3—C4	109.43 (18)	N7—C13—C14	134.45 (19)
C3—C4—C5	102.06 (18)	C15—C14—C13	104.84 (18)
C3—C4—H4A	111.4	C15—C14—H14	127.6
C5—C4—H4A	111.4	C13—C14—H14	127.6
C3—C4—H4B	111.4	N11—C15—C14	106.29 (18)
C5—C4—H4B	111.4	N11—C15—C51	121.66 (18)
H4A—C4—H4B	109.2	C14—C15—C51	132.04 (19)
O1—C5—C4	107.46 (18)	C56—C51—C52	118.0 (2)
O1—C5—H5A	110.2	C56—C51—C15	121.50 (19)
C4—C5—H5A	110.2	C52—C51—C15	120.51 (19)
O1—C5—H5B	110.2	C53—C52—C51	120.7 (2)
C4—C5—H5B	110.2	C53—C52—H52	119.6
H5A—C5—H5B	108.5	C51—C52—H52	119.6
N7—C6—C3	119.55 (18)	C54—C53—C52	120.5 (2)
N7—C6—C61	118.72 (18)	C54—C53—H53	119.7
C3—C6—C61	121.72 (19)	C52—C53—H53	119.7
C6—C61—H61A	109.5	C53—C54—C55	119.4 (2)
C6—C61—H61B	109.5	C53—C54—H54	120.3
H61A—C61—H61B	109.5	C55—C54—H54	120.3
C6—C61—H61C	109.5	C54—C55—C56	120.2 (2)
H61A—C61—H61C	109.5	C54—C55—H55	119.9
H61B—C61—H61C	109.5	C56—C55—H55	119.9
C6—N7—C13	131.88 (17)	C55—C56—C51	121.1 (2)
C6—N7—H7	114.1	C55—C56—H56	119.4
C13—N7—H7	114.1	C51—C56—H56	119.4
C5—O1—C2—O2	−177.4 (2)	C6—N7—C13—C14	6.1 (4)
C5—O1—C2—C3	2.7 (2)	N12—C13—C14—C15	−0.1 (2)
O2—C2—C3—C6	−2.8 (4)	N7—C13—C14—C15	178.4 (2)
O1—C2—C3—C6	177.02 (19)	N12—N11—C15—C14	0.3 (2)
O2—C2—C3—C4	178.5 (2)	N12—N11—C15—C51	−178.84 (17)
O1—C2—C3—C4	−1.6 (2)	C13—C14—C15—N11	−0.1 (2)
C6—C3—C4—C5	−178.6 (2)	C13—C14—C15—C51	178.9 (2)
C2—C3—C4—C5	−0.1 (2)	N11—C15—C51—C56	−16.1 (3)
C2—O1—C5—C4	−2.7 (2)	C14—C15—C51—C56	165.1 (2)
C3—C4—C5—O1	1.6 (2)	N11—C15—C51—C52	162.8 (2)
C2—C3—C6—N7	1.8 (3)	C14—C15—C51—C52	−16.1 (3)
C4—C3—C6—N7	−179.9 (2)	C56—C51—C52—C53	1.9 (3)
C2—C3—C6—C61	−177.1 (2)	C15—C51—C52—C53	−177.0 (2)
C4—C3—C6—C61	1.2 (3)	C51—C52—C53—C54	−1.0 (4)
C3—C6—N7—C13	179.6 (2)	C52—C53—C54—C55	−0.4 (4)
C61—C6—N7—C13	−1.5 (3)	C53—C54—C55—C56	0.7 (4)
C15—N11—N12—C13	−0.3 (2)	C54—C55—C56—C51	0.3 (3)
N11—N12—C13—N7	−178.57 (16)	C52—C51—C56—C55	−1.6 (3)
N11—N12—C13—C14	0.3 (2)	C15—C51—C56—C55	177.4 (2)
C6—N7—C13—N12	−175.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O2	0.88	1.97	2.709 (2)	141
N11—H11···O2^i	0.88	1.97	2.784 (2)	154

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

(II) (3Z)-3-{1-[(5-methyl-1H-pyrazol-3-yl)amino]ethylidene}-4,5- dihydrofuran-2(3H)-one–6-(2-hydroxyethyl)-2,5- dimethylpyrazolo[1,5-a]pyrimidin-7(4H)-one (1/1)

Crystal data

C10H13N3O2·C10H13N3O2	Z = 2
Mr = 414.46	F(000) = 440
Triclinic, P1	Dx = 1.401 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0402 (11) Å	Cell parameters from 3857 reflections
b = 8.2025 (17) Å	θ = 2.7–26.1°
c = 15.348 (3) Å	µ = 0.10 mm^−1
α = 91.999 (14)°	T = 120 K
β = 99.785 (12)°	Block, colourless
γ = 99.172 (15)°	0.38 × 0.23 × 0.16 mm
V = 982.7 (3) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	3857 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2739 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 9.091 pixels mm^-1	θmax = 26.1°, θmin = 2.7°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
Tmin = 0.963, Tmax = 0.984	l = −18→18
21688 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.123	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0572P)^2 + 0.4084P] where P = (Fo^2 + 2Fc^2)/3
3857 reflections	(Δ/σ)max = 0.001
275 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.9005 (2)	0.1184 (2)	0.36250 (10)	0.0249 (4)
C12	1.0571 (3)	0.0890 (2)	0.36009 (13)	0.0244 (4)
C13	1.1747 (3)	0.1491 (2)	0.43683 (13)	0.0249 (4)
H13	1.2929	0.1414	0.4499	0.030*
C13A	1.0813 (2)	0.2210 (2)	0.48849 (12)	0.0217 (4)
N14	1.1170 (2)	0.30378 (19)	0.56890 (10)	0.0231 (4)
H14	1.2225	0.3127	0.5982	0.028*
C15	0.9955 (2)	0.3690 (2)	0.60250 (12)	0.0223 (4)
C16	0.8319 (2)	0.3509 (2)	0.55720 (13)	0.0237 (4)
C17	0.7841 (2)	0.2612 (2)	0.47338 (13)	0.0236 (4)
N17A	0.9174 (2)	0.20143 (19)	0.44295 (10)	0.0217 (4)
C121	1.0913 (3)	0.0033 (3)	0.28026 (13)	0.0310 (5)
H12A	0.9833	−0.0341	0.2393	0.046*
H12B	1.1455	−0.0924	0.2974	0.046*
H12C	1.1679	0.0796	0.2512	0.046*
C151	1.0544 (3)	0.4591 (3)	0.69134 (13)	0.0275 (5)
H15A	1.1753	0.4528	0.7120	0.041*
H15B	0.9859	0.4085	0.7334	0.041*
H15C	1.0407	0.5753	0.6869	0.041*
C161	0.6935 (2)	0.4238 (3)	0.59071 (13)	0.0256 (5)
H16A	0.6182	0.4613	0.5401	0.031*
H16B	0.7460	0.5218	0.6313	0.031*
C162	0.5871 (2)	0.3018 (3)	0.63883 (14)	0.0258 (5)
H16C	0.5456	0.1986	0.6007	0.031*
H16D	0.6597	0.2742	0.6933	0.031*
O16	0.44467 (16)	0.36457 (17)	0.66201 (9)	0.0270 (3)
H16	0.4797	0.4536	0.6957	0.041*
O17	0.64014 (17)	0.23687 (19)	0.42772 (9)	0.0319 (4)
O21	0.92873 (18)	0.16357 (17)	0.97582 (9)	0.0295 (3)
C22	0.8563 (2)	0.2870 (2)	0.93740 (14)	0.0243 (4)
C23	0.8047 (2)	0.3886 (2)	1.00196 (13)	0.0235 (4)
C24	0.8599 (3)	0.3285 (3)	1.09152 (13)	0.0264 (5)
H24A	0.7641	0.3109	1.1249	0.032*
H24B	0.9563	0.4070	1.1266	0.032*
C25	0.9152 (3)	0.1659 (3)	1.06832 (14)	0.0311 (5)
H25A	1.0269	0.1577	1.1051	0.037*
H25B	0.8296	0.0714	1.0793	0.037*
O22	0.84505 (18)	0.29913 (17)	0.85764 (9)	0.0285 (3)
C26	0.7314 (2)	0.5236 (2)	0.98163 (13)	0.0233 (4)
C261	0.6909 (3)	0.6317 (3)	1.05154 (13)	0.0282 (5)
H26A	0.6896	0.5724	1.1058	0.042*
H26B	0.5783	0.6625	1.0318	0.042*
H26C	0.7780	0.7318	1.0633	0.042*
N27	0.6965 (2)	0.5611 (2)	0.89575 (11)	0.0253 (4)
H27	0.7340	0.4987	0.8582	0.030*
N31	0.4713 (2)	0.7896 (2)	0.75191 (11)	0.0263 (4)
H31	0.4145	0.8030	0.6991	0.032*
N32	0.5371 (2)	0.6517 (2)	0.77339 (11)	0.0266 (4)
C33	0.6110 (2)	0.6823 (2)	0.85791 (13)	0.0236 (4)
C34	0.5931 (2)	0.8381 (2)	0.88960 (13)	0.0248 (4)
H34	0.6351	0.8887	0.9475	0.030*
C35	0.5016 (2)	0.9032 (2)	0.81927 (13)	0.0247 (4)
C351	0.4410 (3)	1.0634 (3)	0.81029 (15)	0.0313 (5)
H35A	0.3677	1.0630	0.7523	0.047*
H35B	0.5395	1.1528	0.8155	0.047*
H35C	0.3754	1.0808	0.8571	0.047*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0298 (9)	0.0260 (9)	0.0201 (9)	0.0066 (7)	0.0064 (7)	−0.0006 (7)
C12	0.0301 (11)	0.0209 (10)	0.0251 (11)	0.0079 (9)	0.0088 (9)	0.0058 (8)
C13	0.0239 (10)	0.0260 (11)	0.0264 (11)	0.0074 (9)	0.0056 (8)	0.0033 (9)
C13A	0.0234 (10)	0.0214 (10)	0.0210 (10)	0.0045 (8)	0.0044 (8)	0.0040 (8)
N14	0.0208 (8)	0.0261 (9)	0.0230 (9)	0.0065 (7)	0.0034 (7)	0.0021 (7)
C15	0.0270 (10)	0.0193 (10)	0.0216 (10)	0.0037 (8)	0.0065 (8)	0.0049 (8)
C16	0.0272 (10)	0.0242 (10)	0.0216 (10)	0.0060 (9)	0.0076 (8)	0.0047 (8)
C17	0.0235 (10)	0.0273 (11)	0.0220 (10)	0.0075 (9)	0.0060 (8)	0.0064 (8)
N17A	0.0244 (9)	0.0236 (9)	0.0184 (8)	0.0063 (7)	0.0051 (7)	0.0008 (7)
C121	0.0378 (12)	0.0337 (12)	0.0251 (11)	0.0129 (10)	0.0096 (9)	0.0006 (9)
C151	0.0283 (11)	0.0294 (11)	0.0249 (11)	0.0037 (9)	0.0067 (9)	−0.0010 (9)
C161	0.0261 (10)	0.0275 (11)	0.0254 (11)	0.0098 (9)	0.0056 (8)	0.0025 (9)
C162	0.0223 (10)	0.0280 (11)	0.0297 (11)	0.0090 (9)	0.0078 (8)	0.0019 (9)
O16	0.0202 (7)	0.0296 (8)	0.0314 (8)	0.0057 (6)	0.0055 (6)	−0.0070 (6)
O17	0.0239 (8)	0.0478 (10)	0.0245 (8)	0.0100 (7)	0.0021 (6)	0.0005 (7)
O21	0.0348 (8)	0.0268 (8)	0.0284 (8)	0.0089 (6)	0.0062 (6)	0.0028 (6)
C22	0.0195 (10)	0.0227 (11)	0.0292 (11)	0.0003 (8)	0.0029 (8)	0.0019 (9)
C23	0.0202 (10)	0.0255 (11)	0.0232 (10)	0.0003 (8)	0.0027 (8)	−0.0006 (8)
C24	0.0248 (10)	0.0297 (11)	0.0238 (11)	0.0016 (9)	0.0041 (8)	0.0035 (9)
C25	0.0344 (12)	0.0301 (12)	0.0275 (11)	0.0012 (9)	0.0049 (9)	0.0055 (9)
O22	0.0341 (8)	0.0291 (8)	0.0228 (8)	0.0063 (6)	0.0059 (6)	−0.0011 (6)
C26	0.0169 (9)	0.0276 (11)	0.0237 (10)	−0.0009 (8)	0.0034 (8)	−0.0010 (8)
C261	0.0277 (11)	0.0315 (12)	0.0258 (11)	0.0075 (9)	0.0040 (9)	−0.0002 (9)
N27	0.0275 (9)	0.0269 (9)	0.0227 (9)	0.0077 (7)	0.0052 (7)	−0.0001 (7)
N31	0.0276 (9)	0.0271 (9)	0.0237 (9)	0.0071 (8)	0.0010 (7)	0.0014 (7)
N32	0.0283 (9)	0.0268 (9)	0.0249 (9)	0.0083 (8)	0.0026 (7)	0.0002 (7)
C33	0.0193 (10)	0.0275 (11)	0.0238 (10)	0.0023 (8)	0.0046 (8)	0.0018 (8)
C34	0.0236 (10)	0.0252 (11)	0.0239 (11)	0.0009 (8)	0.0035 (8)	−0.0023 (8)
C35	0.0222 (10)	0.0240 (11)	0.0278 (11)	−0.0006 (8)	0.0088 (8)	0.0009 (8)
C351	0.0322 (12)	0.0261 (11)	0.0360 (12)	0.0032 (9)	0.0088 (10)	0.0024 (9)

Geometric parameters (Å, º)

N11—C12	1.325 (2)	O21—C22	1.351 (2)
C12—C13	1.399 (3)	O21—C25	1.442 (2)
C12—C121	1.479 (3)	C22—O22	1.221 (2)
C13—C13A	1.361 (3)	C22—C23	1.429 (3)
C13—H13	0.9500	C23—C26	1.356 (3)
C13A—N14	1.351 (2)	C23—C24	1.496 (3)
N14—C15	1.351 (2)	C24—C25	1.521 (3)
N14—H14	0.8800	C24—H24A	0.9900
C15—C16	1.362 (3)	C24—H24B	0.9900
C15—C151	1.493 (3)	C25—H25A	0.9900
C16—C17	1.422 (3)	C25—H25B	0.9900
C16—C161	1.499 (3)	C26—N27	1.357 (2)
C17—N17A	1.389 (2)	C26—C261	1.479 (3)
N17A—N11	1.364 (2)	C261—H26A	0.9800
C13A—N17A	1.365 (2)	C261—H26B	0.9800
C17—O17	1.229 (2)	C261—H26C	0.9800
C121—H12A	0.9800	N27—C33	1.386 (2)
C121—H12B	0.9800	N27—H27	0.8800
C121—H12C	0.9800	N31—N32	1.351 (2)
C151—H15A	0.9800	N31—H31	0.8800
C151—H15B	0.9800	N32—C33	1.329 (3)
C151—H15C	0.9800	C33—C34	1.389 (3)
C161—C162	1.508 (3)	C34—C35	1.374 (3)
C161—H16A	0.9900	C35—N31	1.331 (3)
C161—H16B	0.9900	C34—H34	0.9500
C162—O16	1.420 (2)	C35—C351	1.476 (3)
C162—H16C	0.9900	C351—H35A	0.9800
C162—H16D	0.9900	C351—H35B	0.9800
O16—H16	0.8600	C351—H35C	0.9800
C12—N11—N17A	103.52 (16)	C22—O21—C25	109.65 (15)
N11—C12—C13	113.19 (17)	O22—C22—O21	119.58 (18)
N11—C12—C121	119.53 (18)	O22—C22—C23	129.65 (18)
C13—C12—C121	127.27 (18)	O21—C22—C23	110.76 (17)
C13A—C13—C12	104.29 (17)	C26—C23—C22	123.07 (18)
C13A—C13—H13	127.9	C26—C23—C24	128.30 (18)
C12—C13—H13	127.9	C22—C23—C24	108.40 (17)
N14—C13A—C13	134.67 (18)	C23—C24—C25	102.06 (16)
N14—C13A—N17A	118.01 (16)	C23—C24—H24A	111.4
C13—C13A—N17A	107.31 (17)	C25—C24—H24A	111.4
C13A—N14—C15	121.18 (16)	C23—C24—H24B	111.4
C13A—N14—H14	117.0	C25—C24—H24B	111.4
C15—N14—H14	121.8	H24A—C24—H24B	109.2
N14—C15—C16	121.14 (18)	O21—C25—C24	107.28 (16)
N14—C15—C151	115.15 (17)	O21—C25—H25A	110.3
C16—C15—C151	123.71 (18)	C24—C25—H25A	110.3
C15—C16—C17	120.70 (18)	O21—C25—H25B	110.3
C15—C16—C161	123.19 (18)	C24—C25—H25B	110.3
C17—C16—C161	116.11 (17)	H25A—C25—H25B	108.5
O17—C17—N17A	119.91 (18)	C23—C26—N27	119.41 (18)
O17—C17—C16	125.70 (18)	C23—C26—C261	121.15 (18)
N17A—C17—C16	114.38 (17)	N27—C26—C261	119.43 (17)
N11—N17A—C13A	111.70 (15)	C26—C261—H26A	109.5
N11—N17A—C17	123.74 (16)	C26—C261—H26B	109.5
C13A—N17A—C17	124.54 (16)	H26A—C261—H26B	109.5
C12—C121—H12A	109.5	C26—C261—H26C	109.5
C12—C121—H12B	109.5	H26A—C261—H26C	109.5
H12A—C121—H12B	109.5	H26B—C261—H26C	109.5
C12—C121—H12C	109.5	C26—N27—C33	130.19 (17)
H12A—C121—H12C	109.5	C26—N27—H27	114.9
H12B—C121—H12C	109.5	C33—N27—H27	114.9
C15—C151—H15A	109.5	C35—N31—N32	112.72 (16)
C15—C151—H15B	109.5	C35—N31—H31	123.6
H15A—C151—H15B	109.5	N32—N31—H31	123.6
C15—C151—H15C	109.5	C33—N32—N31	104.27 (16)
H15A—C151—H15C	109.5	N32—C33—N27	116.05 (18)
H15B—C151—H15C	109.5	N32—C33—C34	111.33 (18)
C16—C161—C162	112.21 (16)	N27—C33—C34	132.52 (18)
C16—C161—H16A	109.2	C35—C34—C33	105.15 (18)
C162—C161—H16A	109.2	C35—C34—H34	127.4
C16—C161—H16B	109.2	C33—C34—H34	127.4
C162—C161—H16B	109.2	N31—C35—C34	106.53 (17)
H16A—C161—H16B	107.9	N31—C35—C351	121.70 (18)
O16—C162—C161	112.20 (16)	C34—C35—C351	131.77 (19)
O16—C162—H16C	109.2	C35—C351—H35A	109.5
C161—C162—H16C	109.2	C35—C351—H35B	109.5
O16—C162—H16D	109.2	H35A—C351—H35B	109.5
C161—C162—H16D	109.2	C35—C351—H35C	109.5
H16C—C162—H16D	107.9	H35A—C351—H35C	109.5
C162—O16—H16	109.8	H35B—C351—H35C	109.5
N17A—N11—C12—C13	0.5 (2)	C17—C16—C161—C162	85.3 (2)
N17A—N11—C12—C121	−178.29 (17)	C16—C161—C162—O16	−173.50 (16)
N11—C12—C13—C13A	−0.6 (2)	C25—O21—C22—O22	−175.33 (18)
C121—C12—C13—C13A	178.13 (19)	C25—O21—C22—C23	5.5 (2)
C12—C13—C13A—N14	−178.4 (2)	O22—C22—C23—C26	−0.5 (3)
C12—C13—C13A—N17A	0.3 (2)	O21—C22—C23—C26	178.64 (18)
C13—C13A—N14—C15	177.0 (2)	O22—C22—C23—C24	−175.4 (2)
N17A—C13A—N14—C15	−1.7 (3)	O21—C22—C23—C24	3.7 (2)
C13A—N14—C15—C16	1.3 (3)	C26—C23—C24—C25	174.9 (2)
C13A—N14—C15—C151	−179.10 (17)	C22—C23—C24—C25	−10.4 (2)
N14—C15—C16—C17	0.6 (3)	C22—O21—C25—C24	−12.2 (2)
C151—C15—C16—C17	−178.99 (18)	C23—C24—C25—O21	13.5 (2)
N14—C15—C16—C161	−178.69 (17)	C22—C23—C26—N27	3.5 (3)
C151—C15—C16—C161	1.7 (3)	C24—C23—C26—N27	177.42 (18)
C15—C16—C17—O17	179.45 (19)	C22—C23—C26—C261	−175.78 (18)
C161—C16—C17—O17	−1.2 (3)	C24—C23—C26—C261	−1.8 (3)
C15—C16—C17—N17A	−1.9 (3)	C23—C26—N27—C33	174.17 (19)
C161—C16—C17—N17A	177.45 (16)	C261—C26—N27—C33	−6.5 (3)
C12—N11—N17A—C13A	−0.3 (2)	C35—N31—N32—C33	0.1 (2)
C12—N11—N17A—C17	178.48 (17)	N31—N32—C33—N27	−177.14 (16)
N14—C13A—N17A—N11	178.95 (16)	N31—N32—C33—C34	−0.3 (2)
C13—C13A—N17A—N11	−0.1 (2)	C26—N27—C33—N32	−154.14 (19)
N14—C13A—N17A—C17	0.2 (3)	C26—N27—C33—C34	29.9 (3)
C13—C13A—N17A—C17	−178.79 (17)	N32—C33—C34—C35	0.4 (2)
O17—C17—N17A—N11	1.7 (3)	N27—C33—C34—C35	176.6 (2)
C16—C17—N17A—N11	−177.07 (16)	N32—N31—C35—C34	0.2 (2)
O17—C17—N17A—C13A	−179.74 (18)	N32—N31—C35—C351	−179.95 (17)
C16—C17—N17A—C13A	1.5 (3)	C33—C34—C35—N31	−0.3 (2)
C15—C16—C161—C162	−95.4 (2)	C33—C34—C35—C351	179.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O16—H16···N32	0.86	1.93	2.784 (2)	175
N27—H27···O22	0.88	1.99	2.712 (2)	139
N14—H14···O16^i	0.88	1.86	2.736 (2)	172
N31—H31···O17^ii	0.88	1.93	2.740 (2)	153

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