Pyrazolidine-3,5-dione angiotensin-II receptor antagonists

The crystal structures of three angiotensin-II receptor antagonists involving different spacer groups (CO, CONH and NHCO) between the aryl rings are presented, namely 2-{4-[(3-butyl-1,4-dioxo-2,3-di­aza­spiro­[4.4]­non-2-yl)­methyl]­benzoyl}benzoic acid, C₂₆H₂₈N₂O₅, (I), 2-{4-[(3-butyl-1,4-dioxo-2,3-di­aza­spiro­[4.4]­non-2-yl)­methyl]­benz­amido}benzoic acid, C₂₆H₂₉N₃O₅, (II), and 2-{4-[(3-butyl-1,4-dioxo-2,3-di­azaspiro­[4.4]­non-2-yl)­methyl]­anilino­carbonyl}benzoic acid monohydrate, C₂₆H₂₉N₃O₅·H₂O, (III). The aryl rings of (II) are almost coplanar, in contrast with compounds (I) and (III). The conformation of (II) is induced by an intramolecular N—H...O hydrogen bond between the amide and carboxyl­ic acid groups.

S1. Comment

The renin-angiotensin system (RAS) plays an important role in the regulation of blood pressure and electrolyte balance. Non-peptide AT1-selective angiotensin-II receptor antagonists which block the RAS are of great interest in the treatment of hypertension and other cardiovascular diseases (Wexler et al., 1996). Recently, we reported new pyrazolidine-3,5-dione derivatives displaying AT1-binding affinity (Le Bourdonnec et al., 2000). In this paper, we compare the X-ray structures of three compounds from this series, (I), (II) and (III), involving different spacer groups between the two aryl rings. \sch

The atom-numbering schemes and molecular conformations adopted by the compounds (I), (II) and (III) are depicted in Figs. 1, 2 and 3, respectively. For each compound, the pyrazolidine-3,5-dione heterocycle is almost planar. The displacement of the atoms from their mean plane does not exceed 0.096 Å. The C24 and C6 substituents deviate from that plane by a distance ranging from 0.35 to 0.78 Å. In (III), the terminal part of the butyl chain and the spiropentyl groups are disordered. Two orientations were found for these moieties, with occupancy factors of 0.57 and 0.43 for C26—C27 and C26'-C27', and 0.63 and 0.37 for C29—C30 and C29'-C30'.

The three compounds present some differences in the conformation of the Ph—X-PhCO₂H_ortho moiety. Indeed, the orientation of the central aryl ring (C7/C8/C9/C10/C11/C12) is quite different for (I) when compared with the other two. The N1—C6—C7—C8 torsion angle is -2.6 (3), -78.4 (3) and -98.4 (2)° for (I), (II) and (III), respectively. Furthermore, the angle between the planes of the two aryl rings varies depending on the nature of the linkage (carbonyl, amide or retroamide). In compound (I), the two rings form a dihedral angle of 82.8 (1)°, with the carbonyl function almost in the same plane as the central aryl ring [C11—C10—C34—O35 - 10.5 (3)°]. In (II), the two phenyl rings are twisted slightly from coplanarity [dihedral angle between the planes 32.3 (1)°], whereas in (III), they are distorted by 88.0 (1)°. In fact, for these two latter derivatives, the amide function is in the same plane as the central aryl ring [the dihedral angle between the planes is 11.5 (5)° for (II) and 10.5 (2)° for (III)].

There is a difference in the orientation of the terminal phenyl ring (C13/C14/C15/C16/C17/C18) with respect to the amide function. In (II), the aryl and amide moieties are almost coplanar [dihedral angle 21.1 (4)°]. This conformation is stabilized by an intramolecular hydrogen bond between the amide and the carboxylic acid moieties (N36—H36···O21; Table 2). In (III), this intramolecular hydrogen bond is not present and the terminal aryl ring is perpendicular to the retroamide group [dihedral angle 81.7 (1)°]. For all three derivatives, the carboxylic acid function is almost coplanar with the corresponding phenyl ring, with torsion angles C13—C14—C19—O21 of 3.7 (3), -12.1 (5) and 4.9 (3)° for (I), (II) and (III), respectively. The C14—C19 distances, ranging from 1.480 to 1.489 Å, are shorter than common single bonds, indicative of a delocalization between the two groups.

In addition to the intramolecular hydrogen bond observed in (II), some intermolecular donor-acceptor interactions are also found for the three derivatives; details of these are given in Tables 1, 2 and 3. For (I) and (II), the carboxylic acid group is involved in a hydrogen bond with the O33 acceptor atom (O20—H20···O33; Tables 1 and 2). For compound (III), the co-crystallized water molecule is involved in the hydrogen-bonding pattern. It interacts as a double H-donor with the pyrazolidine-3,5-dione heterocycle (O37—H37A···O33 and O37—H37B···O32, Table 3) and as an H-acceptor with the carboxylic acid moiety (O20—H20···O37, Table 3). Furthermore, an intermolecular hydrogen bond exists between the amide functions (N36—H36···O35, Table 3).

Related literature

For related literature, see: Le Bourdonnec, Meulon, Yous, Goossens, Houssin & Hénichart (2000); Sheldrick (1997); Wexler et al. (1996).

S2. Experimental

The synthesis of compounds (I), (II) and (III) has been reported previously by Le Bourdonnec et al. (2000). Crystals were obtained by slow evaporation of an isooctane-ethyl acetate solution for (I), a toluene-ethyl acetate solution for (II) and an ethyl acetate solution (III), at room temperature.

S3. Refinement

H atoms attached to C were treated as riding using the SHELXL97 (Sheldrick, 1997) defaults, whereas the N—H and O—H atoms were refined on position and with isotropic displacement parameters.

Computing details

For all compounds, data collection: CAD-4 EXPRESS (Enraf-Nonius, 1992); cell refinement: CAD-4 EXPRESS; data reduction: PLATON (Spek, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON; software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular view of compound (I), with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.
	Fig. 2. The molecular view of compound (II), with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.
	Fig. 3. The molecular view of compound (III), with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii. Only one conformation of the terminal part of the alkyl chain (C26–27) and the spiropentyl group (C29—C30) is shown.

(I) 2-{4-[(3-butyl-1,4-dioxo-2,3-diazaspiro[4.4]non-2-yl)methyl]benzoyl}benzoic acid

Crystal data

C26H28N2O5	Z = 2
Mr = 448.50	F(000) = 476
Triclinic, P1	Dx = 1.295 Mg m^−3
a = 10.530 (1) Å	Cu Kα radiation, λ = 1.54178 Å
b = 11.469 (1) Å	Cell parameters from 25 reflections
c = 11.491 (1) Å	θ = 40–50°
α = 109.589 (8)°	µ = 0.73 mm^−1
β = 112.690 (8)°	T = 293 K
γ = 97.640 (9)°	Block, colourless
V = 1150.02 (18) Å^3	0.31 × 0.29 × 0.23 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	3537 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 71.9°, θmin = 4.3°
θ/2θ scans	h = −12→12
Absorption correction: ψ-scan (North et al., 1968)	k = 0→14
Tmin = 0.804, Tmax = 0.849	l = −14→13
4750 measured reflections	3 standard reflections every 200 reflections
4511 independent reflections	intensity decay: 2%

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0781P)^2 + 0.3037P] where P = (Fo^2 + 2Fc^2)/3
4511 reflections	(Δ/σ)max = 0.002
302 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.28 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.

# Data for C—H···O interactions # # For Instance, # # Compound (I): # C(6)—H(6 A)···O(21)i D—A= 3.0209 D—H···A=124.48 (i=2 - x,-y,2 - z) # C(9)—H(9)···O(32)ii D—A=3.1716 D—H···A=131.04 (ii=1 - x,-y,1 - z) # C(12)—H(12)···O(21)i D—A=3.2667 D—H···A=135.52 (i=2 - x,-y,2 - z) # C(28)—H(28B)···O(32)ii D—A=3.3832 D—H···A=143.77 (ii=1 - x,-y,1 - z) # # Compound (II): # C(12)—H(12)···O(35)i D—A=3.1459 D—H···A=125.89 (i=1 - x,1/2 + y,1/2 - z) # # But I have decided not to focus on the C—H···O interactions in this paper, # the main aim being to compare the relative orientation of the aromatic rings # depending on the spacer group used. #

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
N1	0.72722 (16)	0.26599 (15)	0.84015 (15)	0.0503 (4)
N2	0.59599 (16)	0.16468 (15)	0.77948 (15)	0.0507 (4)
O20	0.83499 (18)	−0.50818 (15)	0.58895 (17)	0.0691 (4)
O21	0.9737 (2)	−0.31438 (15)	0.75704 (15)	0.0806 (5)
O32	0.37165 (16)	0.10416 (15)	0.59768 (16)	0.0702 (4)
O33	0.82428 (18)	0.41119 (16)	0.78013 (17)	0.0710 (4)
O35	1.22986 (17)	−0.12416 (17)	0.78133 (18)	0.0868 (6)
C3	0.4987 (2)	0.16936 (18)	0.66293 (19)	0.0528 (4)
C4	0.5753 (2)	0.26530 (18)	0.63038 (19)	0.0518 (4)
C5	0.7218 (2)	0.32541 (18)	0.7557 (2)	0.0523 (4)
C6	0.8609 (2)	0.2599 (2)	0.93987 (19)	0.0552 (5)
C7	0.91829 (19)	0.15374 (17)	0.87804 (18)	0.0458 (4)
C8	0.8476 (2)	0.06586 (18)	0.73994 (19)	0.0520 (4)
C9	0.90627 (19)	−0.02782 (18)	0.68734 (19)	0.0499 (4)
C10	1.03793 (18)	−0.03457 (17)	0.77244 (19)	0.0476 (4)
C11	1.1093 (2)	0.05371 (19)	0.91154 (19)	0.0542 (5)
C12	1.0504 (2)	0.14596 (19)	0.96411 (19)	0.0529 (4)
C13	1.01546 (19)	−0.23084 (18)	0.56600 (19)	0.0502 (4)
C14	0.92682 (19)	−0.35290 (18)	0.52749 (18)	0.0481 (4)
C15	0.8484 (2)	−0.4396 (2)	0.3873 (2)	0.0574 (5)
C16	0.8570 (2)	−0.4038 (2)	0.2868 (2)	0.0664 (6)
C17	0.9430 (3)	−0.2832 (3)	0.3244 (2)	0.0685 (6)
C18	1.0232 (2)	−0.1975 (2)	0.4630 (2)	0.0626 (5)
C19	0.9153 (2)	−0.38852 (18)	0.6366 (2)	0.0519 (4)
C24	0.5589 (2)	0.1155 (2)	0.8676 (2)	0.0597 (5)
C25	0.5446 (3)	0.2153 (2)	0.9840 (2)	0.0683 (6)
C26	0.4273 (3)	0.2748 (3)	0.9363 (3)	0.0742 (6)
C27	0.4133 (4)	0.3697 (3)	1.0567 (3)	0.0941 (8)
C28	0.5888 (3)	0.1963 (2)	0.4951 (2)	0.0684 (6)
C29	0.4990 (4)	0.2386 (4)	0.3918 (3)	0.1090 (12)
C30	0.4234 (4)	0.3179 (3)	0.4467 (3)	0.1056 (11)
C31	0.4922 (3)	0.3618 (2)	0.6003 (2)	0.0683 (6)
C34	1.1048 (2)	−0.13075 (19)	0.7155 (2)	0.0546 (5)
H6A	0.8445	0.2469	1.0127	0.066*
H6B	0.9342	0.3429	0.9828	0.066*
H8	0.7594	0.0694	0.6812	0.062*
H9	0.8567	−0.0865	0.5941	0.060*
H11	1.1979	0.0506	0.9700	0.065*
H12	1.0992	0.2035	1.0578	0.063*
H15	0.7904	−0.5214	0.3616	0.069*
H16	0.8045	−0.4614	0.1933	0.080*
H17	0.9473	−0.2591	0.2561	0.082*
H18	1.0829	−0.1168	0.4874	0.075*
H20	0.838 (3)	−0.535 (3)	0.655 (3)	0.104 (10)*
H24A	0.6323	0.0783	0.9083	0.072*
H24B	0.4682	0.0461	0.8094	0.072*
H25A	0.5265	0.1744	1.0398	0.082*
H25B	0.6358	0.2840	1.0434	0.082*
H26A	0.3362	0.2065	0.8740	0.089*
H26B	0.4473	0.3199	0.8844	0.089*
H27A	0.3371	0.4052	1.0213	0.141*
H27B	0.5026	0.4385	1.1176	0.141*
H27C	0.3915	0.3251	1.1072	0.141*
H28A	0.6886	0.2210	0.5132	0.082*
H28B	0.5546	0.1028	0.4612	0.082*
H29A	0.5599	0.2874	0.3681	0.131*
H29B	0.4302	0.1631	0.3076	0.131*
H30A	0.3228	0.2686	0.4056	0.127*
H30B	0.4277	0.3925	0.4247	0.127*
H31A	0.4194	0.3607	0.6324	0.082*
H31B	0.5578	0.4493	0.6470	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0506 (8)	0.0512 (8)	0.0451 (8)	0.0209 (7)	0.0158 (7)	0.0211 (7)
N2	0.0503 (8)	0.0521 (8)	0.0463 (8)	0.0201 (7)	0.0161 (7)	0.0226 (7)
O20	0.0770 (10)	0.0649 (9)	0.0631 (9)	0.0124 (8)	0.0300 (8)	0.0307 (8)
O21	0.1244 (14)	0.0620 (9)	0.0471 (8)	0.0262 (9)	0.0316 (9)	0.0238 (7)
O32	0.0561 (8)	0.0680 (9)	0.0635 (9)	0.0178 (7)	0.0078 (7)	0.0254 (7)
O33	0.0750 (10)	0.0686 (9)	0.0710 (10)	0.0164 (8)	0.0322 (8)	0.0348 (8)
O35	0.0555 (9)	0.0882 (12)	0.0794 (11)	0.0383 (8)	0.0086 (8)	0.0137 (9)
C3	0.0573 (11)	0.0500 (10)	0.0447 (9)	0.0269 (8)	0.0153 (8)	0.0183 (8)
C4	0.0649 (11)	0.0498 (10)	0.0444 (9)	0.0319 (9)	0.0222 (8)	0.0221 (8)
C5	0.0616 (11)	0.0496 (10)	0.0504 (10)	0.0263 (9)	0.0273 (9)	0.0213 (8)
C6	0.0508 (10)	0.0615 (11)	0.0422 (9)	0.0236 (9)	0.0124 (8)	0.0176 (8)
C7	0.0457 (9)	0.0482 (9)	0.0439 (9)	0.0161 (7)	0.0183 (7)	0.0219 (7)
C8	0.0451 (9)	0.0546 (10)	0.0464 (9)	0.0206 (8)	0.0113 (8)	0.0196 (8)
C9	0.0460 (9)	0.0465 (9)	0.0450 (9)	0.0153 (7)	0.0119 (7)	0.0161 (7)
C10	0.0425 (9)	0.0465 (9)	0.0504 (10)	0.0138 (7)	0.0160 (7)	0.0230 (8)
C11	0.0440 (9)	0.0609 (11)	0.0479 (10)	0.0199 (8)	0.0106 (8)	0.0232 (9)
C12	0.0495 (10)	0.0594 (11)	0.0400 (9)	0.0179 (8)	0.0126 (8)	0.0187 (8)
C13	0.0467 (9)	0.0548 (10)	0.0534 (10)	0.0258 (8)	0.0224 (8)	0.0246 (8)
C14	0.0473 (9)	0.0543 (10)	0.0471 (9)	0.0254 (8)	0.0219 (8)	0.0225 (8)
C15	0.0569 (11)	0.0590 (11)	0.0507 (10)	0.0207 (9)	0.0226 (9)	0.0186 (9)
C16	0.0687 (13)	0.0788 (15)	0.0477 (11)	0.0253 (11)	0.0256 (10)	0.0227 (10)
C17	0.0735 (14)	0.0885 (16)	0.0623 (13)	0.0341 (12)	0.0381 (11)	0.0413 (12)
C18	0.0629 (12)	0.0660 (12)	0.0709 (13)	0.0251 (10)	0.0347 (11)	0.0358 (11)
C19	0.0561 (10)	0.0530 (10)	0.0500 (10)	0.0264 (9)	0.0227 (8)	0.0237 (8)
C24	0.0661 (12)	0.0593 (11)	0.0609 (12)	0.0255 (10)	0.0261 (10)	0.0347 (10)
C25	0.0725 (14)	0.0792 (15)	0.0583 (12)	0.0245 (12)	0.0308 (11)	0.0335 (11)
C26	0.0803 (15)	0.0774 (15)	0.0661 (13)	0.0305 (12)	0.0356 (12)	0.0269 (12)
C27	0.103 (2)	0.0919 (19)	0.0842 (18)	0.0361 (16)	0.0506 (16)	0.0217 (15)
C28	0.0931 (16)	0.0683 (13)	0.0513 (11)	0.0424 (12)	0.0353 (11)	0.0245 (10)
C29	0.108 (2)	0.183 (4)	0.0621 (15)	0.077 (2)	0.0406 (16)	0.066 (2)
C30	0.130 (3)	0.0799 (17)	0.0800 (18)	0.0537 (18)	0.0079 (17)	0.0429 (15)
C31	0.0822 (15)	0.0634 (12)	0.0757 (14)	0.0467 (11)	0.0362 (12)	0.0387 (11)
C34	0.0467 (10)	0.0547 (10)	0.0576 (11)	0.0215 (8)	0.0171 (8)	0.0241 (9)

Geometric parameters (Å, º)

N1—N2	1.426 (2)	C11—H11	0.9300
N1—C5	1.350 (2)	C8—H8	0.9300
N1—C6	1.461 (2)	C12—H12	0.9300
N2—C3	1.360 (2)	C18—C17	1.381 (3)
N2—C24	1.458 (2)	C18—H18	0.9300
O20—C19	1.315 (2)	C6—H6A	0.9700
O21—C19	1.196 (2)	C6—H6B	0.9700
O32—C3	1.223 (2)	C4—C31	1.546 (2)
O33—C5	1.228 (2)	C4—C28	1.561 (3)
O35—C34	1.216 (2)	C16—C17	1.372 (3)
O20—H20	0.90 (3)	C16—H16	0.9300
C3—C4	1.508 (3)	C25—C26	1.499 (3)
C7—C6	1.517 (3)	C25—H25A	0.9700
C7—C8	1.380 (2)	C25—H25B	0.9700
C7—C12	1.397 (2)	C17—H17	0.9300
C9—C8	1.389 (3)	C28—C29	1.476 (3)
C9—C10	1.385 (2)	C28—H28A	0.9700
C9—H9	0.9300	C28—H28B	0.9700
C10—C11	1.389 (3)	C31—C30	1.488 (4)
C10—C34	1.489 (3)	C31—H31A	0.9700
C13—C18	1.387 (3)	C31—H31B	0.9700
C13—C14	1.395 (3)	C26—C27	1.519 (3)
C13—C34	1.516 (3)	C26—H26A	0.9700
C15—C16	1.378 (3)	C26—H26B	0.9700
C15—C14	1.396 (3)	C30—C29	1.434 (4)
C15—H15	0.9300	C30—H30A	0.9700
C19—C14	1.484 (3)	C30—H30B	0.9700
C5—C4	1.505 (3)	C27—H27A	0.9600
C24—C25	1.515 (3)	C27—H27B	0.9600
C24—H24A	0.9700	C27—H27C	0.9600
C24—H24B	0.9700	C29—H29A	0.9700
C11—C12	1.380 (3)	C29—H29B	0.9700
C19—O20—H20	115 (2)	N1—C6—H6B	108.6
C3—N2—N1	109.28 (15)	C7—C6—H6B	108.6
C3—N2—C24	124.83 (17)	H6A—C6—H6B	107.6
N1—N2—C24	119.48 (15)	C5—C4—C3	102.61 (15)
C5—N1—N2	110.43 (15)	C5—C4—C31	115.30 (17)
C5—N1—C6	123.91 (17)	C3—C4—C31	112.62 (17)
N2—N1—C6	119.93 (15)	C5—C4—C28	110.62 (17)
C10—C9—C8	120.61 (17)	C3—C4—C28	111.63 (17)
C10—C9—H9	119.7	C31—C4—C28	104.30 (16)
C8—C9—H9	119.7	C17—C16—C15	120.1 (2)
C9—C10—C11	118.52 (17)	C17—C16—H16	120.0
C9—C10—C34	120.96 (17)	C15—C16—H16	120.0
C11—C10—C34	120.48 (16)	C26—C25—C24	114.60 (19)
O32—C3—N2	124.11 (19)	C26—C25—H25A	108.6
O32—C3—C4	127.51 (17)	C24—C25—H25A	108.6
N2—C3—C4	108.38 (17)	C26—C25—H25B	108.6
O21—C19—O20	123.28 (19)	C24—C25—H25B	108.6
O21—C19—C14	122.71 (19)	H25A—C25—H25B	107.6
O20—C19—C14	114.01 (17)	C16—C17—C18	120.5 (2)
C8—C7—C12	118.32 (16)	C16—C17—H17	119.7
C8—C7—C6	123.12 (16)	C18—C17—H17	119.7
C12—C7—C6	118.55 (16)	C29—C28—C4	106.50 (19)
C18—C13—C14	118.96 (18)	C29—C28—H28A	110.4
C18—C13—C34	117.38 (18)	C4—C28—H28A	110.4
C14—C13—C34	123.66 (17)	C29—C28—H28B	110.4
C16—C15—C14	120.0 (2)	C4—C28—H28B	110.4
C16—C15—H15	120.0	H28A—C28—H28B	108.6
C14—C15—H15	120.0	C30—C31—C4	106.15 (18)
O33—C5—N1	123.37 (18)	C30—C31—H31A	110.5
O33—C5—C4	128.08 (18)	C4—C31—H31A	110.5
N1—C5—C4	108.52 (17)	C30—C31—H31B	110.5
C13—C14—C15	119.99 (18)	C4—C31—H31B	110.5
C13—C14—C19	119.40 (17)	H31A—C31—H31B	108.7
C15—C14—C19	120.61 (18)	C25—C26—C27	112.4 (2)
N2—C24—C25	115.18 (17)	C25—C26—H26A	109.1
N2—C24—H24A	108.5	C27—C26—H26A	109.1
C25—C24—H24A	108.5	C25—C26—H26B	109.1
N2—C24—H24B	108.5	C27—C26—H26B	109.1
C25—C24—H24B	108.5	H26A—C26—H26B	107.9
H24A—C24—H24B	107.5	C29—C30—C31	108.6 (2)
C12—C11—C10	120.88 (16)	C29—C30—H30A	110.0
C12—C11—H11	119.6	C31—C30—H30A	110.0
C10—C11—H11	119.6	C29—C30—H30B	110.0
C7—C8—C9	121.01 (16)	C31—C30—H30B	110.0
C7—C8—H8	119.5	H30A—C30—H30B	108.3
C9—C8—H8	119.5	C26—C27—H27A	109.5
O35—C34—C10	121.94 (18)	C26—C27—H27B	109.5
O35—C34—C13	120.38 (18)	H27A—C27—H27B	109.5
C10—C34—C13	117.43 (15)	C26—C27—H27C	109.5
C11—C12—C7	120.66 (17)	H27A—C27—H27C	109.5
C11—C12—H12	119.7	H27B—C27—H27C	109.5
C7—C12—H12	119.7	C30—C29—C28	110.3 (2)
C17—C18—C13	120.4 (2)	C30—C29—H29A	109.6
C17—C18—H18	119.8	C28—C29—H29A	109.6
C13—C18—H18	119.8	C30—C29—H29B	109.6
N1—C6—C7	114.67 (15)	C28—C29—H29B	109.6
N1—C6—H6A	108.6	H29A—C29—H29B	108.1
C7—C6—H6A	108.6
C3—N2—N1—C5	−7.5 (2)	C18—C13—C34—C10	87.8 (2)
C24—N2—N1—C5	−160.70 (16)	C14—C13—C34—C10	−92.0 (2)
C3—N2—N1—C6	−161.83 (16)	C10—C11—C12—C7	−0.8 (3)
C24—N2—N1—C6	45.0 (2)	C8—C7—C12—C11	0.8 (3)
C8—C9—C10—C11	0.5 (3)	C6—C7—C12—C11	−177.88 (18)
C8—C9—C10—C34	−177.18 (18)	C14—C13—C18—C17	0.8 (3)
N1—N2—C3—O32	−171.43 (18)	C34—C13—C18—C17	−179.01 (18)
C24—N2—C3—O32	−20.0 (3)	C5—N1—C6—C7	−82.0 (2)
N1—N2—C3—C4	9.27 (19)	N2—N1—C6—C7	68.7 (2)
C24—N2—C3—C4	160.73 (17)	C8—C7—C6—N1	−2.6 (3)
N2—N1—C5—O33	−175.75 (17)	C12—C7—C6—N1	176.04 (17)
C6—N1—C5—O33	−22.6 (3)	O33—C5—C4—C3	−179.01 (19)
N2—N1—C5—C4	2.3 (2)	N1—C5—C4—C3	3.05 (19)
C6—N1—C5—C4	155.43 (16)	O33—C5—C4—C31	−56.2 (3)
C18—C13—C14—C15	0.4 (3)	N1—C5—C4—C31	125.85 (19)
C34—C13—C14—C15	−179.81 (17)	O33—C5—C4—C28	61.8 (3)
C18—C13—C14—C19	−178.69 (17)	N1—C5—C4—C28	−116.14 (18)
C34—C13—C14—C19	1.1 (3)	O32—C3—C4—C5	173.19 (19)
C16—C15—C14—C13	−0.9 (3)	N2—C3—C4—C5	−7.54 (19)
C16—C15—C14—C19	178.17 (18)	O32—C3—C4—C31	48.6 (3)
O21—C19—C14—C13	3.7 (3)	N2—C3—C4—C31	−132.12 (17)
O20—C19—C14—C13	−176.50 (16)	O32—C3—C4—C28	−68.3 (2)
O21—C19—C14—C15	−175.4 (2)	N2—C3—C4—C28	110.94 (18)
O20—C19—C14—C15	4.4 (3)	C14—C15—C16—C17	0.2 (3)
C3—N2—C24—C25	−89.1 (2)	N2—C24—C25—C26	62.3 (3)
N1—N2—C24—C25	59.7 (2)	C15—C16—C17—C18	1.0 (3)
C9—C10—C11—C12	0.2 (3)	C13—C18—C17—C16	−1.5 (3)
C34—C10—C11—C12	177.82 (18)	C5—C4—C28—C29	−132.7 (2)
C12—C7—C8—C9	−0.2 (3)	C3—C4—C28—C29	113.8 (2)
C6—C7—C8—C9	178.44 (18)	C31—C4—C28—C29	−8.1 (3)
C10—C9—C8—C7	−0.4 (3)	C5—C4—C31—C30	138.9 (2)
C9—C10—C34—O35	167.1 (2)	C3—C4—C31—C30	−103.8 (2)
C11—C10—C34—O35	−10.5 (3)	C28—C4—C31—C30	17.4 (3)
C9—C10—C34—C13	−7.2 (3)	C24—C25—C26—C27	177.5 (2)
C11—C10—C34—C13	175.19 (18)	C4—C31—C30—C29	−21.0 (4)
C18—C13—C34—O35	−86.6 (3)	C31—C30—C29—C28	16.2 (4)
C14—C13—C34—O35	93.6 (3)	C4—C28—C29—C30	−4.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O20—H20···O33^i	0.90 (3)	1.79 (3)	2.687 (3)	174 (3)

Symmetry code: (i) x, y−1, z.

(II) 2-{4-[(3-butyl-1,4-dioxo-2,3-diazaspiro[4.4]non-2-yl)methyl]benzamido}benzoic acid

Crystal data

C26H29N3O5	F(000) = 984
Mr = 463.52	Dx = 1.273 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 16.122 (1) Å	Cell parameters from 25 reflections
b = 12.682 (1) Å	θ = 40–50°
c = 11.920 (1) Å	µ = 0.73 mm^−1
β = 97.139 (7)°	T = 293 K
V = 2418.3 (3) Å^3	Platelet, colourless
Z = 4	0.29 × 0.10 × 0.03 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	1972 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 71.9°, θmin = 2.8°
θ/2θ scans	h = −19→14
Absorption correction: ψ-scan (North et al., 1968)	k = −15→0
Tmin = 0.817, Tmax = 0.979	l = −14→14
6842 measured reflections	3 standard reflections every 200 reflections
4757 independent reflections	intensity decay: 5%

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0743P)^2] where P = (Fo^2 + 2Fc^2)/3
4757 reflections	(Δ/σ)max = 0.001
315 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.19 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
N1	0.75196 (14)	0.31191 (18)	0.08483 (19)	0.0619 (6)
N2	0.79968 (16)	0.3532 (2)	0.1841 (2)	0.0711 (7)
N36	0.42476 (15)	0.24051 (19)	0.4566 (2)	0.0635 (7)
O20	0.26337 (15)	0.4600 (2)	0.5723 (2)	0.0911 (8)
O21	0.37228 (15)	0.43965 (16)	0.47795 (18)	0.0873 (7)
O32	0.92380 (16)	0.3099 (2)	0.2859 (2)	0.1234 (10)
O33	0.74249 (13)	0.15749 (16)	−0.00985 (18)	0.0826 (6)
O35	0.44966 (17)	0.07812 (17)	0.39129 (19)	0.1074 (9)
C3	0.8656 (2)	0.2876 (3)	0.2159 (3)	0.0824 (9)
C4	0.85237 (18)	0.1871 (2)	0.1481 (3)	0.0717 (8)
C5	0.77823 (18)	0.2137 (2)	0.0653 (3)	0.0637 (8)
C6	0.66386 (17)	0.3412 (2)	0.0633 (2)	0.0673 (8)
C7	0.61228 (16)	0.2987 (2)	0.1503 (2)	0.0604 (7)
C8	0.58653 (17)	0.1939 (2)	0.1468 (2)	0.0658 (8)
C9	0.53781 (17)	0.1562 (2)	0.2241 (2)	0.0647 (8)
C10	0.51285 (17)	0.2207 (2)	0.3085 (2)	0.0573 (7)
C11	0.54011 (17)	0.3241 (2)	0.3132 (2)	0.0643 (8)
C12	0.58881 (17)	0.3625 (2)	0.2349 (2)	0.0640 (8)
C13	0.37666 (17)	0.2158 (2)	0.5437 (2)	0.0558 (7)
C14	0.32692 (17)	0.2943 (2)	0.5838 (2)	0.0575 (7)
C15	0.28030 (18)	0.2703 (2)	0.6713 (2)	0.0702 (8)
C16	0.2830 (2)	0.1721 (3)	0.7187 (3)	0.0791 (9)
C17	0.3327 (2)	0.0958 (2)	0.6800 (3)	0.0766 (9)
C18	0.37901 (18)	0.1157 (2)	0.5927 (2)	0.0656 (8)
C19	0.3244 (2)	0.4031 (2)	0.5385 (3)	0.0655 (8)
C24	0.8091 (2)	0.4681 (2)	0.1897 (3)	0.0834 (10)
C25	0.8529 (2)	0.5140 (3)	0.0956 (3)	0.0857 (10)
C26	0.8598 (2)	0.6339 (3)	0.1031 (3)	0.1074 (12)
C27	0.9102 (3)	0.6808 (3)	0.0196 (3)	0.1346 (16)
C28	0.8321 (3)	0.0929 (3)	0.2237 (3)	0.1151 (13)
C29	0.9029 (4)	0.0215 (4)	0.2255 (6)	0.196 (3)
C30	0.9439 (4)	0.0389 (5)	0.1296 (5)	0.178 (2)
C31	0.9306 (2)	0.1511 (3)	0.0975 (3)	0.1104 (13)
C34	0.45959 (18)	0.1732 (2)	0.3879 (2)	0.0650 (8)
H6A	0.6410	0.3152	−0.0107	0.081*
H6B	0.6595	0.4175	0.0618	0.081*
H8	0.6026	0.1492	0.0916	0.079*
H9	0.5210	0.0860	0.2202	0.078*
H11	0.5255	0.3684	0.3697	0.077*
H12	0.6061	0.4325	0.2393	0.077*
H15	0.2467	0.3220	0.6979	0.084*
H16	0.2514	0.1571	0.7769	0.095*
H17	0.3351	0.0294	0.7132	0.092*
H18	0.4117	0.0627	0.5666	0.079*
H20	0.264 (2)	0.520 (3)	0.545 (3)	0.116 (15)*
H24A	0.8404	0.4868	0.2618	0.100*
H24B	0.7541	0.4999	0.1868	0.100*
H25A	0.8223	0.4948	0.0233	0.103*
H25B	0.9085	0.4840	0.0994	0.103*
H26A	0.8040	0.6638	0.0916	0.129*
H26B	0.8847	0.6530	0.1786	0.129*
H27A	0.9107	0.7561	0.0274	0.202*
H27B	0.8861	0.6621	−0.0554	0.202*
H27C	0.9664	0.6545	0.0330	0.202*
H28A	0.8259	0.1168	0.2995	0.138*
H28B	0.7809	0.0583	0.1920	0.138*
H29A	0.9415	0.0331	0.2935	0.235*
H29B	0.8836	−0.0509	0.2260	0.235*
H30A	0.9210	−0.0066	0.0680	0.213*
H30B	1.0032	0.0242	0.1469	0.213*
H31A	0.9224	0.1586	0.0159	0.133*
H31B	0.9785	0.1932	0.1275	0.133*
H36	0.4257 (19)	0.315 (3)	0.447 (2)	0.098 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0600 (15)	0.0527 (15)	0.0715 (16)	−0.0045 (12)	0.0024 (12)	−0.0094 (12)
N2	0.0702 (17)	0.0648 (17)	0.0766 (17)	−0.0085 (14)	0.0030 (14)	−0.0116 (13)
N36	0.0752 (16)	0.0428 (15)	0.0737 (17)	0.0023 (12)	0.0137 (14)	−0.0032 (13)
O20	0.1063 (18)	0.0576 (15)	0.1172 (19)	0.0203 (14)	0.0445 (15)	0.0195 (14)
O21	0.1162 (18)	0.0525 (13)	0.1016 (17)	0.0067 (12)	0.0470 (16)	0.0109 (11)
O32	0.1002 (19)	0.140 (2)	0.117 (2)	−0.0145 (17)	−0.0389 (17)	0.0007 (17)
O33	0.0890 (15)	0.0594 (13)	0.0989 (16)	−0.0102 (11)	0.0098 (13)	−0.0181 (12)
O35	0.172 (2)	0.0478 (14)	0.1143 (19)	−0.0136 (14)	0.0631 (17)	−0.0133 (12)
C3	0.070 (2)	0.092 (3)	0.082 (2)	−0.010 (2)	−0.0011 (19)	0.008 (2)
C4	0.0616 (19)	0.068 (2)	0.086 (2)	0.0016 (16)	0.0122 (17)	0.0152 (18)
C5	0.0654 (19)	0.0530 (19)	0.074 (2)	−0.0086 (16)	0.0128 (17)	−0.0006 (16)
C6	0.0634 (19)	0.0598 (19)	0.076 (2)	0.0039 (15)	−0.0006 (16)	0.0027 (15)
C7	0.0534 (16)	0.0555 (18)	0.0702 (19)	0.0058 (14)	−0.0003 (15)	0.0031 (16)
C8	0.0644 (18)	0.059 (2)	0.074 (2)	0.0008 (15)	0.0100 (16)	−0.0069 (15)
C9	0.0698 (19)	0.0443 (17)	0.079 (2)	0.0005 (14)	0.0042 (17)	−0.0052 (15)
C10	0.0621 (17)	0.0433 (17)	0.0640 (17)	0.0066 (14)	−0.0016 (14)	−0.0003 (14)
C11	0.0706 (19)	0.0465 (18)	0.075 (2)	0.0063 (15)	0.0075 (17)	−0.0023 (14)
C12	0.0643 (19)	0.0462 (17)	0.080 (2)	0.0015 (14)	0.0015 (17)	0.0001 (16)
C13	0.0567 (16)	0.0472 (17)	0.0615 (18)	−0.0050 (14)	−0.0004 (14)	−0.0024 (14)
C14	0.0660 (18)	0.0440 (17)	0.0612 (17)	−0.0019 (14)	0.0035 (15)	−0.0006 (14)
C15	0.077 (2)	0.059 (2)	0.076 (2)	0.0031 (16)	0.0146 (18)	0.0026 (16)
C16	0.090 (2)	0.065 (2)	0.085 (2)	−0.0014 (19)	0.0197 (19)	0.0168 (18)
C17	0.089 (2)	0.0531 (19)	0.088 (2)	−0.0036 (18)	0.010 (2)	0.0160 (17)
C18	0.074 (2)	0.0490 (18)	0.072 (2)	0.0017 (15)	0.0019 (17)	0.0033 (15)
C19	0.076 (2)	0.0513 (19)	0.069 (2)	0.0047 (17)	0.0119 (17)	−0.0026 (15)
C24	0.088 (2)	0.069 (2)	0.092 (2)	−0.0104 (18)	0.008 (2)	−0.0254 (18)
C25	0.084 (2)	0.074 (2)	0.099 (2)	−0.0143 (18)	0.013 (2)	−0.0085 (19)
C26	0.102 (3)	0.081 (3)	0.139 (3)	−0.016 (2)	0.012 (3)	−0.003 (2)
C27	0.129 (3)	0.117 (4)	0.159 (4)	−0.033 (3)	0.023 (3)	0.029 (3)
C28	0.134 (3)	0.096 (3)	0.115 (3)	−0.015 (3)	0.014 (3)	0.042 (2)
C29	0.147 (5)	0.120 (5)	0.309 (9)	0.018 (4)	−0.016 (5)	0.100 (5)
C30	0.174 (6)	0.130 (5)	0.229 (7)	0.078 (4)	0.027 (5)	0.023 (4)
C31	0.079 (2)	0.129 (4)	0.126 (3)	0.011 (2)	0.024 (2)	0.016 (3)
C34	0.079 (2)	0.0463 (19)	0.068 (2)	0.0000 (16)	0.0047 (17)	−0.0036 (15)

Geometric parameters (Å, º)

N1—N2	1.429 (3)	C17—H17	0.9300
N1—C5	1.345 (3)	C18—H18	0.9300
N1—C6	1.460 (3)	C12—H12	0.9300
N2—C3	1.366 (4)	C15—H15	0.9300
N2—C24	1.466 (4)	C4—C3	1.510 (4)
N36—C13	1.407 (3)	C4—C31	1.533 (4)
N36—C34	1.352 (3)	C4—C28	1.555 (4)
N36—H36	0.95 (3)	C6—H6A	0.9700
O20—C19	1.322 (3)	C6—H6B	0.9700
O21—C19	1.213 (3)	C24—C25	1.514 (4)
O20—H20	0.83 (4)	C24—H24A	0.9700
O32—C3	1.209 (3)	C24—H24B	0.9700
O33—C5	1.231 (3)	C25—C26	1.525 (4)
O35—C34	1.218 (3)	C25—H25A	0.9700
C8—C9	1.369 (4)	C25—H25B	0.9700
C8—C7	1.392 (4)	C28—C29	1.455 (6)
C8—H8	0.9300	C28—H28A	0.9700
C10—C11	1.382 (4)	C28—H28B	0.9700
C10—C9	1.394 (3)	C31—C30	1.482 (6)
C11—C12	1.380 (3)	C31—H31A	0.9700
C11—H11	0.9300	C31—H31B	0.9700
C14—C15	1.393 (4)	C26—C27	1.486 (4)
C14—C13	1.399 (4)	C26—H26A	0.9700
C14—C19	1.480 (4)	C26—H26B	0.9700
C5—C4	1.491 (4)	C27—H27A	0.9600
C9—H9	0.9300	C27—H27B	0.9600
C13—C18	1.396 (4)	C27—H27C	0.9600
C7—C12	1.382 (3)	C29—C30	1.408 (6)
C7—C6	1.507 (4)	C34—C10	1.482 (4)
C16—C15	1.366 (4)	C29—H29A	0.9700
C16—C17	1.372 (4)	C29—H29B	0.9700
C16—H16	0.9300	C30—H30A	0.9700
C17—C18	1.377 (4)	C30—H30B	0.9700
C19—O20—H20	110 (2)	C3—C4—C28	111.4 (3)
C5—N1—N2	109.5 (2)	C31—C4—C28	104.0 (3)
C5—N1—C6	121.7 (2)	N1—C6—C7	113.3 (2)
N2—N1—C6	117.7 (2)	N1—C6—H6A	108.9
C34—N36—C13	128.0 (3)	C7—C6—H6A	108.9
C34—N36—H36	122.4 (18)	N1—C6—H6B	108.9
C13—N36—H36	109.4 (18)	C7—C6—H6B	108.9
C3—N2—N1	109.1 (2)	H6A—C6—H6B	107.7
C3—N2—C24	121.4 (3)	O32—C3—N2	124.0 (3)
N1—N2—C24	116.3 (2)	O32—C3—C4	127.8 (3)
O35—C34—N36	122.6 (3)	N2—C3—C4	108.2 (3)
O35—C34—C10	120.8 (3)	N2—C24—C25	113.8 (3)
N36—C34—C10	116.6 (3)	N2—C24—H24A	108.8
C15—C14—C13	119.1 (3)	C25—C24—H24A	108.8
C15—C14—C19	118.9 (3)	N2—C24—H24B	108.8
C13—C14—C19	122.0 (3)	C25—C24—H24B	108.8
C11—C10—C9	117.8 (3)	H24A—C24—H24B	107.7
C11—C10—C34	124.5 (3)	C24—C25—C26	112.1 (3)
C9—C10—C34	117.7 (3)	C24—C25—H25A	109.2
C9—C8—C7	120.5 (3)	C26—C25—H25A	109.2
C9—C8—H8	119.7	C24—C25—H25B	109.2
C7—C8—H8	119.7	C26—C25—H25B	109.2
C12—C11—C10	120.8 (3)	H25A—C25—H25B	107.9
C12—C11—H11	119.6	C29—C28—C4	105.4 (3)
C10—C11—H11	119.6	C29—C28—H28A	110.7
O33—C5—N1	122.2 (3)	C4—C28—H28A	110.7
O33—C5—C4	127.9 (3)	C29—C28—H28B	110.7
N1—C5—C4	109.8 (3)	C4—C28—H28B	110.7
C8—C9—C10	121.5 (3)	H28A—C28—H28B	108.8
C8—C9—H9	119.3	C30—C31—C4	106.5 (3)
C10—C9—H9	119.3	C30—C31—H31A	110.4
C18—C13—C14	119.4 (3)	C4—C31—H31A	110.4
C18—C13—N36	121.5 (3)	C30—C31—H31B	110.4
C14—C13—N36	119.0 (2)	C4—C31—H31B	110.4
C12—C7—C8	118.2 (3)	H31A—C31—H31B	108.6
C12—C7—C6	121.2 (3)	C27—C26—C25	113.7 (3)
C8—C7—C6	120.6 (3)	C27—C26—H26A	108.8
C15—C16—C17	119.6 (3)	C25—C26—H26A	108.8
C15—C16—H16	120.2	C27—C26—H26B	108.8
C17—C16—H16	120.2	C25—C26—H26B	108.8
C16—C17—C18	121.3 (3)	H26A—C26—H26B	107.7
C16—C17—H17	119.4	C26—C27—H27A	109.5
C18—C17—H17	119.4	C26—C27—H27B	109.5
C17—C18—C13	119.6 (3)	H27A—C27—H27B	109.5
C17—C18—H18	120.2	C26—C27—H27C	109.5
C13—C18—H18	120.2	H27A—C27—H27C	109.5
C11—C12—C7	121.2 (3)	H27B—C27—H27C	109.5
C11—C12—H12	119.4	C30—C29—C28	109.7 (5)
C7—C12—H12	119.4	C30—C29—H29A	109.7
C16—C15—C14	121.1 (3)	C28—C29—H29A	109.7
C16—C15—H15	119.4	C30—C29—H29B	109.7
C14—C15—H15	119.4	C28—C29—H29B	109.7
O21—C19—O20	121.7 (3)	H29A—C29—H29B	108.2
O21—C19—C14	125.6 (3)	C29—C30—C31	107.0 (5)
O20—C19—C14	112.7 (3)	C29—C30—H30A	110.3
C5—C4—C3	102.2 (3)	C31—C30—H30A	110.3
C5—C4—C31	116.0 (3)	C29—C30—H30B	110.3
C3—C4—C31	113.1 (3)	C31—C30—H30B	110.3
C5—C4—C28	110.4 (3)	H30A—C30—H30B	108.6
C5—N1—N2—C3	10.4 (3)	C15—C14—C19—O21	166.0 (3)
C6—N1—N2—C3	155.1 (2)	C13—C14—C19—O21	−12.1 (5)
C5—N1—N2—C24	152.2 (2)	C15—C14—C19—O20	−13.2 (4)
C6—N1—N2—C24	−63.1 (3)	C13—C14—C19—O20	168.7 (3)
C13—N36—C34—O35	3.2 (5)	O33—C5—C4—C3	179.8 (3)
C13—N36—C34—C10	−175.5 (2)	N1—C5—C4—C3	−1.7 (3)
O35—C34—C10—C11	−167.4 (3)	O33—C5—C4—C31	56.3 (4)
N36—C34—C10—C11	11.3 (4)	N1—C5—C4—C31	−125.1 (3)
O35—C34—C10—C9	12.0 (4)	O33—C5—C4—C28	−61.7 (4)
N36—C34—C10—C9	−169.3 (2)	N1—C5—C4—C28	116.9 (3)
C9—C10—C11—C12	1.5 (4)	C5—N1—C6—C7	74.6 (3)
C34—C10—C11—C12	−179.2 (2)	N2—N1—C6—C7	−65.5 (3)
N2—N1—C5—O33	173.7 (2)	C12—C7—C6—N1	102.1 (3)
C6—N1—C5—O33	30.7 (4)	C8—C7—C6—N1	−78.4 (3)
N2—N1—C5—C4	−5.0 (3)	N1—N2—C3—O32	168.1 (3)
C6—N1—C5—C4	−147.9 (2)	C24—N2—C3—O32	28.6 (5)
C7—C8—C9—C10	−0.3 (4)	N1—N2—C3—C4	−11.2 (3)
C11—C10—C9—C8	−1.1 (4)	C24—N2—C3—C4	−150.8 (3)
C34—C10—C9—C8	179.5 (2)	C5—C4—C3—O32	−171.4 (3)
C15—C14—C13—C18	−0.5 (4)	C31—C4—C3—O32	−46.0 (5)
C19—C14—C13—C18	177.5 (2)	C28—C4—C3—O32	70.7 (4)
C15—C14—C13—N36	−179.0 (2)	C5—C4—C3—N2	7.9 (3)
C19—C14—C13—N36	−0.9 (4)	C31—C4—C3—N2	133.3 (3)
C34—N36—C13—C18	19.5 (4)	C28—C4—C3—N2	−110.0 (3)
C34—N36—C13—C14	−162.1 (3)	C3—N2—C24—C25	75.9 (4)
C9—C8—C7—C12	1.3 (4)	N1—N2—C24—C25	−60.9 (3)
C9—C8—C7—C6	−178.2 (2)	N2—C24—C25—C26	178.8 (3)
C15—C16—C17—C18	−1.0 (5)	C5—C4—C28—C29	133.4 (4)
C16—C17—C18—C13	1.0 (4)	C3—C4—C28—C29	−113.8 (4)
C14—C13—C18—C17	−0.2 (4)	C31—C4—C28—C29	8.3 (5)
N36—C13—C18—C17	178.2 (3)	C5—C4—C31—C30	−113.4 (4)
C10—C11—C12—C7	−0.5 (4)	C3—C4—C31—C30	129.0 (4)
C8—C7—C12—C11	−0.9 (4)	C28—C4—C31—C30	8.0 (5)
C6—C7—C12—C11	178.6 (2)	C24—C25—C26—C27	173.9 (3)
C17—C16—C15—C14	0.2 (5)	C4—C28—C29—C30	−23.1 (7)
C13—C14—C15—C16	0.6 (4)	C28—C29—C30—C31	28.8 (8)
C19—C14—C15—C16	−177.6 (3)	C4—C31—C30—C29	−22.3 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N36—H36···O21	0.95 (4)	1.86 (4)	2.686 (3)	144 (3)
O20—H20···O33^i	0.83 (4)	1.79 (4)	2.611 (3)	169 (4)

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

(III) 2-{4-[(3-butyl-1,4-dioxo-2,3-diazaspiro[4.4]non-2-yl)methyl]amilinocarbonyl} benzoic acid monohydrate

Crystal data

C26H29N3O5·H2O	F(000) = 1024
Mr = 481.54	Dx = 1.300 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 18.681 (1) Å	Cell parameters from 25 reflections
b = 9.565 (1) Å	θ = 40–50°
c = 14.837 (1) Å	µ = 0.76 mm^−1
β = 111.904 (7)°	T = 293 K
V = 2459.7 (3) Å^3	Platelet, colourless
Z = 4	0.26 × 0.11 × 0.07 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	3166 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.013
Graphite monochromator	θmax = 71.9°, θmin = 2.6°
θ/2θ scans	h = −23→21
Absorption correction: ψ-scan (North et al., 1968)	k = −7→11
Tmin = 0.826, Tmax = 0.948	l = 0→18
6162 measured reflections	3 standard reflections every 200 reflections
4835 independent reflections	intensity decay: 4%

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)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.151	w = 1/[σ^2(Fo^2) + (0.0704P)^2 + 0.7853P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.008
4835 reflections	Δρmax = 0.36 e Å^−3
333 parameters	Δρmin = −0.28 e Å^−3
5 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (2)

Special details

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

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.20910 (10)	0.65699 (18)	−0.24187 (13)	0.0450 (4)
N2	0.21551 (11)	0.50822 (19)	−0.23485 (15)	0.0520 (5)
N36	0.47146 (11)	0.70613 (19)	0.18844 (13)	0.0444 (4)
O20	0.73325 (10)	0.8984 (2)	0.36369 (14)	0.0631 (5)
O21	0.61993 (10)	0.9142 (2)	0.24154 (13)	0.0739 (6)
O32	0.14828 (13)	0.32933 (18)	−0.20050 (18)	0.0850 (7)
O33	0.13980 (10)	0.82122 (17)	−0.19702 (15)	0.0660 (5)
O35	0.45948 (9)	0.92269 (15)	0.24674 (11)	0.0534 (4)
O37	0.80719 (12)	0.9319 (2)	0.24565 (18)	0.0747 (6)
C3	0.16194 (15)	0.4545 (3)	−0.2033 (2)	0.0587 (6)
C4	0.12390 (13)	0.5729 (2)	−0.17191 (18)	0.0516 (6)
C5	0.15534 (13)	0.6992 (2)	−0.20510 (17)	0.0476 (5)
C6	0.28283 (12)	0.7339 (2)	−0.21603 (16)	0.0461 (5)
C7	0.33114 (12)	0.7256 (2)	−0.10923 (16)	0.0424 (5)
C8	0.33048 (13)	0.8342 (2)	−0.04800 (17)	0.0498 (6)
C9	0.37475 (13)	0.8312 (2)	0.05066 (17)	0.0491 (6)
C10	0.42171 (12)	0.7168 (2)	0.08979 (16)	0.0412 (5)
C11	0.42244 (12)	0.6065 (2)	0.02945 (16)	0.0441 (5)
C12	0.37805 (13)	0.6109 (2)	−0.06867 (17)	0.0447 (5)
C13	0.54829 (12)	0.7636 (2)	0.35450 (15)	0.0405 (5)
C14	0.62581 (12)	0.8059 (2)	0.38871 (15)	0.0413 (5)
C15	0.67317 (13)	0.7757 (2)	0.48425 (16)	0.0482 (5)
C16	0.64443 (15)	0.7061 (2)	0.54480 (17)	0.0534 (6)
C17	0.56916 (15)	0.6604 (3)	0.51045 (18)	0.0546 (6)
C18	0.52165 (13)	0.6880 (2)	0.41534 (17)	0.0492 (6)
C19	0.65765 (13)	0.8791 (2)	0.32326 (17)	0.0461 (5)
C24	0.24654 (16)	0.4375 (3)	−0.2992 (2)	0.0681 (8)
C25	0.20546 (19)	0.4738 (4)	−0.4042 (3)	0.0942 (11)
C26	0.1245 (4)	0.3987 (8)	−0.4314 (4)	0.0898 (11)	0.57
C27	0.0830 (4)	0.4083 (7)	−0.5413 (4)	0.0898 (11)	0.57
C28	0.15115 (17)	0.5785 (3)	−0.0595 (2)	0.0712 (8)
C29	0.0881 (5)	0.6323 (15)	−0.0352 (10)	0.129 (3)	0.63
C30	0.0184 (6)	0.5929 (11)	−0.1157 (7)	0.129 (3)	0.63
C31	0.03508 (15)	0.5652 (3)	−0.2068 (2)	0.0722 (8)
C26'	0.1175 (5)	0.4801 (9)	−0.4639 (6)	0.0898 (11)	0.43
C27'	0.0940 (5)	0.3306 (9)	−0.4895 (6)	0.0898 (11)	0.43
C29'	0.0755 (10)	0.581 (3)	−0.0424 (19)	0.129 (3)	0.37
C30'	0.0151 (11)	0.523 (2)	−0.1257 (13)	0.129 (3)	0.37
C34	0.49034 (12)	0.8070 (2)	0.25730 (16)	0.0417 (5)
H6A	0.2720	0.8312	−0.2344	0.055*
H6B	0.3119	0.6956	−0.2525	0.055*
H8	0.2994	0.9116	−0.0737	0.060*
H9	0.3729	0.9053	0.0903	0.059*
H11	0.4531	0.5288	0.0553	0.053*
H12	0.3795	0.5363	−0.1082	0.054*
H15	0.7247	0.8029	0.5074	0.058*
H16	0.6761	0.6900	0.6092	0.064*
H17	0.5503	0.6112	0.5510	0.065*
H18	0.4711	0.6553	0.3919	0.059*
H20	0.753 (2)	0.925 (4)	0.316 (3)	0.111 (13)*
H24A	0.2434	0.3373	−0.2914	0.082*
H24B	0.3006	0.4617	−0.2800	0.082*
H25A	0.2331	0.4384	−0.4433	0.113*
H25B	0.1993	0.5742	−0.4132	0.113*
H26A	0.1317	0.3016	−0.4111	0.108*	0.57
H26B	0.0943	0.4444	−0.3990	0.108*	0.57
H27A	0.0337	0.3630	−0.5602	0.135*	0.57
H27B	0.1135	0.3631	−0.5725	0.135*	0.57
H27C	0.0758	0.5047	−0.5605	0.135*	0.57
H28A	0.1654	0.4858	−0.0323	0.085*
H28B	0.1958	0.6391	−0.0330	0.085*
H29A	0.0916	0.7331	−0.0280	0.155*	0.63
H29B	0.0887	0.5914	0.0249	0.155*	0.63
H30A	−0.0194	0.6673	−0.1283	0.155*	0.63
H30B	−0.0033	0.5095	−0.0987	0.155*	0.63
H26C	0.0904	0.5200	−0.4255	0.108*	0.43
H26D	0.1066	0.5360	−0.5220	0.108*	0.43
H27D	0.0396	0.3263	−0.5268	0.135*	0.43
H27E	0.1057	0.2770	−0.4310	0.135*	0.43
H27F	0.1217	0.2930	−0.5270	0.135*	0.43
H29C	0.0808	0.5266	0.0150	0.155*	0.37
H29D	0.0626	0.6762	−0.0319	0.155*	0.37
H30C	−0.0348	0.5600	−0.1319	0.155*	0.37
H30D	0.0138	0.4217	−0.1212	0.155*	0.37
H31A	0.0110	0.6354	−0.2559	0.087*
H31B	0.0164	0.4736	−0.2333	0.087*
H36	0.4957 (14)	0.619 (3)	0.2035 (18)	0.055 (7)*
H37A	0.8276 (19)	1.002 (4)	0.231 (2)	0.094 (12)*
H37B	0.8247 (19)	0.850 (4)	0.235 (2)	0.097 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0445 (10)	0.0367 (9)	0.0517 (11)	−0.0056 (8)	0.0155 (9)	−0.0038 (8)
N2	0.0529 (11)	0.0372 (10)	0.0684 (13)	−0.0032 (8)	0.0254 (10)	−0.0078 (9)
N36	0.0489 (10)	0.0348 (9)	0.0436 (10)	0.0041 (8)	0.0103 (8)	−0.0006 (8)
O20	0.0503 (10)	0.0775 (13)	0.0597 (11)	−0.0114 (9)	0.0185 (8)	0.0043 (9)
O21	0.0600 (11)	0.1109 (16)	0.0482 (10)	−0.0076 (10)	0.0171 (9)	0.0178 (11)
O32	0.0988 (15)	0.0388 (10)	0.136 (2)	−0.0097 (10)	0.0649 (15)	−0.0013 (11)
O33	0.0706 (11)	0.0418 (9)	0.0971 (14)	0.0047 (8)	0.0447 (11)	0.0038 (9)
O35	0.0586 (10)	0.0370 (8)	0.0547 (10)	0.0065 (7)	0.0096 (8)	−0.0026 (7)
O37	0.0782 (13)	0.0483 (11)	0.1174 (19)	0.0002 (10)	0.0595 (13)	0.0083 (12)
C3	0.0582 (14)	0.0439 (13)	0.0753 (18)	−0.0030 (11)	0.0265 (13)	0.0015 (12)
C4	0.0483 (12)	0.0453 (12)	0.0612 (15)	−0.0015 (10)	0.0205 (11)	0.0052 (11)
C5	0.0440 (12)	0.0425 (12)	0.0549 (14)	−0.0003 (9)	0.0168 (10)	0.0022 (10)
C6	0.0428 (11)	0.0435 (12)	0.0508 (13)	−0.0065 (9)	0.0161 (10)	0.0019 (10)
C7	0.0391 (11)	0.0373 (11)	0.0494 (13)	−0.0061 (8)	0.0150 (10)	−0.0005 (9)
C8	0.0460 (12)	0.0365 (11)	0.0587 (15)	0.0043 (9)	0.0102 (11)	−0.0002 (10)
C9	0.0513 (13)	0.0372 (11)	0.0517 (14)	0.0049 (10)	0.0110 (11)	−0.0061 (10)
C10	0.0400 (11)	0.0341 (10)	0.0480 (12)	−0.0037 (8)	0.0146 (9)	−0.0008 (9)
C11	0.0465 (12)	0.0326 (10)	0.0525 (13)	0.0014 (9)	0.0174 (10)	0.0027 (9)
C12	0.0501 (12)	0.0346 (11)	0.0486 (13)	−0.0014 (9)	0.0176 (10)	−0.0024 (9)
C13	0.0442 (11)	0.0344 (10)	0.0442 (12)	0.0039 (9)	0.0181 (9)	−0.0024 (9)
C14	0.0456 (11)	0.0358 (10)	0.0429 (12)	0.0026 (9)	0.0171 (9)	−0.0037 (9)
C15	0.0493 (13)	0.0473 (13)	0.0446 (13)	0.0045 (10)	0.0135 (10)	−0.0029 (10)
C16	0.0665 (15)	0.0516 (13)	0.0401 (12)	0.0091 (11)	0.0174 (11)	0.0031 (10)
C17	0.0681 (16)	0.0496 (13)	0.0551 (14)	0.0098 (12)	0.0335 (13)	0.0095 (11)
C18	0.0485 (12)	0.0452 (12)	0.0573 (15)	0.0057 (10)	0.0237 (11)	0.0047 (11)
C19	0.0480 (12)	0.0429 (12)	0.0469 (13)	−0.0015 (10)	0.0172 (10)	−0.0040 (10)
C24	0.0651 (16)	0.0517 (15)	0.097 (2)	−0.0040 (12)	0.0405 (16)	−0.0197 (15)
C25	0.077 (2)	0.120 (3)	0.091 (2)	−0.003 (2)	0.0370 (19)	−0.051 (2)
C26	0.086 (2)	0.107 (4)	0.063 (3)	0.002 (2)	0.013 (2)	−0.0032 (18)
C27	0.086 (2)	0.107 (4)	0.063 (3)	0.002 (2)	0.013 (2)	−0.0032 (18)
C28	0.0757 (18)	0.0744 (19)	0.0662 (18)	0.0026 (15)	0.0297 (15)	0.0116 (15)
C29	0.090 (3)	0.200 (10)	0.118 (3)	−0.021 (5)	0.064 (3)	−0.025 (6)
C30	0.090 (3)	0.200 (10)	0.118 (3)	−0.021 (5)	0.064 (3)	−0.025 (6)
C31	0.0486 (14)	0.0685 (17)	0.096 (2)	−0.0054 (13)	0.0222 (14)	0.0082 (16)
C26'	0.086 (2)	0.107 (4)	0.063 (3)	0.002 (2)	0.013 (2)	−0.0032 (18)
C27'	0.086 (2)	0.107 (4)	0.063 (3)	0.002 (2)	0.013 (2)	−0.0032 (18)
C29'	0.090 (3)	0.200 (10)	0.118 (3)	−0.021 (5)	0.064 (3)	−0.025 (6)
C30'	0.090 (3)	0.200 (10)	0.118 (3)	−0.021 (5)	0.064 (3)	−0.025 (6)
C34	0.0433 (11)	0.0338 (10)	0.0480 (12)	−0.0008 (9)	0.0172 (10)	0.0006 (9)

Geometric parameters (Å, º)

N1—N2	1.429 (2)	C26—C27	1.525 (7)
N1—C5	1.371 (3)	C26—H26A	0.9700
N1—C6	1.480 (3)	C26—H26B	0.9700
N2—C3	1.354 (3)	C27—H27A	0.9600
N36—C10	1.415 (3)	C27—H27B	0.9600
N36—C34	1.353 (3)	C27—H27C	0.9600
N36—H36	0.93 (3)	C26'—C27'	1.503 (10)
O20—C19	1.325 (3)	C26'—H26C	0.9700
O20—H20	0.94 (4)	C26'—H26D	0.9700
O21—C19	1.201 (3)	C27'—H27D	0.9600
O32—C3	1.228 (3)	C27'—H27E	0.9600
O33—C5	1.219 (3)	C27'—H27F	0.9600
O35—C34	1.231 (2)	C13—C18	1.386 (3)
C31—C30'	1.444 (13)	C13—C14	1.403 (3)
C31—C30	1.519 (7)	C13—C34	1.503 (3)
C31—C4	1.545 (3)	C7—C8	1.383 (3)
C31—H31A	0.9700	C7—C12	1.393 (3)
C31—H31B	0.9700	C7—C6	1.505 (3)
C28—C29	1.449 (9)	C6—H6A	0.9700
C28—C29'	1.527 (12)	C6—H6B	0.9700
C28—C4	1.552 (4)	C14—C15	1.393 (3)
C28—H28A	0.9700	C14—C19	1.489 (3)
C28—H28B	0.9700	C11—C12	1.381 (3)
C24—N2	1.455 (3)	C11—C10	1.387 (3)
C24—C25	1.498 (4)	C11—H11	0.9300
C24—H24A	0.9700	C8—C9	1.387 (3)
C24—H24B	0.9700	C8—H8	0.9300
C25—C26'	1.550 (8)	C5—C4	1.505 (3)
C25—C26	1.586 (7)	C15—C16	1.378 (3)
C25—H25A	0.9700	C15—H15	0.9300
C25—H25B	0.9700	C9—C10	1.387 (3)
C30—C29	1.450 (9)	C9—H9	0.9300
C30—H30A	0.9700	C12—H12	0.9300
C30—H30B	0.9700	C16—C17	1.376 (4)
C29—H29A	0.9700	C16—H16	0.9300
C29—H29B	0.9700	C17—C18	1.384 (3)
C30'—C29'	1.438 (13)	C17—H17	0.9300
C30'—H30C	0.9700	C18—H18	0.9300
C30'—H30D	0.9700	C4—C3	1.500 (3)
C29'—H29C	0.9700	O37—H37A	0.84 (4)
C29'—H29D	0.9700	O37—H37B	0.89 (4)
C30'—C31—C4	108.3 (9)	C26'—C27'—H27E	109.5
C30—C31—C4	104.2 (5)	H27D—C27'—H27E	109.5
C30'—C31—H31A	129.0	C26'—C27'—H27F	109.5
C30—C31—H31A	110.9	H27D—C27'—H27F	109.5
C4—C31—H31A	110.9	H27E—C27'—H27F	109.5
C30'—C31—H31B	85.4	C19—O20—H20	110 (2)
C30—C31—H31B	110.9	C34—N36—C10	128.00 (18)
C4—C31—H31B	110.9	C34—N36—H36	119.1 (15)
H31A—C31—H31B	108.9	C10—N36—H36	112.7 (15)
C29—C28—C4	108.0 (6)	C3—N2—N1	110.53 (18)
C29'—C28—C4	103.1 (10)	C3—N2—C24	125.2 (2)
C29—C28—H28A	110.1	N1—N2—C24	117.2 (2)
C29'—C28—H28A	94.1	C5—N1—N2	108.58 (17)
C4—C28—H28A	110.1	C5—N1—C6	119.97 (18)
C29—C28—H28B	110.1	N2—N1—C6	115.57 (17)
C29'—C28—H28B	129.3	C18—C13—C14	119.2 (2)
C4—C28—H28B	110.1	C18—C13—C34	117.64 (19)
H28A—C28—H28B	108.4	C14—C13—C34	122.97 (19)
N2—C24—C25	113.6 (2)	O35—C34—N36	124.6 (2)
N2—C24—H24A	108.9	O35—C34—C13	120.38 (19)
C25—C24—H24A	108.9	N36—C34—C13	114.81 (17)
N2—C24—H24B	108.9	C8—C7—C12	117.8 (2)
C25—C24—H24B	108.9	C8—C7—C6	120.20 (19)
H24A—C24—H24B	107.7	C12—C7—C6	122.0 (2)
C24—C25—C26'	128.7 (4)	N1—C6—C7	112.40 (17)
C24—C25—C26	103.3 (3)	N1—C6—H6A	109.1
C24—C25—H25A	111.1	C7—C6—H6A	109.1
C26'—C25—H25A	111.1	N1—C6—H6B	109.1
C26—C25—H25A	111.1	C7—C6—H6B	109.1
C24—C25—H25B	111.1	H6A—C6—H6B	107.9
C26'—C25—H25B	80.6	C15—C14—C13	119.1 (2)
C26—C25—H25B	111.1	C15—C14—C19	120.3 (2)
H25A—C25—H25B	109.1	C13—C14—C19	120.59 (19)
C29—C30—C31	111.0 (7)	C12—C11—C10	120.70 (19)
C29—C30—H30A	109.4	C12—C11—H11	119.6
C31—C30—H30A	109.4	C10—C11—H11	119.6
C29—C30—H30B	109.4	C7—C8—C9	122.0 (2)
C31—C30—H30B	109.4	C7—C8—H8	119.0
H30A—C30—H30B	108.0	C9—C8—H8	119.0
C28—C29—C30	105.4 (8)	O33—C5—N1	123.9 (2)
C28—C29—H29A	110.7	O33—C5—C4	126.9 (2)
C30—C29—H29A	110.7	N1—C5—C4	109.08 (19)
C28—C29—H29B	110.6	C16—C15—C14	120.6 (2)
C30—C29—H29B	110.7	C16—C15—H15	119.7
H29A—C29—H29B	108.8	C14—C15—H15	119.7
C29'—C30'—C31	104.1 (14)	O21—C19—O20	122.9 (2)
C29'—C30'—H30C	110.9	O21—C19—C14	124.3 (2)
C31—C30'—H30C	110.9	O20—C19—C14	112.8 (2)
C29'—C30'—H30D	110.9	C10—C9—C8	119.6 (2)
C31—C30'—H30D	110.9	C10—C9—H9	120.2
H30C—C30'—H30D	108.9	C8—C9—H9	120.2
C30'—C29'—C28	109.2 (14)	C11—C10—C9	119.1 (2)
C30'—C29'—H29C	109.8	C11—C10—N36	116.89 (18)
C28—C29'—H29C	109.8	C9—C10—N36	123.97 (19)
C30'—C29'—H29D	109.8	C11—C12—C7	120.9 (2)
C28—C29'—H29D	109.8	C11—C12—H12	119.6
H29C—C29'—H29D	108.3	C7—C12—H12	119.6
C27—C26—C25	107.5 (5)	C17—C16—C15	120.3 (2)
C27—C26—H26A	110.2	C17—C16—H16	119.8
C25—C26—H26A	110.2	C15—C16—H16	119.8
C27—C26—H26B	110.2	C16—C17—C18	119.7 (2)
C25—C26—H26B	110.2	C16—C17—H17	120.2
H26A—C26—H26B	108.5	C18—C17—H17	120.2
C26—C27—H27A	109.5	C17—C18—C13	120.9 (2)
C26—C27—H27B	109.5	C17—C18—H18	119.5
H27A—C27—H27B	109.5	C13—C18—H18	119.5
C26—C27—H27C	109.5	C3—C4—C5	102.53 (19)
H27A—C27—H27C	109.5	C3—C4—C31	115.7 (2)
H27B—C27—H27C	109.5	C5—C4—C31	115.5 (2)
C27'—C26'—C25	104.8 (6)	C3—C4—C28	110.9 (2)
C27'—C26'—H26C	110.8	C5—C4—C28	108.2 (2)
C25—C26'—H26C	110.8	C31—C4—C28	104.0 (2)
C27'—C26'—H26D	110.8	O32—C3—N2	124.8 (2)
C25—C26'—H26D	110.8	O32—C3—C4	126.7 (2)
H26C—C26'—H26D	108.9	N2—C3—C4	108.5 (2)
C26'—C27'—H27D	109.5	H37A—O37—H37B	116 (3)
N2—C24—C25—C26'	−46.7 (6)	C7—C8—C9—C10	0.5 (4)
N2—C24—C25—C26	−71.0 (4)	C12—C11—C10—C9	1.0 (3)
C4—C31—C30—C29	7.0 (8)	C12—C11—C10—N36	−177.3 (2)
C4—C28—C29—C30	28.0 (9)	C8—C9—C10—C11	−1.0 (3)
C31—C30—C29—C28	−21.9 (10)	C8—C9—C10—N36	177.2 (2)
C4—C31—C30'—C29'	31.8 (14)	C34—N36—C10—C11	168.6 (2)
C31—C30'—C29'—C28	−34.1 (18)	C34—N36—C10—C9	−9.7 (4)
C4—C28—C29'—C30'	22.6 (17)	C10—C11—C12—C7	−0.4 (3)
C24—C25—C26—C27	−170.6 (5)	C8—C7—C12—C11	−0.1 (3)
C24—C25—C26'—C27'	−80.2 (8)	C6—C7—C12—C11	179.3 (2)
C26—C25—C26'—C27'	−33.3 (6)	C14—C15—C16—C17	2.6 (3)
C25—C24—N2—C3	94.5 (3)	C15—C16—C17—C18	−1.8 (4)
C25—C24—N2—N1	−53.4 (3)	C16—C17—C18—C13	−1.3 (3)
C3—N2—N1—C5	5.9 (3)	C14—C13—C18—C17	3.5 (3)
C24—N2—N1—C5	158.2 (2)	C34—C13—C18—C17	−171.3 (2)
C3—N2—N1—C6	144.0 (2)	O33—C5—C4—C3	178.7 (3)
C24—N2—N1—C6	−63.6 (3)	N1—C5—C4—C3	−4.9 (2)
C10—N36—C34—O35	8.7 (4)	O33—C5—C4—C31	51.9 (4)
C10—N36—C34—C13	−176.98 (19)	N1—C5—C4—C31	−131.7 (2)
C18—C13—C34—O35	94.0 (3)	O33—C5—C4—C28	−64.1 (3)
C14—C13—C34—O35	−80.7 (3)	N1—C5—C4—C28	112.3 (2)
C18—C13—C34—N36	−80.6 (2)	C30'—C31—C4—C3	104.2 (9)
C14—C13—C34—N36	104.7 (2)	C30—C31—C4—C3	131.6 (5)
C5—N1—C6—C7	63.8 (3)	C30'—C31—C4—C5	−136.0 (9)
N2—N1—C6—C7	−69.3 (2)	C30—C31—C4—C5	−108.7 (5)
C8—C7—C6—N1	−98.4 (2)	C30'—C31—C4—C28	−17.7 (9)
C12—C7—C6—N1	82.2 (3)	C30—C31—C4—C28	9.7 (5)
C18—C13—C14—C15	−2.7 (3)	C29—C28—C4—C3	−148.6 (6)
C34—C13—C14—C15	171.93 (19)	C29'—C28—C4—C3	−127.7 (11)
C18—C13—C14—C19	175.96 (19)	C29—C28—C4—C5	99.8 (6)
C34—C13—C14—C19	−9.5 (3)	C29'—C28—C4—C5	120.6 (11)
C12—C7—C8—C9	0.1 (3)	C29—C28—C4—C31	−23.5 (6)
C6—C7—C8—C9	−179.4 (2)	C29'—C28—C4—C31	−2.7 (11)
N2—N1—C5—O33	176.4 (2)	N1—N2—C3—O32	171.6 (3)
C6—N1—C5—O33	40.4 (3)	C24—N2—C3—O32	21.9 (4)
N2—N1—C5—C4	−0.1 (2)	N1—N2—C3—C4	−9.1 (3)
C6—N1—C5—C4	−136.1 (2)	C24—N2—C3—C4	−158.7 (2)
C13—C14—C15—C16	−0.4 (3)	C5—C4—C3—O32	−172.3 (3)
C19—C14—C15—C16	−179.0 (2)	C31—C4—C3—O32	−45.6 (4)
C15—C14—C19—O21	−176.5 (2)	C28—C4—C3—O32	72.5 (3)
C13—C14—C19—O21	4.9 (3)	C5—C4—C3—N2	8.4 (3)
C15—C14—C19—O20	5.3 (3)	C31—C4—C3—N2	135.0 (2)
C13—C14—C19—O20	−173.33 (19)	C28—C4—C3—N2	−106.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O20—H20···O37	0.95 (4)	1.70 (4)	2.623 (3)	163 (4)
O37—H37A···O33^i	0.84 (4)	1.93 (4)	2.759 (3)	171 (4)
O37—H37B···O32^ii	0.89 (4)	1.91 (4)	2.793 (3)	174 (3)
N36—H36···O35^iii	0.93 (3)	2.08 (3)	3.002 (2)	171 (2)

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