The ternary complex 4-(2-pyridyl)pyridinium–3,5-di­nitro­benzoate–3,5-di­nitro­benzoic acid (1/1/1)

In the title ternary complex, C₁₀H₉N₂⁺·C₇H₃N₂O₆⁻·C₇H₄N₂O₆, the pyridinium cation adopts the role of the donor in an intermolecular N—H...O hydrogen-bonding interaction with the carboxyl­ate group of the 3,5-di­nitro­benzoate anion. The mol­ecules of the ternary complex form molecular ribbons perpendicular to the b direction, which are stabilized by one N—H...O, one O—H...O and five C—H...O intermolecular hydrogen bonds. The ribbons are further interconnected by three intermolecular C—H...O hydrogen bonds into a three-dimensional network.

S1. Comment

In the crystals of adducts of carboxylic acids with organic amine bases, there is complete or occasionally only partial transfer of H atoms from the acid to the base (Burchell et al., 2001). In our previous study of such bases, the trigonally substituted 3,5-dinitrobenzoic acid, (O₂N)₂C₆H₃COOH, readily formed the anion (O₂N)₂C₆H₃COO^- and therefore can act as a multiple acceptor of hydrogen bonds (Chantrapromma et al., 2002). Our ongoing studies of 3,5-dinitrobenzoic acid complexes with amine bases led to the title adduct, (I), in which 2,4'-bipyridine was selected as the amine base. The crystal structure, hydrogen bonds and weak interactions are reported here for (I) from data collected at 153 K.

3,5-Dinitrobenzoic acid forms a 2:1 salt with 2,4'-bipyridine, in which one of the acid molecules tranfers an H atom to the bipyridine, making a ternary complex involving a 3,5-dinitrobenzoate anion, a 2'-pyridyl-4-pyridinium cation and a neutral 3,5-dinitrobenzoic acid molecule.

The bond lengths and angles in (I) are within normal ranges (Allen et al., 1987). The values within the 3,5-dinitrobenzoate anion and neutral 3,5-dinitrobenzoic acid agree with each other, except for those of the carboxylate group; O1—C17 is shorter than O7—C24, whereas O2—C17 is longer than O8—C24. This is due to the H-atom transfer process.

The benzoate anion and benzoic acid molecule are nearly planar. For the benzoate anion, the two O atoms of the nitro groups are slightly displaced from the aromatic ring, so that the O3/O4/N4/C15 and O5/O6/N3/C13 planes are twisted around the N—C bond by angles of 8.3 (1) and 4.8 (1)°, respectively. Similarly, the O9/O10/N6/C22 and O11/O12/N5/C20 planes are twisted by 8.3 (1) and 3.5 (1)°, respectively, from the plane of the benzoic acid aromatic ring. Though the dihedral angle of the neutral carboxylic acid group (O7/O8/C24/C18) with respect to its attached aromatic ring is 6.9 (1)°, that of the carboxylate group (O1/O2/C17/C11) with respect to its attached aromatic ring is 22.7 (1)°. This implies that the H-atom tranfer process leads to geometric changes in the carboxylate anion, but does not make any significant changes in the pyridinium cation, since the C—N bonds within both the charged and uncharged heterocyclic rings are almost the same. This is due to the bond-length constraints within the aromatic rings.

Within the asymmetric unit of (I), both the benzoate anion and benzoic acid molecule are interconnected by an intermolecular C14—H14···O9 interaction. The pyridinium cation is nearly planar; the dihedral angle between the two aromatic rings is 2.0 (1)°. In the packing, this cation is interconnected to the benzoate anion and benzoic acid molecule by one N—H···O and six C—H···O interactions, while both the benzoate anion and benzoic acid molecule are linked by one O—H···O and one C—H···O interactions (see Table 2). The N2—H111···O1 and O7—H117···O1 hydrogen bonds, together with the five C—H···O hydrogen bonds (C1—H1···O5, C2—H2···O12, C8—H8···O8, C9—H9···O2 and C12—H12···O7) interconnect the molecules into molecular ribbons perpendicular to the b direction (Fig. 2). There are three other hydrogen bonds (C3—H3···O10, C7—H7···O4 and C14—H14···O9), which interconnect the ribbons into a three-dimensional moleuclar arrangement.

S2. Experimental

3,5-Dinitrobenzoic acid (1.06 g, 5 mmol) and 2',4-bipyridine (0.39 g, 2.5 mmol) were thoroughly mixed and dissolved in acetone (40 ml), and water (2 ml) was added. The resulting mixture was stirred and warmed for 15 min. A clear light-yellow solution was obtained which was filtered and left to evaporate slowly in air. Single crystals for suitable X-ray diffraction studies were obtained after a few days.

S3. Refinement

All H atoms were located from difference Fourier maps and were refined isotropically; C—H distances were in the range 0.91 (2)–1.00 (2) Å.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of the title ternary complex, showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. Packing diagram of the title ternary complex, showing the molecular ribbons perpendicular to the b direction.

(I)

Crystal data

C10H9N2^+·C7H3N2O6^−·C7H4N2O6	F(000) = 1192
Mr = 580.43	Dx = 1.567 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5786 reflections
a = 9.0193 (1) Å	θ = 2.5–28.3°
b = 20.6107 (2) Å	µ = 0.13 mm^−1
c = 13.6609 (3) Å	T = 153 K
β = 104.372 (1)°	Block, colorless
V = 2460.01 (7) Å^3	0.40 × 0.40 × 0.30 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	5931 independent reflections
Radiation source: fine-focus sealed tube	4473 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
Detector resolution: 8.33 pixels mm^-1	θmax = 28.3°, θmin = 2.5°
ω scans	h = −11→12
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −27→19
Tmin = 0.950, Tmax = 0.962	l = −17→17
14651 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)] = 0.059	All H-atom parameters refined
wR(F^2) = 0.144	w = 1/[σ^2(Fo^2) + (0.066P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.98	(Δ/σ)max = 0.001
5931 reflections	Δρmax = 0.60 e Å^−3
444 parameters	Δρmin = −0.56 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (3)

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible.

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

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

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

	x	y	z	Uiso*/Ueq
O1	0.15016 (14)	0.36713 (5)	0.83796 (9)	0.0257 (3)
O2	0.08295 (16)	0.46887 (6)	0.86487 (10)	0.0332 (3)
O3	−0.00916 (15)	0.61118 (6)	0.56459 (11)	0.0360 (3)
O4	0.14167 (17)	0.60431 (6)	0.46409 (10)	0.0370 (3)
O5	0.45866 (15)	0.41558 (6)	0.47414 (10)	0.0343 (3)
O6	0.47123 (18)	0.34290 (7)	0.59077 (12)	0.0467 (4)
O7	0.22231 (15)	0.22730 (5)	0.23480 (9)	0.0288 (3)
O8	0.17238 (19)	0.29327 (6)	0.35206 (12)	0.0485 (4)
O9	0.2316 (2)	0.52882 (6)	0.30898 (10)	0.0454 (4)
O10	0.29633 (18)	0.56535 (6)	0.17667 (11)	0.0422 (4)
O11	0.47864 (17)	0.41716 (7)	−0.03973 (11)	0.0402 (4)
O12	0.46440 (17)	0.31345 (6)	−0.01737 (10)	0.0404 (3)
N1	0.29030 (15)	0.64763 (6)	0.75907 (10)	0.0216 (3)
N2	0.00691 (16)	0.66272 (7)	1.02621 (10)	0.0233 (3)
N3	0.42668 (16)	0.39497 (7)	0.55092 (11)	0.0261 (3)
N4	0.09294 (16)	0.58466 (6)	0.53490 (10)	0.0240 (3)
N5	0.44243 (16)	0.36984 (7)	0.00374 (11)	0.0270 (3)
N6	0.27081 (17)	0.52090 (7)	0.22986 (11)	0.0268 (3)
C1	0.36239 (18)	0.65592 (8)	0.68567 (12)	0.0229 (3)
C2	0.39027 (18)	0.71601 (8)	0.64781 (12)	0.0231 (3)
C3	0.34298 (19)	0.77095 (8)	0.69023 (13)	0.0260 (4)
C4	0.26697 (19)	0.76379 (8)	0.76654 (13)	0.0233 (3)
C5	0.24184 (16)	0.70142 (7)	0.79883 (11)	0.0173 (3)
C6	0.16066 (16)	0.68889 (7)	0.87991 (11)	0.0176 (3)
C7	0.10055 (18)	0.73914 (8)	0.92752 (12)	0.0217 (3)
C8	0.02382 (19)	0.72475 (8)	1.00031 (12)	0.0246 (3)
C9	0.06328 (19)	0.61333 (8)	0.98266 (12)	0.0236 (3)
C10	0.14090 (18)	0.62491 (7)	0.90956 (12)	0.0216 (3)
C11	0.18754 (17)	0.45003 (7)	0.72428 (12)	0.0197 (3)
C12	0.29060 (18)	0.41387 (7)	0.68450 (12)	0.0209 (3)
C13	0.32539 (17)	0.43507 (7)	0.59611 (12)	0.0202 (3)
C14	0.26406 (18)	0.49099 (7)	0.54576 (12)	0.0202 (3)
C15	0.16357 (17)	0.52560 (7)	0.58758 (11)	0.0193 (3)
C16	0.12477 (17)	0.50697 (7)	0.67563 (12)	0.0202 (3)
C17	0.13661 (18)	0.42816 (7)	0.81677 (12)	0.0220 (3)
C18	0.25913 (17)	0.33942 (7)	0.21703 (11)	0.0185 (3)
C19	0.32403 (17)	0.32812 (7)	0.13548 (12)	0.0192 (3)
C20	0.36793 (17)	0.38137 (7)	0.08692 (11)	0.0201 (3)
C21	0.35013 (18)	0.44487 (8)	0.11450 (12)	0.0212 (3)
C22	0.28635 (17)	0.45383 (7)	0.19606 (11)	0.0198 (3)
C23	0.24125 (18)	0.40277 (7)	0.24857 (12)	0.0196 (3)
C24	0.21311 (18)	0.28457 (7)	0.27569 (12)	0.0223 (3)
H12	0.342 (2)	0.3763 (9)	0.7146 (15)	0.029 (5)*
H21	0.383 (2)	0.4794 (9)	0.0814 (14)	0.025 (5)*
H19	0.343 (3)	0.2834 (11)	0.1132 (17)	0.045 (6)*
H111	−0.048 (2)	0.6539 (11)	1.0721 (17)	0.037 (6)*
H2	0.442 (2)	0.7199 (9)	0.5983 (16)	0.033 (5)*
H14	0.291 (2)	0.5054 (9)	0.4889 (15)	0.030 (5)*
H8	−0.021 (2)	0.7568 (10)	1.0364 (16)	0.036 (5)*
H10	0.180 (2)	0.5893 (10)	0.8804 (16)	0.033 (5)*
H1	0.396 (2)	0.6155 (10)	0.6573 (16)	0.033 (5)*
H16	0.052 (2)	0.5321 (9)	0.7038 (15)	0.027 (5)*
H4	0.237 (2)	0.8002 (10)	0.7988 (15)	0.030 (5)*
H117	0.176 (3)	0.1942 (14)	0.273 (2)	0.072 (8)*
H3	0.365 (2)	0.8137 (10)	0.6667 (16)	0.039 (6)*
H7	0.102 (2)	0.7857 (10)	0.9090 (16)	0.034 (5)*
H9	0.044 (2)	0.5721 (10)	1.0024 (15)	0.028 (5)*
H23	0.196 (2)	0.4113 (9)	0.3048 (15)	0.029 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0455 (7)	0.0127 (5)	0.0253 (6)	0.0018 (4)	0.0210 (5)	0.0014 (4)
O2	0.0605 (8)	0.0164 (6)	0.0331 (7)	0.0036 (5)	0.0310 (6)	−0.0006 (5)
O3	0.0427 (7)	0.0250 (7)	0.0430 (8)	0.0139 (5)	0.0154 (6)	0.0036 (5)
O4	0.0676 (9)	0.0205 (6)	0.0272 (7)	0.0088 (6)	0.0197 (6)	0.0087 (5)
O5	0.0466 (8)	0.0339 (7)	0.0313 (7)	0.0051 (5)	0.0263 (6)	0.0026 (5)
O6	0.0659 (9)	0.0377 (8)	0.0460 (9)	0.0313 (7)	0.0320 (8)	0.0155 (6)
O7	0.0484 (7)	0.0143 (6)	0.0285 (6)	−0.0010 (5)	0.0189 (6)	0.0035 (4)
O8	0.0911 (12)	0.0210 (7)	0.0543 (9)	0.0060 (7)	0.0575 (9)	0.0068 (6)
O9	0.0934 (12)	0.0242 (7)	0.0273 (7)	0.0062 (7)	0.0311 (8)	−0.0021 (5)
O10	0.0752 (10)	0.0165 (6)	0.0464 (8)	−0.0051 (6)	0.0367 (8)	0.0035 (5)
O11	0.0598 (9)	0.0343 (8)	0.0379 (8)	−0.0122 (6)	0.0337 (7)	0.0004 (6)
O12	0.0639 (9)	0.0298 (7)	0.0374 (8)	0.0092 (6)	0.0315 (7)	−0.0013 (6)
N1	0.0265 (7)	0.0166 (6)	0.0237 (7)	−0.0027 (5)	0.0102 (6)	−0.0023 (5)
N2	0.0278 (7)	0.0274 (7)	0.0163 (6)	−0.0036 (5)	0.0085 (6)	0.0001 (5)
N3	0.0325 (7)	0.0247 (7)	0.0249 (7)	0.0054 (6)	0.0145 (6)	0.0013 (5)
N4	0.0370 (8)	0.0138 (6)	0.0208 (7)	0.0005 (5)	0.0063 (6)	−0.0013 (5)
N5	0.0332 (7)	0.0283 (8)	0.0236 (7)	−0.0017 (6)	0.0151 (6)	−0.0005 (6)
N6	0.0438 (8)	0.0156 (7)	0.0237 (7)	−0.0003 (6)	0.0137 (6)	−0.0003 (5)
C1	0.0240 (7)	0.0233 (8)	0.0228 (8)	−0.0017 (6)	0.0086 (6)	−0.0042 (6)
C2	0.0241 (8)	0.0291 (9)	0.0170 (7)	−0.0026 (6)	0.0069 (6)	0.0011 (6)
C3	0.0332 (9)	0.0204 (8)	0.0254 (9)	−0.0027 (6)	0.0091 (7)	0.0062 (6)
C4	0.0325 (8)	0.0143 (7)	0.0247 (8)	−0.0013 (6)	0.0099 (7)	−0.0004 (6)
C5	0.0211 (7)	0.0159 (7)	0.0144 (7)	−0.0021 (5)	0.0034 (6)	−0.0020 (5)
C6	0.0214 (7)	0.0153 (7)	0.0153 (7)	−0.0020 (5)	0.0028 (6)	−0.0014 (5)
C7	0.0287 (8)	0.0163 (7)	0.0208 (8)	−0.0030 (6)	0.0074 (7)	−0.0027 (6)
C8	0.0297 (8)	0.0242 (8)	0.0212 (8)	−0.0008 (6)	0.0087 (7)	−0.0044 (6)
C9	0.0305 (8)	0.0204 (8)	0.0203 (8)	−0.0023 (6)	0.0071 (7)	0.0051 (6)
C10	0.0283 (8)	0.0164 (8)	0.0211 (8)	0.0010 (6)	0.0081 (7)	0.0004 (6)
C11	0.0295 (8)	0.0129 (7)	0.0191 (7)	−0.0023 (6)	0.0108 (6)	−0.0008 (5)
C12	0.0294 (8)	0.0142 (7)	0.0211 (8)	0.0006 (6)	0.0103 (6)	0.0014 (6)
C13	0.0259 (7)	0.0164 (7)	0.0207 (8)	0.0000 (6)	0.0102 (6)	−0.0017 (6)
C14	0.0299 (8)	0.0155 (7)	0.0174 (7)	−0.0030 (6)	0.0099 (6)	0.0000 (5)
C15	0.0284 (8)	0.0108 (7)	0.0190 (7)	−0.0010 (5)	0.0064 (6)	−0.0002 (5)
C16	0.0276 (8)	0.0137 (7)	0.0219 (8)	−0.0014 (6)	0.0113 (6)	−0.0025 (5)
C17	0.0332 (8)	0.0156 (7)	0.0212 (8)	−0.0003 (6)	0.0140 (7)	0.0005 (6)
C18	0.0219 (7)	0.0145 (7)	0.0195 (7)	0.0016 (5)	0.0057 (6)	0.0032 (5)
C19	0.0225 (7)	0.0163 (7)	0.0196 (7)	0.0003 (5)	0.0068 (6)	0.0000 (6)
C20	0.0247 (7)	0.0212 (8)	0.0166 (7)	−0.0014 (6)	0.0090 (6)	−0.0004 (6)
C21	0.0274 (8)	0.0181 (8)	0.0196 (7)	−0.0044 (6)	0.0088 (6)	0.0022 (6)
C22	0.0278 (8)	0.0141 (7)	0.0180 (7)	−0.0011 (5)	0.0068 (6)	−0.0010 (5)
C23	0.0256 (7)	0.0182 (8)	0.0169 (7)	0.0022 (6)	0.0086 (6)	0.0020 (6)
C24	0.0276 (8)	0.0163 (7)	0.0268 (8)	0.0042 (6)	0.0138 (7)	0.0040 (6)

Geometric parameters (Å, º)

O1—C17	1.2896 (18)	C5—C6	1.494 (2)
O2—C17	1.2361 (18)	C6—C7	1.402 (2)
O3—N4	1.2235 (18)	C6—C10	1.404 (2)
O4—N4	1.2262 (18)	C7—C8	1.377 (2)
O5—N3	1.2304 (18)	C7—H7	0.99 (2)
O6—N3	1.2252 (19)	C8—H8	0.97 (2)
O7—C24	1.3173 (19)	C9—C10	1.375 (2)
O7—H117	1.01 (3)	C9—H9	0.92 (2)
O8—C24	1.202 (2)	C10—H10	0.94 (2)
O9—N6	1.2287 (18)	C11—C16	1.397 (2)
O10—N6	1.2261 (18)	C11—C12	1.402 (2)
O11—N5	1.2275 (18)	C11—C17	1.516 (2)
O12—N5	1.2253 (18)	C12—C13	1.391 (2)
N1—C1	1.334 (2)	C12—H12	0.94 (2)
N1—C5	1.3539 (19)	C13—C14	1.385 (2)
N2—C9	1.341 (2)	C14—C15	1.383 (2)
N2—C8	1.345 (2)	C14—H14	0.92 (2)
N2—H111	0.91 (2)	C15—C16	1.388 (2)
N3—C13	1.4761 (19)	C16—H16	0.984 (18)
N4—C15	1.4758 (19)	C18—C23	1.397 (2)
N5—C20	1.476 (2)	C18—C19	1.401 (2)
N6—C22	1.4751 (19)	C18—C24	1.503 (2)
C1—C2	1.389 (2)	C19—C20	1.390 (2)
C1—H1	1.00 (2)	C19—H19	1.00 (2)
C2—C3	1.387 (2)	C20—C21	1.382 (2)
C2—H2	0.91 (2)	C21—C22	1.387 (2)
C3—C4	1.390 (2)	C21—H21	0.932 (19)
C3—H3	0.97 (2)	C22—C23	1.390 (2)
C4—C5	1.396 (2)	C23—H23	0.97 (2)
C4—H4	0.94 (2)
C24—O7—H117	108.0 (15)	C9—C10—H10	118.7 (13)
C1—N1—C5	117.56 (13)	C6—C10—H10	121.5 (13)
C9—N2—C8	121.63 (14)	C16—C11—C12	119.44 (14)
C9—N2—H111	119.1 (14)	C16—C11—C17	118.38 (13)
C8—N2—H111	119.2 (14)	C12—C11—C17	122.14 (13)
O6—N3—O5	124.12 (14)	C13—C12—C11	118.91 (14)
O6—N3—C13	118.25 (13)	C13—C12—H12	116.5 (12)
O5—N3—C13	117.62 (13)	C11—C12—H12	124.6 (12)
O3—N4—O4	124.09 (14)	C14—C13—C12	122.96 (14)
O3—N4—C15	118.43 (13)	C14—C13—N3	118.07 (13)
O4—N4—C15	117.47 (13)	C12—C13—N3	118.91 (13)
O12—N5—O11	124.19 (14)	C15—C14—C13	116.47 (14)
O12—N5—C20	117.71 (13)	C15—C14—H14	121.2 (12)
O11—N5—C20	118.11 (14)	C13—C14—H14	122.3 (12)
O10—N6—O9	124.01 (14)	C14—C15—C16	123.18 (14)
O10—N6—C22	117.93 (14)	C14—C15—N4	118.14 (13)
O9—N6—C22	118.06 (13)	C16—C15—N4	118.67 (13)
N1—C1—C2	124.12 (15)	C15—C16—C11	119.02 (14)
N1—C1—H1	115.9 (12)	C15—C16—H16	121.9 (11)
C2—C1—H1	120.0 (12)	C11—C16—H16	119.1 (11)
C3—C2—C1	118.01 (15)	O2—C17—O1	124.79 (14)
C3—C2—H2	120.2 (12)	O2—C17—C11	118.73 (14)
C1—C2—H2	121.7 (12)	O1—C17—C11	116.46 (13)
C2—C3—C4	119.12 (15)	C23—C18—C19	120.26 (14)
C2—C3—H3	119.5 (12)	C23—C18—C24	118.06 (13)
C4—C3—H3	121.4 (12)	C19—C18—C24	121.63 (13)
C3—C4—C5	118.93 (15)	C20—C19—C18	118.24 (14)
C3—C4—H4	121.0 (12)	C20—C19—H19	119.5 (13)
C5—C4—H4	120.0 (12)	C18—C19—H19	122.2 (13)
N1—C5—C4	122.23 (14)	C21—C20—C19	123.47 (14)
N1—C5—C6	114.99 (12)	C21—C20—N5	117.92 (13)
C4—C5—C6	122.78 (13)	C19—C20—N5	118.58 (13)
C7—C6—C10	117.96 (14)	C20—C21—C22	116.37 (14)
C7—C6—C5	122.24 (13)	C20—C21—H21	121.2 (12)
C10—C6—C5	119.79 (13)	C22—C21—H21	122.4 (12)
C8—C7—C6	119.82 (15)	C21—C22—C23	123.13 (14)
C8—C7—H7	115.6 (12)	C21—C22—N6	117.81 (13)
C6—C7—H7	124.4 (12)	C23—C22—N6	119.02 (13)
N2—C8—C7	120.30 (15)	C22—C23—C18	118.52 (14)
N2—C8—H8	115.3 (13)	C22—C23—H23	120.3 (11)
C7—C8—H8	124.4 (13)	C18—C23—H23	121.1 (11)
N2—C9—C10	120.52 (15)	O8—C24—O7	124.51 (15)
N2—C9—H9	116.9 (12)	O8—C24—C18	122.34 (14)
C10—C9—H9	122.6 (12)	O7—C24—C18	113.16 (13)
C9—C10—C6	119.77 (15)
C5—N1—C1—C2	−0.1 (2)	O3—N4—C15—C16	−7.6 (2)
N1—C1—C2—C3	1.3 (2)	O4—N4—C15—C16	171.86 (15)
C1—C2—C3—C4	−1.5 (2)	C14—C15—C16—C11	−1.1 (2)
C2—C3—C4—C5	0.6 (2)	N4—C15—C16—C11	178.06 (14)
C1—N1—C5—C4	−0.9 (2)	C12—C11—C16—C15	1.4 (2)
C1—N1—C5—C6	179.42 (13)	C17—C11—C16—C15	−176.33 (14)
C3—C4—C5—N1	0.7 (2)	C16—C11—C17—O2	−22.7 (2)
C3—C4—C5—C6	−179.70 (14)	C12—C11—C17—O2	159.60 (16)
N1—C5—C6—C7	−178.70 (13)	C16—C11—C17—O1	155.84 (15)
C4—C5—C6—C7	1.6 (2)	C12—C11—C17—O1	−21.8 (2)
N1—C5—C6—C10	0.4 (2)	C23—C18—C19—C20	−0.7 (2)
C4—C5—C6—C10	−179.25 (14)	C24—C18—C19—C20	−178.06 (14)
C10—C6—C7—C8	−0.5 (2)	C18—C19—C20—C21	−0.4 (2)
C5—C6—C7—C8	178.59 (14)	C18—C19—C20—N5	177.43 (13)
C9—N2—C8—C7	0.0 (2)	O12—N5—C20—C21	176.69 (15)
C6—C7—C8—N2	0.3 (2)	O11—N5—C20—C21	−3.2 (2)
C8—N2—C9—C10	0.1 (2)	O12—N5—C20—C19	−1.2 (2)
N2—C9—C10—C6	−0.3 (2)	O11—N5—C20—C19	178.89 (14)
C7—C6—C10—C9	0.5 (2)	C19—C20—C21—C22	0.8 (2)
C5—C6—C10—C9	−178.60 (14)	N5—C20—C21—C22	−177.02 (13)
C16—C11—C12—C13	−1.3 (2)	C20—C21—C22—C23	−0.2 (2)
C17—C11—C12—C13	176.38 (14)	C20—C21—C22—N6	177.85 (13)
C11—C12—C13—C14	0.8 (2)	O10—N6—C22—C21	9.2 (2)
C11—C12—C13—N3	−176.41 (14)	O9—N6—C22—C21	−171.51 (16)
O6—N3—C13—C14	−174.23 (16)	O10—N6—C22—C23	−172.68 (15)
O5—N3—C13—C14	4.4 (2)	O9—N6—C22—C23	6.6 (2)
O6—N3—C13—C12	3.1 (2)	C21—C22—C23—C18	−0.8 (2)
O5—N3—C13—C12	−178.26 (15)	N6—C22—C23—C18	−178.83 (13)
C12—C13—C14—C15	−0.4 (2)	C19—C18—C23—C22	1.3 (2)
N3—C13—C14—C15	176.82 (13)	C24—C18—C23—C22	178.73 (13)
C13—C14—C15—C16	0.5 (2)	C23—C18—C24—O8	−5.4 (2)
C13—C14—C15—N4	−178.60 (13)	C19—C18—C24—O8	172.01 (17)
O3—N4—C15—C14	171.54 (14)	C23—C18—C24—O7	174.58 (14)
O4—N4—C15—C14	−9.0 (2)	C19—C18—C24—O7	−8.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H111···O1^i	0.91 (2)	1.76 (2)	2.671 (2)	177 (2)
O7—H117···O1^ii	1.01 (3)	1.59 (3)	2.579 (2)	164 (3)
C1—H1···O5^iii	1.00 (2)	2.55 (2)	3.360 (2)	138 (2)
C2—H2···O12^iv	0.92 (2)	2.47 (2)	3.176 (2)	134 (2)
C3—H3···O10^v	0.98 (2)	2.58 (2)	3.399 (2)	142 (2)
C7—H7···O4^v	0.99 (2)	2.39 (2)	3.272 (2)	148 (2)
C8—H8···O8^vi	0.97 (2)	2.40 (2)	3.311 (2)	155 (2)
C9—H9···O2^i	0.92 (2)	2.52 (2)	3.211 (2)	132 (2)
C12—H12···O7^vii	0.94 (2)	2.44 (2)	3.087 (2)	126 (2)
C14—H14···O9	0.92 (2)	2.43 (2)	3.269 (2)	152 (2)

Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) −x+1, y+1/2, −z+1/2; (v) x, −y+3/2, z+1/2; (vi) −x, y+1/2, −z+3/2; (vii) x, −y+1/2, z+1/2.