1,2-Bis(pyridin-4-yl)diazene–3,4,5-trihy­droxy­benzoic acid–methanol (3/2/2)

Rusu, E.; Shova, S.; Rusu, G.

doi:10.1107/S1600536812031029

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2436

https://doi.org/10.1107/S1600536812031029

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1,2-Bis(pyridin-4-yl)diazene–3,4,5-trihydroxybenzoic acid–methanol (3/2/2)

Elena Rusu,^a Sergiu Shova ^b ^* and Gheorghe Rusu ^c

^aInstitute of Macromolecular Chemistry `Petru Poni', Polymer Chemistry and Physics Department, 41A Grigore Ghica Voda Alley, Iasi-700487, Romania, ^bInstitute of Applied Physics of the Academy of Science of Moldova, 5 Academiei Street, Chisinau MD-2028, Moldova, and ^cInstitute of Macromolecular Chemistry `Petru Poni', Inorganic Polymers Department, 41A Grigore Ghica Voda Alley, Iasi-700487, Romania
^*Correspondence e-mail: shova@usm.md

(Received 14 June 2012; accepted 7 July 2012; online 14 July 2012)

The title compound, 3C₁₀H₈N₄·2C₇H₆O₅·2CH₄O, has a molecular crystal structure which results from the cocrystallization of gallic acid (GA), 4,4′-azodipyridine (AzPy) and methanol in a 2:3:2 molar ratio. The asymmetric unit comprises one molecule each of GA, AzPy and methanol in general positions and half a molecule of AzPy as this is located about a centre of inversion. In the crystal, all the components of the structure are associated via the extended system of hydrogen bonds (O—H⋯O and O—H⋯N) and π–π stacking interactions [centroid–centroid distance = 3.637 (3) Å] into two-dimensional supramolecular layers which are packed parallel to the [101] plane. The shortest perpendicular distance and the slippage between aromatic groups are 3.395 (3) and 2.152 (3) Å, respectively. The AzPy molecules display a trans conformation with respect to the azo groups.

Related literature

For the photosensitive properties of azo compounds, see: Qiu et al. (2011 ). For potential applications of gallic acid, see: Fazary et al. (2009 ). For the synthesis and cocrystallization ability of 4,4′-azodipyridine, see: Launay et al. (1991 ); Zhuang et al. (2006 ); Kanoo et al. (2012 ).

Experimental

Crystal data

3C₁₀H₈N₄·2C₇H₆O₅·2CH₄O
M_r = 956.93
Monoclinic, P 2₁ /n
a = 13.555 (5) Å
b = 11.711 (5) Å
c = 14.213 (5) Å
β = 93.427 (5)°
V = 2252.2 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 200 K
0.2 × 0.2 × 0.1 mm

Data collection

Agilent Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.982, T_max = 1.000
9591 measured reflections
4431 independent reflections
3050 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.124
S = 1.03
4431 reflections
339 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O4ⁱ	0.84 (3)	1.91 (3)	2.750 (2)	175 (2)
O2—H2⋯O6ⁱⁱ	0.86 (3)	1.83 (3)	2.650 (2)	158 (2)
O3—H3⋯N2	0.88 (3)	1.90 (3)	2.730 (2)	157 (3)
O5—H5⋯N3ⁱ	0.99 (3)	1.64 (3)	2.623 (2)	174 (2)
O6—H6A⋯N6ⁱⁱⁱ	0.82	1.94	2.755 (2)	173
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) x+1, y, z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812031029/nk2169sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812031029/nk2169Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812031029/nk2169Isup3.cml

checkCIF report

Comment top

As a part of our research interest in the photosensitive compounds, we report analysis of the crystal structure of the title compound that comprises 1:1.5:1 gallic acid, 4,4'-azodipyridine and methanol molecules. The asymmetric unit of the title compound along with the atom numbering scheme is depicted in Figure 1. Gallic acid has a great potential for structure extension by the three hydroxyl groups and carboxyl function (Fazary et al., 2009). 4,4'-Azodipyridine has been widely used for its bidentate type ligand ability (Zhuang et al.,2006; Kanoo, et al., 2012) and photoswitchable properties (Qiu, et al., 2011). In the crystal all components of the structure are interacting via an extended system of O-H_ _ _O and O-H_ _ _N hydrogen bonds, the formation of which is completely realised. The geometry of the hydrogen bonds is listed in the Table 1. The crystal structure essentially results from the packing of two-dimensional supramolecular layers in parallel orientation to the [101] plane (Figure 2). In addition, each layer is consolidated by π-π stacking interaction, which is evidenced by centroid-to-centroid distance of 3.637 Å between adjacent centrosymmetrically related AzPy rings denoted by C18 C19 C20 C21 C22 and N6 atoms.

Related literature top

For the photosensitive properties of azo compounds, see: Qiu et al. (2011). For potential applications of gallic acid, see: Fazary et al. (2009). For the synthesis and cocrystallization ability of 4,4'-azodipyridine, see: Launay et al. (1991); Zhuang et al. (2006); Kanoo et al. (2012).

Experimental top

AzPy were synthesized in our laboratory (Launay et al., 1991). Gallic acid (0.085 g, 0.5 mmol) was dissolved in 5.0 ml MeOH and the solution was poured slowly into a methanol solution (5.0 ml) of the synthesized azodipyridine (0.092 g, 0.5 mmol). The resulting mixture was stirred for 30 min and was allowed to stand at room temperature. Slow evaporation for several weeks afforded red block-like crystals.

Structure description top

For the photosensitive properties of azo compounds, see: Qiu et al. (2011). For potential applications of gallic acid, see: Fazary et al. (2009). For the synthesis and cocrystallization ability of 4,4'-azodipyridine, see: Launay et al. (1991); Zhuang et al. (2006); Kanoo et al. (2012).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the asymmetric unit for title compound with displacement ellipsoids shown at the 50% probability level.
	Fig. 2. View of two-dimensional supramolecular layer. Only H atoms involved in hydrogen bonding are shown. Hydrogen bonds are shown with dashed lines. Symmetry codes: (i) 3/2 - x,1/2 + y,1/2 - z, (ii) 1 - x,1 - y,1 - z, (iii) -x,1 - y,1 - z.

1,2-Bis(pyridin-4-yl)diazene–3,4,5-trihydroxybenzoic acid–methanol (3/2/2) top

Crystal data top

3C₁₀H₈N₄·2C₇H₆O₅·2CH₄O	F(000) = 1000
M_r = 956.93	D_x = 1.411 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
a = 13.555 (5) Å	Cell parameters from 2093 reflections
b = 11.711 (5) Å	θ = 2.7–29.4°
c = 14.213 (5) Å	µ = 0.11 mm⁻¹
β = 93.427 (5)°	T = 200 K
V = 2252.2 (15) Å³	Plate, light red
Z = 2	0.2 × 0.2 × 0.1 mm

Data collection top

Agilent Xcalibur Eos diffractometer	4431 independent reflections
Radiation source: Enhance (Mo) X-ray Source	3050 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 16.1593 pixels mm^-1	θ_max = 26.0°, θ_min = 2.7°
ω scans	h = −16→15
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −14→14
T_min = 0.982, T_max = 1.000	l = −17→12
9591 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0513P)²] where P = (F_o² + 2F_c²)/3
4431 reflections	(Δ/σ)_max < 0.001
339 parameters	Δρ_max = 0.22 e Å⁻³
2 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

3C₁₀H₈N₄·2C₇H₆O₅·2CH₄O	V = 2252.2 (15) Å³
M_r = 956.93	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.555 (5) Å	µ = 0.11 mm⁻¹
b = 11.711 (5) Å	T = 200 K
c = 14.213 (5) Å	0.2 × 0.2 × 0.1 mm
β = 93.427 (5)°

Data collection top

Agilent Xcalibur Eos diffractometer	4431 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	3050 reflections with I > 2σ(I)
T_min = 0.982, T_max = 1.000	R_int = 0.038
9591 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	2 restraints
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.22 e Å⁻³
4431 reflections	Δρ_min = −0.26 e Å⁻³
339 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.52177 (11)	0.94158 (12)	0.30966 (11)	0.0315 (4)
H1	0.5624 (19)	0.993 (2)	0.2971 (18)	0.062 (9)*
O2	0.41107 (10)	0.75077 (13)	0.34448 (11)	0.0324 (4)
H2	0.390 (2)	0.819 (2)	0.3522 (18)	0.061 (9)*
O3	0.49212 (11)	0.53785 (11)	0.33081 (12)	0.0367 (4)
H3	0.433 (2)	0.554 (2)	0.349 (2)	0.089 (11)*
O4	0.83875 (11)	0.59942 (12)	0.23623 (12)	0.0440 (5)
O5	0.84265 (11)	0.78510 (11)	0.20145 (11)	0.0349 (4)
H5	0.909 (2)	0.769 (2)	0.1798 (19)	0.067 (8)*
O6	0.68514 (11)	0.06508 (12)	0.60317 (11)	0.0395 (4)
H6A	0.7410	0.0866	0.5943	0.065 (9)*
N1	0.03690 (16)	0.5003 (2)	0.52750 (17)	0.0405 (10)	0.833 (8)
N1X	0.0184 (6)	0.4849 (11)	0.4631 (5)	0.039 (5)*	0.167 (8)
N2	0.31064 (13)	0.52709 (15)	0.40387 (15)	0.0383 (5)
N3	0.47633 (13)	0.25366 (14)	0.34904 (14)	0.0329 (5)
N4	0.18017 (12)	0.21047 (14)	0.41139 (13)	0.0325 (5)
N5	0.16762 (13)	0.18525 (15)	0.49493 (14)	0.0341 (5)
N6	−0.12425 (13)	0.12055 (16)	0.56342 (14)	0.0378 (5)
C1	0.56417 (14)	0.83667 (15)	0.29803 (14)	0.0229 (5)
C2	0.50510 (14)	0.74231 (16)	0.31668 (14)	0.0236 (5)
C3	0.54455 (14)	0.63231 (16)	0.30990 (14)	0.0256 (5)
C4	0.63951 (14)	0.61786 (17)	0.28240 (14)	0.0266 (5)
H4	0.6651	0.5446	0.2771	0.032*
C5	0.69760 (14)	0.71213 (16)	0.26244 (14)	0.0237 (5)
C6	0.65943 (14)	0.82173 (16)	0.27075 (14)	0.0238 (5)
H6	0.6980	0.8849	0.2580	0.029*
C7	0.79932 (15)	0.69343 (17)	0.23271 (15)	0.0273 (5)
C8	0.29820 (17)	0.5386 (2)	0.49523 (19)	0.0443 (6)
H8	0.3534	0.5549	0.5350	0.053*
C9	0.23096 (18)	0.50213 (18)	0.34829 (18)	0.0411 (6)
H9	0.2388	0.4915	0.2843	0.049*
C10	0.13696 (17)	0.49117 (18)	0.38069 (18)	0.0423 (6)
H10	0.0829	0.4743	0.3396	0.051*
C11	0.12626 (16)	0.50610 (18)	0.47611 (19)	0.0399 (6)
C12	0.20885 (19)	0.5279 (2)	0.53435 (19)	0.0484 (7)
H12	0.2040	0.5353	0.5991	0.058*
C13	0.40522 (17)	0.22890 (17)	0.28328 (17)	0.0355 (6)
H13	0.4229	0.2178	0.2217	0.043*
C14	0.30687 (16)	0.21897 (17)	0.30187 (16)	0.0331 (5)
H14	0.2587	0.2060	0.2536	0.040*
C15	0.28212 (15)	0.22895 (16)	0.39459 (16)	0.0282 (5)
C16	0.35448 (16)	0.25523 (17)	0.46419 (16)	0.0324 (5)
H16	0.3391	0.2640	0.5267	0.039*
C17	0.45017 (16)	0.26794 (17)	0.43762 (17)	0.0339 (5)
H17	0.4990	0.2874	0.4836	0.041*
C18	0.06578 (15)	0.16613 (17)	0.51343 (15)	0.0289 (5)
C19	−0.01382 (16)	0.20737 (18)	0.45826 (17)	0.0345 (5)
H19	−0.0049	0.2499	0.4042	0.041*
C20	−0.10726 (16)	0.18273 (19)	0.48684 (16)	0.0367 (6)
H20	−0.1614	0.2109	0.4509	0.044*
C21	−0.04618 (17)	0.08113 (19)	0.61452 (16)	0.0376 (6)
H21	−0.0569	0.0363	0.6669	0.045*
C22	0.05013 (16)	0.10366 (18)	0.59334 (15)	0.0347 (5)
H22	0.1030	0.0773	0.6321	0.042*
C23	0.64365 (18)	0.0384 (2)	0.5119 (2)	0.0531 (7)
H23A	0.6324	0.1076	0.4767	0.080*
H23B	0.5820	−0.0008	0.5172	0.080*
H23C	0.6884	−0.0096	0.4801	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0246 (8)	0.0227 (8)	0.0484 (11)	0.0012 (6)	0.0116 (7)	0.0021 (7)
O2	0.0200 (8)	0.0320 (9)	0.0462 (11)	−0.0011 (6)	0.0106 (7)	0.0002 (8)
O3	0.0309 (9)	0.0264 (8)	0.0544 (11)	−0.0063 (7)	0.0152 (8)	−0.0023 (7)
O4	0.0367 (9)	0.0286 (8)	0.0691 (13)	0.0075 (7)	0.0231 (9)	0.0008 (8)
O5	0.0245 (8)	0.0313 (8)	0.0505 (11)	0.0008 (7)	0.0163 (8)	0.0045 (7)
O6	0.0238 (9)	0.0459 (9)	0.0497 (11)	−0.0007 (7)	0.0099 (8)	0.0033 (8)
N1	0.0297 (16)	0.0532 (16)	0.0384 (19)	−0.0021 (12)	0.0018 (11)	0.0007 (13)
N2	0.0312 (11)	0.0305 (10)	0.0549 (14)	−0.0016 (8)	0.0157 (11)	0.0038 (10)
N3	0.0270 (10)	0.0294 (10)	0.0432 (12)	−0.0012 (8)	0.0098 (9)	0.0027 (9)
N4	0.0252 (10)	0.0367 (10)	0.0360 (12)	−0.0015 (8)	0.0056 (9)	−0.0010 (9)
N5	0.0282 (10)	0.0387 (10)	0.0360 (12)	−0.0020 (8)	0.0056 (9)	0.0026 (9)
N6	0.0315 (11)	0.0436 (11)	0.0392 (12)	−0.0022 (9)	0.0102 (10)	−0.0029 (10)
C1	0.0211 (10)	0.0229 (10)	0.0247 (12)	0.0007 (8)	0.0020 (9)	0.0013 (9)
C2	0.0175 (10)	0.0303 (11)	0.0233 (11)	−0.0013 (8)	0.0049 (9)	−0.0006 (9)
C3	0.0248 (11)	0.0259 (11)	0.0264 (12)	−0.0071 (9)	0.0043 (9)	−0.0008 (9)
C4	0.0260 (11)	0.0251 (11)	0.0290 (12)	0.0017 (9)	0.0037 (10)	−0.0036 (9)
C5	0.0214 (10)	0.0277 (10)	0.0224 (11)	0.0004 (9)	0.0040 (9)	−0.0009 (9)
C6	0.0214 (11)	0.0246 (10)	0.0256 (12)	−0.0028 (8)	0.0042 (9)	0.0027 (9)
C7	0.0262 (11)	0.0285 (11)	0.0277 (12)	0.0007 (9)	0.0068 (10)	−0.0018 (10)
C8	0.0334 (14)	0.0476 (15)	0.0518 (18)	−0.0066 (11)	0.0013 (13)	−0.0032 (13)
C9	0.0535 (16)	0.0340 (13)	0.0365 (15)	0.0042 (11)	0.0079 (13)	0.0055 (11)
C10	0.0348 (14)	0.0366 (13)	0.0541 (18)	−0.0029 (10)	−0.0087 (13)	0.0043 (12)
C11	0.0286 (13)	0.0331 (12)	0.0596 (18)	0.0022 (10)	0.0152 (13)	0.0077 (12)
C12	0.0465 (16)	0.0569 (16)	0.0432 (16)	0.0024 (12)	0.0133 (13)	−0.0028 (13)
C13	0.0370 (13)	0.0336 (12)	0.0372 (14)	−0.0034 (10)	0.0139 (11)	−0.0009 (11)
C14	0.0325 (13)	0.0341 (12)	0.0327 (14)	−0.0016 (10)	0.0015 (11)	−0.0001 (10)
C15	0.0244 (11)	0.0245 (10)	0.0360 (13)	−0.0001 (9)	0.0049 (10)	0.0016 (10)
C16	0.0292 (12)	0.0375 (12)	0.0313 (13)	−0.0018 (10)	0.0076 (10)	0.0010 (10)
C17	0.0266 (12)	0.0371 (12)	0.0379 (14)	−0.0028 (9)	0.0014 (11)	0.0026 (11)
C18	0.0237 (11)	0.0295 (11)	0.0339 (13)	0.0010 (9)	0.0051 (10)	−0.0044 (10)
C19	0.0315 (13)	0.0365 (12)	0.0361 (14)	0.0006 (10)	0.0076 (11)	0.0026 (11)
C20	0.0257 (12)	0.0434 (13)	0.0410 (15)	0.0040 (10)	0.0017 (11)	−0.0029 (12)
C21	0.0387 (14)	0.0421 (13)	0.0330 (14)	−0.0031 (11)	0.0107 (11)	0.0010 (11)
C22	0.0319 (12)	0.0402 (13)	0.0318 (13)	0.0020 (10)	0.0011 (10)	0.0012 (11)
C23	0.0410 (15)	0.0501 (15)	0.068 (2)	0.0060 (12)	−0.0027 (14)	−0.0099 (14)

Geometric parameters (Å, º) top

O1—H1	0.84 (3)	C5—C6	1.392 (3)
O1—C1	1.371 (2)	C5—C7	1.482 (3)
O2—H2	0.86 (3)	C6—H6	0.9300
O2—C2	1.360 (2)	C8—H8	0.9300
O3—H3	0.88 (3)	C8—C12	1.368 (3)
O3—C3	1.357 (2)	C9—H9	0.9300
O4—C7	1.224 (2)	C9—C10	1.386 (3)
O5—H5	0.99 (3)	C10—H10	0.9300
O5—C7	1.314 (2)	C10—C11	1.384 (3)
O6—H6A	0.8154	C11—C12	1.376 (3)
O6—C23	1.417 (3)	C12—H12	0.9300
N1—N1ⁱ	1.232 (4)	C13—H13	0.9300
N1—C11	1.453 (3)	C13—C14	1.379 (3)
N1X—N1Xⁱ	1.239 (10)	C14—H14	0.9300
N1X—C11	1.483 (9)	C14—C15	1.384 (3)
N2—C8	1.326 (3)	C15—C16	1.385 (3)
N2—C9	1.332 (3)	C16—H16	0.9300
N3—C13	1.334 (3)	C16—C17	1.380 (3)
N3—C17	1.339 (3)	C17—H17	0.9300
N4—N5	1.245 (2)	C18—C19	1.383 (3)
N4—C15	1.433 (3)	C18—C22	1.378 (3)
N5—C18	1.438 (3)	C19—H19	0.9300
N6—C20	1.341 (3)	C19—C20	1.383 (3)
N6—C21	1.330 (3)	C20—H20	0.9300
C1—C2	1.399 (3)	C21—H21	0.9300
C1—C6	1.381 (3)	C21—C22	1.383 (3)
C2—C3	1.400 (3)	C22—H22	0.9300
C3—C4	1.378 (3)	C23—H23A	0.9600
C4—H4	0.9300	C23—H23B	0.9600
C4—C5	1.395 (3)	C23—H23C	0.9600

C1—O1—H1	109.4 (17)	C10—C11—N1X	91.0 (3)
C2—O2—H2	115.5 (17)	C12—C11—N1	112.3 (2)
C3—O3—H3	112.6 (19)	C12—C11—N1X	150.0 (3)
C7—O5—H5	112.8 (14)	C12—C11—C10	119.0 (2)
C23—O6—H6A	104.3	C8—C12—C11	118.7 (2)
N1ⁱ—N1—C11	110.5 (3)	C8—C12—H12	120.6
N1Xⁱ—N1X—C11	106.9 (10)	C11—C12—H12	120.6
C8—N2—C9	117.2 (2)	N3—C13—H13	118.3
C13—N3—C17	117.73 (19)	N3—C13—C14	123.4 (2)
N5—N4—C15	112.51 (19)	C14—C13—H13	118.3
N4—N5—C18	113.50 (19)	C13—C14—H14	121.1
C21—N6—C20	117.52 (19)	C13—C14—C15	117.9 (2)
O1—C1—C2	115.87 (17)	C15—C14—H14	121.1
O1—C1—C6	123.58 (16)	C14—C15—N4	115.9 (2)
C6—C1—C2	120.54 (17)	C14—C15—C16	119.80 (19)
O2—C2—C1	123.65 (17)	C16—C15—N4	124.3 (2)
O2—C2—C3	117.08 (16)	C15—C16—H16	121.1
C1—C2—C3	119.23 (17)	C17—C16—C15	117.7 (2)
O3—C3—C2	121.84 (17)	C17—C16—H16	121.1
O3—C3—C4	118.18 (17)	N3—C17—C16	123.4 (2)
C4—C3—C2	119.97 (17)	N3—C17—H17	118.3
C3—C4—H4	119.7	C16—C17—H17	118.3
C3—C4—C5	120.58 (18)	C19—C18—N5	124.54 (19)
C5—C4—H4	119.7	C22—C18—N5	115.48 (19)
C4—C5—C7	119.14 (17)	C22—C18—C19	119.97 (19)
C6—C5—C4	119.70 (18)	C18—C19—H19	121.4
C6—C5—C7	121.15 (17)	C18—C19—C20	117.2 (2)
C1—C6—C5	119.95 (17)	C20—C19—H19	121.4
C1—C6—H6	120.0	N6—C20—C19	123.8 (2)
C5—C6—H6	120.0	N6—C20—H20	118.1
O4—C7—O5	123.09 (19)	C19—C20—H20	118.1
O4—C7—C5	122.20 (18)	N6—C21—H21	118.5
O5—C7—C5	114.71 (17)	N6—C21—C22	123.1 (2)
N2—C8—H8	118.1	C22—C21—H21	118.5
N2—C8—C12	123.8 (2)	C18—C22—C21	118.3 (2)
C12—C8—H8	118.1	C18—C22—H22	120.8
N2—C9—H9	118.2	C21—C22—H22	120.8
N2—C9—C10	123.5 (2)	O6—C23—H23A	109.5
C10—C9—H9	118.2	O6—C23—H23B	109.5
C9—C10—H10	121.1	O6—C23—H23C	109.5
C11—C10—C9	117.8 (2)	H23A—C23—H23B	109.5
C11—C10—H10	121.1	H23A—C23—H23C	109.5
N1—C11—N1X	37.8 (3)	H23B—C23—H23C	109.5
C10—C11—N1	128.8 (2)

O1—C1—C2—O2	0.2 (3)	C3—C4—C5—C6	0.3 (3)
O1—C1—C2—C3	−177.56 (18)	C3—C4—C5—C7	−179.79 (19)
O1—C1—C6—C5	178.69 (18)	C4—C5—C6—C1	−0.5 (3)
O2—C2—C3—O3	−0.6 (3)	C4—C5—C7—O4	−9.3 (3)
O2—C2—C3—C4	−179.80 (19)	C4—C5—C7—O5	169.88 (19)
O3—C3—C4—C5	−178.34 (19)	C6—C1—C2—O2	179.48 (19)
N1ⁱ—N1—C11—N1X	−12.9 (8)	C6—C1—C2—C3	1.7 (3)
N1ⁱ—N1—C11—C10	−12.1 (4)	C6—C5—C7—O4	170.6 (2)
N1ⁱ—N1—C11—C12	168.9 (3)	C6—C5—C7—O5	−10.2 (3)
N1—C11—C12—C8	−178.3 (2)	C7—C5—C6—C1	179.6 (2)
N1Xⁱ—N1X—C11—N1	12.6 (8)	C8—N2—C9—C10	1.9 (3)
N1Xⁱ—N1X—C11—C10	−166.8 (14)	C9—N2—C8—C12	−0.9 (3)
N1Xⁱ—N1X—C11—C12	16 (2)	C9—C10—C11—N1	179.4 (2)
N1X—C11—C12—C8	179.4 (10)	C9—C10—C11—N1X	179.9 (5)
N2—C8—C12—C11	−1.3 (4)	C9—C10—C11—C12	−1.7 (3)
N2—C9—C10—C11	−0.6 (3)	C10—C11—C12—C8	2.6 (3)
N3—C13—C14—C15	−3.8 (3)	C13—N3—C17—C16	1.8 (3)
N4—N5—C18—C19	−21.4 (3)	C13—C14—C15—N4	−175.97 (17)
N4—N5—C18—C22	159.80 (19)	C13—C14—C15—C16	4.0 (3)
N4—C15—C16—C17	178.45 (18)	C14—C15—C16—C17	−1.5 (3)
N5—N4—C15—C14	158.93 (18)	C15—N4—N5—C18	−179.91 (16)
N5—N4—C15—C16	−21.0 (3)	C15—C16—C17—N3	−1.5 (3)
N5—C18—C19—C20	−179.0 (2)	C17—N3—C13—C14	0.9 (3)
N5—C18—C22—C21	−179.25 (19)	C18—C19—C20—N6	−0.9 (3)
N6—C21—C22—C18	−2.6 (3)	C19—C18—C22—C21	1.9 (3)
C1—C2—C3—O3	177.32 (19)	C20—N6—C21—C22	1.6 (3)
C1—C2—C3—C4	−1.9 (3)	C21—N6—C20—C19	0.3 (3)
C2—C1—C6—C5	−0.6 (3)	C22—C18—C19—C20	−0.2 (3)
C2—C3—C4—C5	0.9 (3)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱⁱ	0.84 (3)	1.91 (3)	2.750 (2)	175 (2)
O2—H2···O6ⁱⁱⁱ	0.86 (3)	1.83 (3)	2.650 (2)	158 (2)
O3—H3···N2	0.88 (3)	1.90 (3)	2.730 (2)	157 (3)
O5—H5···N3ⁱⁱ	0.99 (3)	1.64 (3)	2.623 (2)	174 (2)
O6—H6A···N6^iv	0.82	1.94	2.755 (2)	173

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

Experimental details

Crystal data
Chemical formula	3C₁₀H₈N₄·2C₇H₆O₅·2CH₄O
M_r	956.93
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	13.555 (5), 11.711 (5), 14.213 (5)
β (°)	93.427 (5)
V (Å³)	2252.2 (15)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.2 × 0.2 × 0.1

Data collection
Diffractometer	Agilent Xcalibur Eos
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.982, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9591, 4431, 3050
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.124, 1.03
No. of reflections	4431
No. of parameters	339
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.26

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4ⁱ	0.84 (3)	1.91 (3)	2.750 (2)	175 (2)
O2—H2···O6ⁱⁱ	0.86 (3)	1.83 (3)	2.650 (2)	158 (2)
O3—H3···N2	0.88 (3)	1.90 (3)	2.730 (2)	157 (3)
O5—H5···N3ⁱ	0.99 (3)	1.64 (3)	2.623 (2)	174 (2)
O6—H6A···N6ⁱⁱⁱ	0.82	1.94	2.755 (2)	172.8

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

Acknowledgements

This research was supported financially by the European Regional Development Fund, Sectoral Operational Programme `Increase of Economic Competitiveness', Priority Axis 2 (SOP IEC-A2-O2.1.2-2009-2, ID 570, COD SMIS-CSNR: 12473, Contract No. 129/2010-POLISILMET).

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