Adipic acid–2,6-bis­(1H-benzimidazol-2-yl)pyridine–water (1/2/4)

Lin, S.; Jia, R.; Gao, F.; Zhou, X.

doi:10.1107/S1600536812047861

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3457

doi:10.1107/S1600536812047861

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Adipic acid–2,6-bis(1H-benzimidazol-2-yl)pyridine–water (1/2/4)

Songzhu Lin,^a ^* Ruokun Jia,^a Feng Gao ^a and Xiaoqing Zhou ^a

^aNortheast Dianli University, Jilin 132012, People's Republic of China
^*Correspondence e-mail: songzhulin@hotmail.com

(Received 19 October 2012; accepted 21 November 2012; online 28 November 2012)

The asymmetric unit of the title hydrated co-crystal, 2C₁₉H₁₃N₅·C₆H₁₀O₄·4H₂O, consists of one 2,6-bis(1H-benzimidazol-2-yl)pyridine molecule, half of an adipic acid molecule (bisected by an inversion center) and two water solvates. In the crystal, N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds and π–π interactions [centroid–centroid distances = 3.769 (2) and 3.731 (2) Å] form a three-dimensional supramolecular structure.

Related literature

For related structures, see: Boča et al. (2000 ); Chetia & Iyer (2006 , 2007 ); Xiao et al. (2010 ); Freire et al. (2003 ); Lin et al. (2012 ).

Experimental

Crystal data

2C₁₉H₁₃N₅·C₆H₁₀O₄·4H₂O
M_r = 840.90
Triclinic, $[P \overline 1]$
a = 9.0709 (18) Å
b = 9.6882 (19) Å
c = 12.311 (3) Å
α = 88.93 (3)°
β = 83.12 (3)°
γ = 75.14 (3)°
V = 1038.1 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.25 × 0.18 × 0.16 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
10214 measured reflections
4705 independent reflections
3555 reflections with I > 2σ(I)
R_int = 0.024
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.163
S = 1.15
4705 reflections
368 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H4⋯O2W	0.95 (2)	2.16 (2)	3.084 (2)	163.3 (18)
N4—H5⋯O2W	0.88 (2)	2.08 (2)	2.945 (2)	167.6 (18)
O1—H1⋯N5	0.87 (1)	1.83 (1)	2.6731 (19)	163 (2)
O1W—H1WA⋯N1ⁱ	0.85 (1)	1.99 (1)	2.8169 (18)	162 (2)
O1W—H1WB⋯O2ⁱⁱ	0.85 (1)	1.99 (1)	2.815 (2)	165 (2)
O2W—H2WB⋯O1Wⁱⁱⁱ	0.86 (1)	2.05 (1)	2.898 (2)	170 (3)
O2W—H2WA⋯O1W^iv	0.87 (1)	2.01 (1)	2.867 (2)	171 (3)
Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y, -z+1; (iii) -x, -y+1, -z+1; (iv) x, y+1, z-1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812047861/bg2486sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047861/bg2486Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812047861/bg2486Isup3.cml

checkCIF report

Comment top

Structures containing 2,6-bis(benzimidazol-2-yl)pyridine have been reported in recent year (Xiao et al., 2010; Freire et al., 2003; Lin et al., 2012). As a continuation of our previous works devoted to structures with 2,6-bis(benzimidazol-2-yl)pyridine, here we report the crystal structures of the title compound (C₁₉H₁₃N₅)0.5(C₆H₁₀O₄)2(H₂O)(I). Its asymmetric unit consists of one 2-pyridin-4-yl-1H-benzoimidazole molecule, half of an adipic acid molecule (bisected by an inversion center) and two water solvates. The aromatic C—C and C—N distances in both the benzimidazole and pyridine rings are within the usual range. All C and N atoms of the 2,6-bis(benzimidazol-2-yl)pyridine molecule lay in a plane (largest deviation: 0.084 Å for C16). The compound is similar to other related compounds consisting of 2,6-bis(benzimidazol-2-yl)pyridine and organic molecules (Boča et al., 2000; Chetia and Iyer, 2006; Chetia and Iyer, 2007; Xiao et al., 2010; Lin et al., 2012).

The crystal structure in (I) is a 3D array, definend by N—H···O, O—H···O, O—H···N inter- and intramolecular interactions (Table 1) and π–π stacking interactions between rings with center-to-center distances Cg1···Cg2 = 3.769 (2) (symmetry code 1 - x, 1 - y, -z), Cg2···Cg3=3.731 (2) Å (symmetry code -x, 1 - y, -z), where Cg1, Cg2 and Cg3 refer to imidazole ring N4—C13—N5—C14—C19, pyridine ring N3—C8—C9—C10—C11—C12 and phenyl ring C1—C2—C3—C4—C5—C6, respectively.

Related literature top

For related structures, see: Boča et al. (2000); Chetia & Iyer (2006, 2007); Xiao et al. (2010); Freire et al. (2003); Lin et al. (2012).

Experimental top

The title compound was obtained by 2,6-bis(benzimidazol-2-yl)pyridine (0.062 g, 0.20 mmol) and adipic acid (0.029 g, 0.20 mmol) dissolved in 30 ml solution mixed with ethanol and water by 2:1(V/V) was heated to refluxed for 8 h and cooled to the room temperature. Single crystals suitable for X-ray measurements were obtained by recrystallization at room temperature.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

Adipic acid–2,6-bis(1H-benzimidazol-2-yl)pyridine–water (1/2/4) top

Crystal data top

2C₁₉H₁₃N₅·C₆H₁₀O₄·4H₂O	Z = 1
M_r = 840.90	F(000) = 442
Triclinic, P1	D_x = 1.345 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.0709 (18) Å	Cell parameters from 25 reflections
b = 9.6882 (19) Å	θ = 4–14°
c = 12.311 (3) Å	µ = 0.10 mm⁻¹
α = 88.93 (3)°	T = 295 K
β = 83.12 (3)°	Block, yellow
γ = 75.14 (3)°	0.25 × 0.18 × 0.16 mm
V = 1038.1 (4) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.024
Radiation source: fine-focus sealed tube	θ_max = 27.5°, θ_min = 3.0°
Graphite monochromator	h = −11→11
ω scans	k = −12→12
10214 measured reflections	l = −15→15
4705 independent reflections	3 standard reflections every 100 reflections
3555 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	w = 1/[σ²(F_o²) + (0.1P)² + 0.0268P] where P = (F_o² + 2F_c²)/3
4705 reflections	(Δ/σ)_max < 0.001
368 parameters	Δρ_max = 0.36 e Å⁻³
7 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

2C₁₉H₁₃N₅·C₆H₁₀O₄·4H₂O	γ = 75.14 (3)°
M_r = 840.90	V = 1038.1 (4) Å³
Triclinic, P1	Z = 1
a = 9.0709 (18) Å	Mo Kα radiation
b = 9.6882 (19) Å	µ = 0.10 mm⁻¹
c = 12.311 (3) Å	T = 295 K
α = 88.93 (3)°	0.25 × 0.18 × 0.16 mm
β = 83.12 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.024
10214 measured reflections	3 standard reflections every 100 reflections
4705 independent reflections	intensity decay: none
3555 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.047	7 restraints
wR(F²) = 0.163	H atoms treated by a mixture of independent and constrained refinement
S = 1.15	Δρ_max = 0.36 e Å⁻³
4705 reflections	Δρ_min = −0.19 e Å⁻³
368 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N1	0.13159 (14)	0.33800 (13)	−0.15941 (10)	0.0488 (3)
N2	0.11534 (14)	0.56273 (13)	−0.10937 (10)	0.0469 (3)
H4	0.142 (2)	0.632 (2)	−0.0672 (17)	0.070 (5)*
N3	0.30720 (13)	0.47411 (12)	0.04908 (9)	0.0425 (3)
N4	0.35862 (15)	0.69020 (12)	0.16663 (10)	0.0461 (3)
H5	0.296 (2)	0.718 (2)	0.1169 (17)	0.071 (6)*
N5	0.51881 (14)	0.53946 (12)	0.26517 (10)	0.0467 (3)
C1	0.03749 (17)	0.43165 (17)	−0.22421 (12)	0.0502 (3)
C2	−0.0392 (2)	0.4018 (2)	−0.30889 (15)	0.0660 (5)
H2B	−0.029 (3)	0.302 (3)	−0.331 (2)	0.108 (9)*
C3	−0.1263 (2)	0.5167 (3)	−0.36062 (17)	0.0737 (5)
H3B	−0.177 (2)	0.500 (2)	−0.4221 (17)	0.075 (6)*
C4	−0.1367 (2)	0.6559 (3)	−0.32926 (17)	0.0738 (6)
H4B	−0.203 (2)	0.737 (2)	−0.3704 (18)	0.083 (6)*
C5	−0.0618 (2)	0.6887 (2)	−0.24504 (16)	0.0625 (4)
H5B	−0.071 (2)	0.784 (2)	−0.2255 (17)	0.072 (6)*
C6	0.02658 (16)	0.57252 (17)	−0.19362 (12)	0.0495 (4)
C7	0.17580 (15)	0.42054 (14)	−0.09313 (11)	0.0436 (3)
C8	0.28186 (15)	0.37145 (14)	−0.01174 (11)	0.0423 (3)
C9	0.35464 (18)	0.22746 (15)	−0.00130 (13)	0.0500 (4)
H9A	0.3296 (19)	0.1624 (19)	−0.0465 (15)	0.053 (4)*
C10	0.45920 (19)	0.18978 (15)	0.07321 (13)	0.0533 (4)
H10A	0.517 (2)	0.086 (2)	0.0801 (15)	0.064 (5)*
C11	0.48672 (19)	0.29346 (15)	0.13676 (13)	0.0496 (4)
H11A	0.553 (2)	0.2771 (19)	0.1892 (15)	0.058 (5)*
C12	0.40660 (15)	0.43502 (14)	0.12290 (11)	0.0423 (3)
C13	0.42912 (15)	0.55179 (14)	0.18674 (11)	0.0424 (3)
C14	0.50736 (17)	0.67897 (15)	0.29760 (12)	0.0461 (3)
C15	0.5824 (2)	0.72962 (19)	0.37449 (15)	0.0590 (4)
H15A	0.653 (3)	0.659 (2)	0.4172 (19)	0.085 (6)*
C16	0.5557 (2)	0.8759 (2)	0.38559 (16)	0.0678 (5)
H16A	0.607 (2)	0.915 (2)	0.4359 (18)	0.080 (6)*
C17	0.4553 (2)	0.96933 (19)	0.32354 (16)	0.0686 (5)
H17A	0.442 (2)	1.074 (2)	0.3320 (17)	0.080 (6)*
C18	0.3784 (2)	0.92146 (17)	0.24903 (14)	0.0588 (4)
H18A	0.308 (2)	0.984 (2)	0.2049 (17)	0.072 (6)*
C19	0.40766 (17)	0.77399 (15)	0.23620 (12)	0.0465 (3)
O1	0.67965 (16)	0.37143 (12)	0.40769 (11)	0.0688 (4)
H1	0.630 (2)	0.411 (2)	0.3538 (14)	0.084 (7)*
O2	0.74254 (17)	0.17221 (13)	0.30895 (11)	0.0732 (4)
C20	0.75243 (17)	0.23700 (16)	0.38907 (13)	0.0491 (3)
C21	0.8489 (2)	0.17588 (17)	0.47764 (14)	0.0538 (4)
H21A	0.784 (3)	0.179 (2)	0.5432 (19)	0.079 (6)*
H21B	0.915 (2)	0.250 (2)	0.4912 (16)	0.073 (6)*
C22	0.9496 (2)	0.02613 (17)	0.45481 (14)	0.0543 (4)
H22A	0.883 (2)	−0.040 (2)	0.4464 (16)	0.069 (5)*
H22B	1.019 (2)	0.022 (2)	0.3830 (17)	0.071 (5)*
O1W	0.14244 (18)	0.04491 (14)	0.85092 (11)	0.0742 (4)
O2W	0.14234 (16)	0.82851 (14)	0.01294 (13)	0.0751 (4)
H1WA	0.153 (3)	0.1282 (13)	0.8350 (18)	0.102 (8)*
H1WB	0.172 (3)	−0.0080 (19)	0.7943 (13)	0.093 (8)*
H2WB	0.064 (3)	0.870 (3)	0.058 (2)	0.152 (13)*
H2WA	0.151 (3)	0.896 (2)	−0.0326 (18)	0.126 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0533 (7)	0.0439 (7)	0.0461 (7)	−0.0062 (5)	−0.0072 (5)	−0.0025 (5)
N2	0.0474 (6)	0.0400 (6)	0.0505 (7)	−0.0060 (5)	−0.0065 (5)	0.0026 (5)
N3	0.0460 (6)	0.0359 (5)	0.0420 (6)	−0.0054 (5)	−0.0027 (5)	0.0022 (4)
N4	0.0533 (7)	0.0361 (6)	0.0453 (7)	−0.0042 (5)	−0.0081 (5)	0.0051 (5)
N5	0.0524 (7)	0.0387 (6)	0.0450 (6)	−0.0034 (5)	−0.0080 (5)	−0.0001 (5)
C1	0.0489 (8)	0.0545 (8)	0.0434 (8)	−0.0071 (7)	−0.0036 (6)	−0.0008 (6)
C2	0.0642 (10)	0.0800 (13)	0.0525 (10)	−0.0130 (9)	−0.0134 (8)	−0.0017 (9)
C3	0.0645 (11)	0.0970 (15)	0.0574 (11)	−0.0116 (10)	−0.0188 (9)	0.0053 (10)
C4	0.0572 (10)	0.0880 (14)	0.0688 (12)	−0.0038 (10)	−0.0142 (9)	0.0243 (11)
C5	0.0539 (9)	0.0595 (10)	0.0681 (11)	−0.0048 (8)	−0.0074 (8)	0.0158 (8)
C6	0.0429 (7)	0.0524 (8)	0.0491 (8)	−0.0068 (6)	−0.0025 (6)	0.0079 (6)
C7	0.0452 (7)	0.0374 (7)	0.0438 (7)	−0.0047 (6)	−0.0005 (6)	0.0003 (5)
C8	0.0449 (7)	0.0379 (7)	0.0403 (7)	−0.0060 (6)	−0.0005 (5)	0.0001 (5)
C9	0.0589 (8)	0.0353 (7)	0.0522 (8)	−0.0058 (6)	−0.0058 (7)	−0.0029 (6)
C10	0.0638 (9)	0.0345 (7)	0.0552 (9)	−0.0002 (7)	−0.0097 (7)	0.0018 (6)
C11	0.0568 (8)	0.0379 (7)	0.0498 (8)	−0.0027 (6)	−0.0110 (7)	0.0047 (6)
C12	0.0461 (7)	0.0363 (6)	0.0410 (7)	−0.0056 (6)	−0.0025 (5)	0.0021 (5)
C13	0.0451 (7)	0.0354 (6)	0.0424 (7)	−0.0034 (5)	−0.0038 (5)	0.0042 (5)
C14	0.0520 (8)	0.0401 (7)	0.0423 (7)	−0.0064 (6)	−0.0018 (6)	−0.0031 (6)
C15	0.0625 (9)	0.0558 (9)	0.0554 (9)	−0.0064 (8)	−0.0111 (7)	−0.0087 (7)
C16	0.0759 (11)	0.0624 (10)	0.0662 (11)	−0.0187 (9)	−0.0073 (9)	−0.0187 (9)
C17	0.0898 (13)	0.0429 (8)	0.0714 (12)	−0.0168 (9)	−0.0015 (10)	−0.0101 (8)
C18	0.0761 (11)	0.0375 (7)	0.0587 (10)	−0.0090 (7)	−0.0035 (8)	0.0002 (7)
C19	0.0543 (8)	0.0387 (7)	0.0430 (7)	−0.0078 (6)	−0.0006 (6)	0.0009 (6)
O1	0.0873 (9)	0.0462 (6)	0.0612 (7)	0.0133 (6)	−0.0288 (7)	−0.0021 (5)
O2	0.0936 (9)	0.0482 (6)	0.0773 (8)	0.0008 (6)	−0.0494 (7)	−0.0055 (6)
C20	0.0528 (8)	0.0410 (7)	0.0520 (8)	−0.0055 (6)	−0.0152 (6)	0.0062 (6)
C21	0.0598 (9)	0.0492 (8)	0.0475 (9)	−0.0009 (7)	−0.0154 (7)	0.0048 (6)
C22	0.0600 (9)	0.0463 (8)	0.0543 (9)	−0.0033 (7)	−0.0209 (8)	0.0062 (7)
O1W	0.1059 (10)	0.0511 (7)	0.0632 (8)	−0.0195 (7)	−0.0014 (7)	−0.0007 (6)
O2W	0.0710 (8)	0.0589 (7)	0.0809 (10)	0.0058 (6)	−0.0037 (7)	0.0200 (7)

Geometric parameters (Å, º) top

N1—C7	1.3166 (19)	C11—C12	1.3957 (19)
N1—C1	1.388 (2)	C11—H11A	0.917 (19)
N2—C7	1.3664 (17)	C12—C13	1.459 (2)
N2—C6	1.375 (2)	C14—C15	1.394 (2)
N2—H4	0.95 (2)	C14—C19	1.395 (2)
N3—C8	1.3375 (18)	C15—C16	1.381 (3)
N3—C12	1.3381 (19)	C15—H15A	1.00 (2)
N4—C13	1.3617 (17)	C16—C17	1.397 (3)
N4—C19	1.376 (2)	C16—H16A	0.96 (2)
N4—H5	0.88 (2)	C17—C18	1.370 (3)
N5—C13	1.3201 (18)	C17—H17A	1.00 (2)
N5—C14	1.3911 (18)	C18—C19	1.393 (2)
C1—C2	1.394 (2)	C18—H18A	0.98 (2)
C1—C6	1.398 (2)	O1—C20	1.3109 (19)
C2—C3	1.383 (3)	O1—H1	0.873 (10)
C2—H2B	0.99 (3)	O2—C20	1.203 (2)
C3—C4	1.386 (3)	C20—C21	1.498 (2)
C3—H3B	0.97 (2)	C21—C22	1.514 (2)
C4—C5	1.388 (3)	C21—H21A	0.94 (2)
C4—H4B	1.03 (2)	C21—H21B	1.07 (2)
C5—C6	1.394 (2)	C22—C22ⁱ	1.522 (3)
C5—H5B	0.94 (2)	C22—H22A	1.001 (19)
C7—C8	1.461 (2)	C22—H22B	1.02 (2)
C8—C9	1.3927 (19)	O1W—H1WA	0.854 (10)
C9—C10	1.376 (2)	O1W—H1WB	0.848 (9)
C9—H9A	0.935 (18)	O2W—H2WB	0.860 (10)
C10—C11	1.374 (2)	O2W—H2WA	0.865 (10)
C10—H10A	1.012 (18)

C7—N1—C1	104.88 (12)	N3—C12—C11	122.93 (14)
C7—N2—C6	106.77 (13)	N3—C12—C13	115.23 (12)
C7—N2—H4	120.0 (12)	C11—C12—C13	121.82 (14)
C6—N2—H4	133.2 (12)	N5—C13—N4	112.69 (13)
C8—N3—C12	117.85 (12)	N5—C13—C12	126.24 (12)
C13—N4—C19	107.10 (13)	N4—C13—C12	121.05 (13)
C13—N4—H5	125.1 (13)	N5—C14—C15	129.82 (15)
C19—N4—H5	127.8 (13)	N5—C14—C19	109.63 (13)
C13—N5—C14	105.00 (12)	C15—C14—C19	120.50 (15)
N1—C1—C2	129.23 (17)	C16—C15—C14	117.41 (17)
N1—C1—C6	109.80 (14)	C16—C15—H15A	124.0 (13)
C2—C1—C6	120.96 (16)	C14—C15—H15A	118.6 (13)
C3—C2—C1	117.3 (2)	C15—C16—C17	121.28 (17)
C3—C2—H2B	122.5 (16)	C15—C16—H16A	120.3 (13)
C1—C2—H2B	120.2 (16)	C17—C16—H16A	118.4 (13)
C2—C3—C4	121.2 (2)	C18—C17—C16	122.09 (16)
C2—C3—H3B	119.3 (13)	C18—C17—H17A	119.2 (12)
C4—C3—H3B	119.5 (13)	C16—C17—H17A	118.7 (12)
C3—C4—C5	122.70 (18)	C17—C18—C19	116.66 (17)
C3—C4—H4B	117.8 (13)	C17—C18—H18A	123.8 (12)
C5—C4—H4B	119.5 (13)	C19—C18—H18A	119.6 (12)
C4—C5—C6	115.93 (19)	N4—C19—C18	132.36 (15)
C4—C5—H5B	121.0 (13)	N4—C19—C14	105.57 (12)
C6—C5—H5B	123.1 (13)	C18—C19—C14	122.03 (15)
N2—C6—C5	132.52 (16)	C20—O1—H1	113.3 (16)
N2—C6—C1	105.55 (13)	O2—C20—O1	123.00 (14)
C5—C6—C1	121.93 (17)	O2—C20—C21	124.71 (14)
N1—C7—N2	112.99 (13)	O1—C20—C21	112.28 (14)
N1—C7—C8	125.67 (12)	C20—C21—C22	114.80 (14)
N2—C7—C8	121.32 (13)	C20—C21—H21A	108.3 (13)
N3—C8—C9	122.74 (14)	C22—C21—H21A	110.4 (13)
N3—C8—C7	115.52 (12)	C20—C21—H21B	106.6 (10)
C9—C8—C7	121.71 (13)	C22—C21—H21B	111.9 (11)
C10—C9—C8	118.51 (14)	H21A—C21—H21B	104.2 (17)
C10—C9—H9A	124.2 (11)	C21—C22—C22ⁱ	111.97 (18)
C8—C9—H9A	117.3 (11)	C21—C22—H22A	109.3 (11)
C11—C10—C9	119.71 (13)	C22ⁱ—C22—H22A	109.8 (11)
C11—C10—H10A	120.1 (10)	C21—C22—H22B	110.5 (11)
C9—C10—H10A	120.2 (10)	C22ⁱ—C22—H22B	108.1 (11)
C10—C11—C12	118.22 (14)	H22A—C22—H22B	107.0 (15)
C10—C11—H11A	125.1 (11)	H1WA—O1W—H1WB	108.7 (18)
C12—C11—H11A	116.6 (11)	H2WB—O2W—H2WA	102.4 (18)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H4···O2W	0.95 (2)	2.16 (2)	3.084 (2)	163.3 (18)
N4—H5···O2W	0.88 (2)	2.08 (2)	2.945 (2)	167.6 (18)
O1—H1···N5	0.87 (1)	1.83 (1)	2.6731 (19)	163 (2)
O1W—H1WA···N1ⁱⁱ	0.85 (1)	1.99 (1)	2.8169 (18)	162 (2)
O1W—H1WB···O2ⁱⁱⁱ	0.85 (1)	1.99 (1)	2.815 (2)	165 (2)
O2W—H2WB···O1W^iv	0.86 (1)	2.05 (1)	2.898 (2)	170 (3)
O2W—H2WA···O1W^v	0.87 (1)	2.01 (1)	2.867 (2)	171 (3)

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

Experimental details

Crystal data
Chemical formula	2C₁₉H₁₃N₅·C₆H₁₀O₄·4H₂O
M_r	840.90
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	9.0709 (18), 9.6882 (19), 12.311 (3)
α, β, γ (°)	88.93 (3), 83.12 (3), 75.14 (3)
V (Å³)	1038.1 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.18 × 0.16

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10214, 4705, 3555
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.163, 1.15
No. of reflections	4705
No. of parameters	368
No. of restraints	7
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.19

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H4···O2W	0.95 (2)	2.16 (2)	3.084 (2)	163.3 (18)
N4—H5···O2W	0.88 (2)	2.08 (2)	2.945 (2)	167.6 (18)
O1—H1···N5	0.873 (10)	1.825 (12)	2.6731 (19)	163 (2)
O1W—H1WA···N1ⁱ	0.854 (10)	1.993 (11)	2.8169 (18)	162 (2)
O1W—H1WB···O2ⁱⁱ	0.848 (9)	1.989 (11)	2.815 (2)	165 (2)
O2W—H2WB···O1Wⁱⁱⁱ	0.860 (10)	2.046 (12)	2.898 (2)	170 (3)
O2W—H2WA···O1W^iv	0.865 (10)	2.009 (11)	2.867 (2)	171 (3)

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

Acknowledgements

The authors would like to thank the National Natural Science Foundation of China (51003010), the Natural Science Foundation of Jilin Province (201115178) and the Science and Technology Development Project of Jilin Province (SKLSSM201132).

References

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