2,6-Bis(1H-benzimidazol-2-yl)pyridine butyric acid monosolvate dihydrate

Lin, S.; Jia, R.; He, A.

doi:10.1107/S1600536812021915

organic compounds

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Volume 68| Part 6| June 2012| Page o1820

doi:10.1107/S1600536812021915

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2,6-Bis(1H-benzimidazol-2-yl)pyridine butyric acid monosolvate dihydrate

Songzhu Lin,^a ^* Ruokun Jia ^a and Aimin He ^a

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

(Received 2 May 2012; accepted 15 May 2012; online 19 May 2012)

In the title compound, C₁₉H₁₃N₅·C₄H₈O₂·2H₂O, the molecular skeleton of the 2,6-bis(benzimidazol-2-yl)pyridine (bbip) molecule is essentially planar (r.m.s. deviation = 0.023 Å). An extensive three-dimensional network of intermolecular N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds consolidates the crystal packing, which also exhibits π–π interactions between the five- and six-membered rings from neighbouring bbip molecules.

Related literature

For background to supramolecular interactions, see: Dale et al. (2004 ); Braga et al. (2005 ); Ring et al. (2006 ). For related structures, see: Freire et al. (2003 ); Xiao et al. (2010 ).

Experimental

Crystal data

C₁₉H₁₃N₅·C₄H₈O₂·2H₂O
M_r = 435.48
Triclinic, $[P \overline 1]$
a = 9.3950 (19) Å
b = 9.5611 (19) Å
c = 13.805 (3) Å
α = 103.27 (2)°
β = 99.91 (3)°
γ = 104.76 (3)°
V = 1131.5 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.20 × 0.18 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.982, T_max = 0.987
8683 measured reflections
3981 independent reflections
3195 reflections with I > 2σ(I)
R_int = 0.019
3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.144
S = 1.10
3981 reflections
318 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H2⋯O2W	0.90 (2)	2.12 (1)	3.006 (2)	166 (2)
N5—H1⋯O2W	0.86 (2)	2.234 (19)	3.083 (2)	169.1 (17)
O1W—H2W1⋯N4	0.83 (2)	1.96 (1)	2.7901 (19)	178 (3)
O2W—H2W2⋯O1Wⁱ	0.82 (2)	2.04 (1)	2.852 (2)	168 (3)
O2W—H1W2⋯O1Wⁱⁱ	0.81 (2)	2.06 (1)	2.856 (2)	168 (3)
O1W—H1W1⋯O1ⁱⁱⁱ	0.82 (2)	2.00 (1)	2.795 (2)	166 (3)
O2—H3⋯N2	0.85 (2)	1.89 (1)	2.712 (2)	164 (2)
Symmetry codes: (i) -x, -y+2, -z; (ii) x+1, y, z; (iii) -x-1, -y+1, -z.

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, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812021915/cv5296sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812021915/cv5296Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812021915/cv5296Isup3.cml

checkCIF report

Comment top

Crystal engineering of extended frameworks can readily be achieved using a variety of supramolecular interactions (Braga et al., 2005; Ring et al., 2006). However, the prediction of the solid state packing of simple organic cocrystals still remains an ongoing challenge (Dale et al., 2004). The supramolecular interactions, such as hydrogen bonding and π-π stacking interactions, can create network materials with infinite 1-D, 2-D or 3-D structural motifs. The supramolecular structures with 2,6-bis(benzimidazol-2-yl)pyridine have been reported in recent year (Freire et al., 2003; Xiao et al., 2010). As a continuation of those works, we report the crystal structure of the title compound (I).

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those observed in the related structures (Freire et al., 2003; Xiao et al., 2010). The aromatic C—C and C—N bond lengths in both the benzimidazole and pyridine rings are within the usual range. All C and N atoms in the 2,6-bis(benzimidazol-2-yl)pyridine molecule are almost coplanr with the largest deviation of 0.060 Å for C4.

In the crystal, the N—H···O, N—H···O and O—H···O hydrogen bonds (Table 1) consolidate the packing, which exhibits π–π interactions with the following center-to-center distances - Cg1···Cg1=3.625 (2) Å and Cg2···Cg3=3.775 (2) Å, where Cg1, Cg2 and Cg3 are centroids of N4/C13/N5/C19/C14, C14—C19 and N3/C8—C12, respectively.

Related literature top

For background to supramolecular interactions, see: Dale et al. (2004); Braga et al. (2005); Ring et al. (2006). For related structures, see: Freire et al. (2003); Xiao et al. (2010).

Experimental top

2,6-Bis(benzimidazol-2-yl)pyridine (0.062 g, 0.20 mmol) and butyric acid (0.018 g, 0.20 mmol) were dissolved in 30 ml solution mixed with ethanol and water by 2:1(V/V), then heated to refluxed for 6 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, 1999).

Figures top

Fig. 1. View of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme. Dashed lines indicate hydrogen bonds.

2,6-Bis(1H-benzimidazol-2-yl)pyridine butyric acid monosolvate dihydrate top

Crystal data top

C₁₉H₁₃N₅·C₄H₈O₂·2H₂O	Z = 2
M_r = 435.48	F(000) = 460
Triclinic, P1	D_x = 1.278 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3950 (19) Å	Cell parameters from 25 reflections
b = 9.5611 (19) Å	θ = 4–14°
c = 13.805 (3) Å	µ = 0.09 mm⁻¹
α = 103.27 (2)°	T = 295 K
β = 99.91 (3)°	Block, colourless
γ = 104.76 (3)°	0.20 × 0.18 × 0.15 mm
V = 1131.5 (4) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	3195 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
Graphite monochromator	θ_max = 25.0°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = −11→10
T_min = 0.982, T_max = 0.987	l = −16→16
8683 measured reflections	3 standard reflections every 100 reflections
3981 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.144	w = 1/[σ²(F_o²) + (0.0925P)² + 0.059P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
3981 reflections	Δρ_max = 0.22 e Å⁻³
318 parameters	Δρ_min = −0.25 e Å⁻³
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.007 (3)

Crystal data top

C₁₉H₁₃N₅·C₄H₈O₂·2H₂O	γ = 104.76 (3)°
M_r = 435.48	V = 1131.5 (4) Å³
Triclinic, P1	Z = 2
a = 9.3950 (19) Å	Mo Kα radiation
b = 9.5611 (19) Å	µ = 0.09 mm⁻¹
c = 13.805 (3) Å	T = 295 K
α = 103.27 (2)°	0.20 × 0.18 × 0.15 mm
β = 99.91 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	3195 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.019
T_min = 0.982, T_max = 0.987	3 standard reflections every 100 reflections
8683 measured reflections	intensity decay: none
3981 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	6 restraints
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.22 e Å⁻³
3981 reflections	Δρ_min = −0.25 e Å⁻³
318 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
N1	0.12979 (14)	0.51453 (15)	−0.18153 (10)	0.0466 (3)
N2	−0.05854 (14)	0.30191 (14)	−0.26517 (10)	0.0482 (3)
N3	−0.04327 (13)	0.62903 (14)	−0.06414 (9)	0.0407 (3)
N4	−0.10826 (15)	0.91520 (15)	0.12949 (10)	0.0473 (3)
N5	0.10055 (14)	0.91107 (14)	0.07405 (10)	0.0423 (3)
C1	0.06996 (18)	0.29713 (18)	−0.30066 (12)	0.0491 (4)
C2	0.0931 (2)	0.1845 (2)	−0.37465 (15)	0.0685 (5)
H2B	0.0151	0.0957	−0.4100	0.082*
C3	0.2354 (2)	0.2091 (2)	−0.39367 (18)	0.0796 (6)
H3B	0.2528	0.1363	−0.4437	0.095*
C4	0.3535 (2)	0.3401 (3)	−0.33982 (19)	0.0801 (7)
H4B	0.4485	0.3517	−0.3538	0.096*
C5	0.3335 (2)	0.4530 (2)	−0.26625 (15)	0.0652 (5)
H5B	0.4126	0.5406	−0.2303	0.078*
C6	0.18948 (18)	0.42972 (18)	−0.24846 (12)	0.0479 (4)
C7	−0.01687 (16)	0.43359 (16)	−0.19367 (11)	0.0424 (4)
C8	−0.11129 (17)	0.49146 (16)	−0.13058 (11)	0.0422 (4)
C9	−0.25971 (18)	0.40738 (18)	−0.13928 (13)	0.0526 (4)
H9A	−0.3028	0.3116	−0.1857	0.063*
C10	−0.34091 (19)	0.46967 (19)	−0.07748 (14)	0.0575 (5)
H10A	−0.4405	0.4162	−0.0816	0.069*
C11	−0.27421 (18)	0.61135 (18)	−0.00955 (13)	0.0511 (4)
H11A	−0.3277	0.6555	0.0326	0.061*
C12	−0.12534 (16)	0.68670 (16)	−0.00542 (11)	0.0408 (4)
C13	−0.04638 (16)	0.83768 (16)	0.06640 (11)	0.0409 (3)
C14	0.00703 (18)	1.04751 (17)	0.18249 (11)	0.0464 (4)
C15	0.0069 (2)	1.1702 (2)	0.25982 (14)	0.0621 (5)
H15A	−0.0794	1.1716	0.2839	0.075*
C16	0.1385 (2)	1.2887 (2)	0.29928 (15)	0.0689 (5)
H16A	0.1412	1.3716	0.3511	0.083*
C17	0.2687 (2)	1.2877 (2)	0.26338 (14)	0.0633 (5)
H17A	0.3556	1.3705	0.2918	0.076*
C18	0.27226 (19)	1.16824 (18)	0.18751 (13)	0.0536 (4)
H18A	0.3589	1.1682	0.1636	0.064*
C19	0.13926 (17)	1.04728 (17)	0.14830 (11)	0.0438 (4)
O1	−0.44196 (15)	0.06635 (14)	−0.27630 (11)	0.0743 (4)
O2	−0.28356 (15)	0.04486 (15)	−0.37563 (10)	0.0657 (4)
C20	−0.7674 (3)	−0.3547 (3)	−0.4697 (2)	0.1110 (10)
H20A	−0.8595	−0.3850	−0.4481	0.167*
H20B	−0.7183	−0.4317	−0.4725	0.167*
H20C	−0.7909	−0.3404	−0.5366	0.167*
C21	−0.6624 (2)	−0.2079 (2)	−0.39388 (18)	0.0824 (7)
H21A	−0.7139	−0.1315	−0.3902	0.099*
H21B	−0.6411	−0.2228	−0.3263	0.099*
C22	−0.5148 (2)	−0.1512 (2)	−0.42169 (14)	0.0611 (5)
H22A	−0.4618	−0.2261	−0.4227	0.073*
H22B	−0.5366	−0.1408	−0.4905	0.073*
C23	−0.41213 (18)	−0.00337 (18)	−0.35032 (13)	0.0500 (4)
O1W	−0.40511 (15)	0.92334 (16)	0.11934 (11)	0.0647 (4)
O2W	0.32779 (16)	0.81969 (16)	−0.04472 (12)	0.0690 (4)
H2	0.1745 (19)	0.6070 (13)	−0.1365 (11)	0.057 (5)*
H1	0.156 (2)	0.873 (2)	0.0390 (14)	0.056 (5)*
H2W1	−0.3168 (14)	0.920 (3)	0.1236 (19)	0.100 (8)*
H2W2	0.350 (3)	0.885 (2)	−0.0747 (19)	0.116 (10)*
H1W2	0.407 (2)	0.839 (3)	−0.0027 (17)	0.129 (12)*
H1W1	−0.435 (3)	0.928 (3)	0.1717 (13)	0.106 (9)*
H3	−0.228 (2)	0.1309 (16)	−0.3376 (16)	0.096 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0350 (7)	0.0439 (7)	0.0510 (7)	0.0049 (5)	0.0084 (6)	0.0045 (6)
N2	0.0399 (7)	0.0449 (7)	0.0514 (7)	0.0072 (6)	0.0116 (6)	0.0037 (6)
N3	0.0329 (6)	0.0430 (7)	0.0420 (6)	0.0082 (5)	0.0075 (5)	0.0094 (5)
N4	0.0398 (7)	0.0497 (7)	0.0466 (7)	0.0087 (6)	0.0125 (6)	0.0070 (6)
N5	0.0336 (7)	0.0437 (7)	0.0456 (7)	0.0076 (5)	0.0109 (5)	0.0089 (6)
C1	0.0409 (9)	0.0491 (9)	0.0513 (9)	0.0088 (7)	0.0121 (7)	0.0078 (7)
C2	0.0587 (11)	0.0579 (11)	0.0726 (12)	0.0080 (9)	0.0231 (9)	−0.0063 (9)
C3	0.0684 (13)	0.0722 (13)	0.0897 (14)	0.0193 (10)	0.0379 (11)	−0.0039 (11)
C4	0.0530 (12)	0.0789 (13)	0.1034 (16)	0.0164 (10)	0.0377 (11)	0.0069 (12)
C5	0.0414 (9)	0.0656 (11)	0.0781 (12)	0.0069 (8)	0.0204 (9)	0.0071 (10)
C6	0.0401 (8)	0.0490 (8)	0.0510 (9)	0.0116 (7)	0.0120 (7)	0.0094 (7)
C7	0.0351 (8)	0.0431 (8)	0.0445 (8)	0.0082 (6)	0.0065 (6)	0.0106 (6)
C8	0.0364 (8)	0.0405 (7)	0.0456 (8)	0.0082 (6)	0.0073 (6)	0.0104 (6)
C9	0.0399 (9)	0.0417 (8)	0.0638 (10)	0.0011 (7)	0.0123 (8)	0.0048 (7)
C10	0.0368 (8)	0.0498 (9)	0.0759 (12)	−0.0013 (7)	0.0209 (8)	0.0102 (8)
C11	0.0403 (9)	0.0485 (9)	0.0615 (10)	0.0072 (7)	0.0215 (7)	0.0104 (7)
C12	0.0337 (8)	0.0426 (8)	0.0441 (8)	0.0075 (6)	0.0092 (6)	0.0138 (6)
C13	0.0340 (8)	0.0431 (8)	0.0415 (8)	0.0064 (6)	0.0079 (6)	0.0114 (6)
C14	0.0438 (9)	0.0447 (8)	0.0432 (8)	0.0073 (7)	0.0080 (7)	0.0076 (7)
C15	0.0603 (11)	0.0585 (10)	0.0579 (10)	0.0134 (9)	0.0179 (8)	0.0011 (8)
C16	0.0769 (14)	0.0522 (10)	0.0569 (10)	0.0108 (9)	0.0056 (9)	−0.0058 (8)
C17	0.0569 (11)	0.0499 (9)	0.0618 (11)	−0.0010 (8)	−0.0030 (9)	0.0077 (8)
C18	0.0413 (9)	0.0513 (9)	0.0569 (10)	0.0023 (7)	0.0027 (7)	0.0138 (8)
C19	0.0387 (8)	0.0453 (8)	0.0416 (8)	0.0073 (6)	0.0041 (6)	0.0118 (7)
O1	0.0559 (8)	0.0539 (7)	0.0927 (10)	0.0011 (6)	0.0302 (7)	−0.0089 (7)
O2	0.0543 (8)	0.0667 (8)	0.0587 (7)	0.0007 (6)	0.0171 (6)	0.0021 (6)
C20	0.103 (2)	0.0735 (15)	0.1010 (18)	−0.0274 (14)	−0.0127 (15)	0.0078 (13)
C21	0.0645 (13)	0.0620 (12)	0.0910 (15)	−0.0090 (10)	0.0110 (11)	0.0033 (11)
C22	0.0641 (12)	0.0533 (9)	0.0529 (9)	0.0096 (9)	0.0011 (8)	0.0096 (8)
C23	0.0453 (9)	0.0477 (9)	0.0533 (9)	0.0119 (7)	0.0087 (7)	0.0123 (7)
O1W	0.0420 (7)	0.0799 (9)	0.0668 (8)	0.0146 (6)	0.0135 (6)	0.0150 (7)
O2W	0.0487 (8)	0.0607 (8)	0.0793 (9)	−0.0024 (6)	0.0019 (7)	0.0172 (7)

Geometric parameters (Å, º) top

N1—C7	1.358 (2)	C11—H11A	0.9300
N1—C6	1.375 (2)	C12—C13	1.470 (2)
N1—H2	0.90 (2)	C14—C15	1.393 (2)
N2—C7	1.3259 (19)	C14—C19	1.403 (2)
N2—C1	1.386 (2)	C15—C16	1.371 (3)
N3—C12	1.3350 (19)	C15—H15A	0.9300
N3—C8	1.3401 (19)	C16—C17	1.398 (3)
N4—C13	1.3203 (19)	C16—H16A	0.9300
N4—C14	1.383 (2)	C17—C18	1.373 (3)
N5—C13	1.3533 (19)	C17—H17A	0.9300
N5—C19	1.377 (2)	C18—C19	1.391 (2)
N5—H1	0.86 (2)	C18—H18A	0.9300
C1—C2	1.393 (2)	O1—C23	1.203 (2)
C1—C6	1.401 (2)	O2—C23	1.315 (2)
C2—C3	1.379 (3)	O2—H3	0.85 (2)
C2—H2B	0.9300	C20—C21	1.518 (3)
C3—C4	1.391 (3)	C20—H20A	0.9600
C3—H3B	0.9300	C20—H20B	0.9600
C4—C5	1.378 (3)	C20—H20C	0.9600
C4—H4B	0.9300	C21—C22	1.504 (3)
C5—C6	1.388 (2)	C21—H21A	0.9700
C5—H5B	0.9300	C21—H21B	0.9700
C7—C8	1.465 (2)	C22—C23	1.496 (2)
C8—C9	1.390 (2)	C22—H22A	0.9700
C9—C10	1.374 (2)	C22—H22B	0.9700
C9—H9A	0.9300	O1W—H2W1	0.83 (2)
C10—C11	1.374 (2)	O1W—H1W1	0.82 (2)
C10—H10A	0.9300	O2W—H2W2	0.82 (2)
C11—C12	1.385 (2)	O2W—H1W2	0.81 (2)

C7—N1—C6	107.54 (13)	N4—C13—N5	113.13 (13)
C7—N1—H2	123.1 (12)	N4—C13—C12	124.76 (13)
C6—N1—H2	129.3 (12)	N5—C13—C12	122.12 (13)
C7—N2—C1	104.86 (13)	N4—C14—C15	129.84 (16)
C12—N3—C8	117.15 (13)	N4—C14—C19	110.09 (13)
C13—N4—C14	104.64 (13)	C15—C14—C19	120.07 (16)
C13—N5—C19	107.30 (13)	C16—C15—C14	117.73 (18)
C13—N5—H1	123.4 (13)	C16—C15—H15A	121.1
C19—N5—H1	129.3 (13)	C14—C15—H15A	121.1
N2—C1—C2	130.11 (16)	C15—C16—C17	121.52 (17)
N2—C1—C6	109.96 (14)	C15—C16—H16A	119.2
C2—C1—C6	119.92 (16)	C17—C16—H16A	119.2
C3—C2—C1	117.73 (18)	C18—C17—C16	122.03 (17)
C3—C2—H2B	121.1	C18—C17—H17A	119.0
C1—C2—H2B	121.1	C16—C17—H17A	119.0
C2—C3—C4	121.61 (18)	C17—C18—C19	116.43 (17)
C2—C3—H3B	119.2	C17—C18—H18A	121.8
C4—C3—H3B	119.2	C19—C18—H18A	121.8
C5—C4—C3	121.71 (18)	N5—C19—C18	132.95 (15)
C5—C4—H4B	119.1	N5—C19—C14	104.84 (14)
C3—C4—H4B	119.1	C18—C19—C14	122.20 (15)
C4—C5—C6	116.72 (18)	C23—O2—H3	113.9 (17)
C4—C5—H5B	121.6	C21—C20—H20A	109.5
C6—C5—H5B	121.6	C21—C20—H20B	109.5
N1—C6—C5	132.63 (16)	H20A—C20—H20B	109.5
N1—C6—C1	105.07 (14)	C21—C20—H20C	109.5
C5—C6—C1	122.27 (16)	H20A—C20—H20C	109.5
N2—C7—N1	112.57 (13)	H20B—C20—H20C	109.5
N2—C7—C8	126.42 (14)	C22—C21—C20	113.3 (2)
N1—C7—C8	121.00 (13)	C22—C21—H21A	108.9
N3—C8—C9	123.26 (14)	C20—C21—H21A	108.9
N3—C8—C7	115.06 (13)	C22—C21—H21B	108.9
C9—C8—C7	121.67 (14)	C20—C21—H21B	108.9
C10—C9—C8	118.15 (15)	H21A—C21—H21B	107.7
C10—C9—H9A	120.9	C23—C22—C21	114.24 (16)
C8—C9—H9A	120.9	C23—C22—H22A	108.7
C9—C10—C11	119.67 (15)	C21—C22—H22A	108.7
C9—C10—H10A	120.2	C23—C22—H22B	108.7
C11—C10—H10A	120.2	C21—C22—H22B	108.7
C10—C11—C12	118.33 (15)	H22A—C22—H22B	107.6
C10—C11—H11A	120.8	O1—C23—O2	122.25 (16)
C12—C11—H11A	120.8	O1—C23—C22	124.19 (16)
N3—C12—C11	123.43 (14)	O2—C23—C22	113.56 (15)
N3—C12—C13	115.37 (13)	H2W1—O1W—H1W1	117 (3)
C11—C12—C13	121.19 (14)	H2W2—O2W—H1W2	102 (3)

C7—N2—C1—C2	178.8 (2)	C8—N3—C12—C13	179.95 (13)
C7—N2—C1—C6	−0.07 (19)	C10—C11—C12—N3	0.1 (3)
N2—C1—C2—C3	−178.9 (2)	C10—C11—C12—C13	−179.18 (15)
C6—C1—C2—C3	−0.1 (3)	C14—N4—C13—N5	−0.62 (17)
C1—C2—C3—C4	1.3 (4)	C14—N4—C13—C12	179.13 (14)
C2—C3—C4—C5	−1.3 (4)	C19—N5—C13—N4	0.37 (18)
C3—C4—C5—C6	0.0 (4)	C19—N5—C13—C12	−179.38 (13)
C7—N1—C6—C5	−177.18 (19)	N3—C12—C13—N4	178.66 (14)
C7—N1—C6—C1	0.76 (18)	C11—C12—C13—N4	−2.0 (2)
C4—C5—C6—N1	178.9 (2)	N3—C12—C13—N5	−1.6 (2)
C4—C5—C6—C1	1.2 (3)	C11—C12—C13—N5	177.75 (14)
N2—C1—C6—N1	−0.43 (19)	C13—N4—C14—C15	−178.98 (18)
C2—C1—C6—N1	−179.43 (17)	C13—N4—C14—C19	0.63 (17)
N2—C1—C6—C5	177.78 (16)	N4—C14—C15—C16	−179.71 (17)
C2—C1—C6—C5	−1.2 (3)	C19—C14—C15—C16	0.7 (3)
C1—N2—C7—N1	0.58 (18)	C14—C15—C16—C17	0.2 (3)
C1—N2—C7—C8	−178.33 (15)	C15—C16—C17—C18	−0.4 (3)
C6—N1—C7—N2	−0.87 (19)	C16—C17—C18—C19	−0.3 (3)
C6—N1—C7—C8	178.11 (14)	C13—N5—C19—C18	−179.13 (17)
C12—N3—C8—C9	−1.1 (2)	C13—N5—C19—C14	0.05 (17)
C12—N3—C8—C7	179.62 (13)	C17—C18—C19—N5	−179.70 (17)
N2—C7—C8—N3	−179.30 (14)	C17—C18—C19—C14	1.2 (2)
N1—C7—C8—N3	1.9 (2)	N4—C14—C19—N5	−0.42 (17)
N2—C7—C8—C9	1.4 (3)	C15—C14—C19—N5	179.24 (15)
N1—C7—C8—C9	−177.42 (15)	N4—C14—C19—C18	178.87 (14)
N3—C8—C9—C10	0.9 (3)	C15—C14—C19—C18	−1.5 (3)
C7—C8—C9—C10	−179.91 (15)	C20—C21—C22—C23	177.6 (2)
C8—C9—C10—C11	−0.1 (3)	C21—C22—C23—O1	0.2 (3)
C9—C10—C11—C12	−0.4 (3)	C21—C22—C23—O2	−179.94 (17)
C8—N3—C12—C11	0.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O2W	0.90 (2)	2.12 (1)	3.006 (2)	166 (2)
N5—H1···O2W	0.86 (2)	2.234 (19)	3.083 (2)	169.1 (17)
O1W—H2W1···N4	0.83 (2)	1.96 (1)	2.7901 (19)	178 (3)
O2W—H2W2···O1Wⁱ	0.82 (2)	2.04 (1)	2.852 (2)	168 (3)
O2W—H1W2···O1Wⁱⁱ	0.81 (2)	2.06 (1)	2.856 (2)	168 (3)
O1W—H1W1···O1ⁱⁱⁱ	0.82 (2)	2.00 (1)	2.795 (2)	166 (3)
O2—H3···N2	0.85 (2)	1.89 (1)	2.712 (2)	164 (2)

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

Experimental details

Crystal data
Chemical formula	C₁₉H₁₃N₅·C₄H₈O₂·2H₂O
M_r	435.48
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	9.3950 (19), 9.5611 (19), 13.805 (3)
α, β, γ (°)	103.27 (2), 99.91 (3), 104.76 (3)
V (Å³)	1131.5 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.18 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.982, 0.987
No. of measured, independent and observed [I > 2σ(I)] reflections	8683, 3981, 3195
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.144, 1.10
No. of reflections	3981
No. of parameters	318
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.25

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H2···O2W	0.90 (2)	2.124 (10)	3.006 (2)	165.6 (16)
N5—H1···O2W	0.86 (2)	2.234 (19)	3.083 (2)	169.1 (17)
O1W—H2W1···N4	0.83 (2)	1.961 (10)	2.7901 (19)	178 (3)
O2W—H2W2···O1Wⁱ	0.82 (2)	2.042 (12)	2.852 (2)	168 (3)
O2W—H1W2···O1Wⁱⁱ	0.81 (2)	2.056 (12)	2.856 (2)	168 (3)
O1W—H1W1···O1ⁱⁱⁱ	0.82 (2)	1.996 (12)	2.795 (2)	166 (3)
O2—H3···N2	0.85 (2)	1.890 (12)	2.712 (2)	164 (2)

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

Acknowledgements

The authors thank the National Natural Science Foundation of China (grant No. 51003010), the Natural Science Foundation of Jilin Province (grant No. 201115178) and the Science and Technology Development Project of Jilin Province (grant No. SKLSSM201132).

References

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