1,4-Bis(4,5-dihydro-1H-imidazol-2-yl)benzene–terephthalic acid–water (1/1/4)

Shang, S.-M.; Li, S.-Y.; Ren, C.-X.; Wang, X.; Lu, L.-D.

doi:10.1107/S1600536809040616

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Pages o2682-o2683

https://doi.org/10.1107/S1600536809040616

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1,4-Bis(4,5-dihydro-1H-imidazol-2-yl)benzene–terephthalic acid–water (1/1/4)

Shao-Ming Shang,^a Su-Yun Li,^b Chun-Xia Ren,^c Xin Wang ^a ^* and Lu-De Lu ^a

^aSchool of Chemical and Material Engineering, Nanjing University of Science and Technology, 200 Xiaolingwei Road, Nanjing, Jiangsu Province 210094, People's Republic of China, ^bDepartment of Public Education, Jiangxi Vocational & Technical College of Electricity, 8 Mailu Road, Nanchang, Jiangxi Province 330032, People's Republic of China, and ^cSchool of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu Province 214122, People's Republic of China
^*Correspondence e-mail: liweijun947@163.com

(Received 21 September 2009; accepted 6 October 2009; online 10 October 2009)

The asymmetric unit of the title compound, C₁₂H₁₄N₄·C₈H₆O₄·4H₂O, consists of one half of the 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib) molecule, one half of the terephthalic acid (TA) molecule and two water molecules. Both the bib and the TA molecules reside on crystallographic inversion centers, which coincide with the centroids of the respective benzene rings. The bib and the TA, together with the water molecules, are linked through intermolecular O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds, forming a three-dimensional network of stacked layers. Weak intermolecular C—H⋯O contacts support the stability of the crystal structure.

Related literature

For general background, see: Jeffrey (1997 ). For hydrogen bonding in molecular complexes of disubstituted biphenyls, see: Thaimattam et al. (1998 ). For the synthesis of the title compound, see: Ren et al. (2007 ). For related structures, see: Ren et al. (2007, 2009 and literature cited therein); Shang et al. (2009 ). For experimental refinement details, see: Nardelli, (1999 ).

Experimental

Crystal data

C₁₂H₁₄N₄·C₈H₆O₄·4H₂O
M_r = 452.46
Monoclinic, P 2₁ /c
a = 7.9929 (13) Å
b = 16.847 (3) Å
c = 7.9615 (12) Å
β = 94.899 (3)°
V = 1068.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 273 K
0.50 × 0.35 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.947, T_max = 0.968
5588 measured reflections
2300 independent reflections
832 reflections with I > 2σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.090
wR(F²) = 0.257
S = 0.79
2300 reflections
158 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H2WB⋯O1ⁱ	0.85 (4)	2.37 (6)	2.904 (5)	121 (7)
O2W—H2WA⋯O1ⁱⁱ	0.85	1.96	2.815 (5)	180
O1W—H1WB⋯O2Wⁱⁱⁱ	0.85 (4)	2.08 (4)	2.926 (5)	172 (5)
O1W—H1WA⋯O2^iv	0.86 (3)	1.851 (15)	2.707 (5)	172 (3)
O2—H2D⋯N1	0.82	2.13	2.934 (4)	165
N2—H2C⋯O1W^v	0.86	1.98	2.828 (4)	167
C5—H5⋯O1	0.93	2.50	3.407 (4)	165
C6—H6⋯O1W^v	0.93	2.47	3.380 (6)	166
Symmetry codes: (i) x, y, z+1; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x+1, y, z; (v) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040616/si2204sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040616/si2204Isup2.hkl

checkCIF report

Comment top

Attention has recently focused on the use of supramolecular interactions such as hydrogen bonding and π–π interactions, in addition to coordinate bonds, in the controlled assembly of supramolecular architectures (Jeffrey, 1997). Hydrogen bonds often play a dominant role in crystal engineering because of their combine strength with directionality (Thaimattam, et al., 1998). On the other hand, supramolecular systems sustained by soft connections, such as hydrogen bonds, are comparatively more flexible and sensitive to the chemical environment. We described previously a number of such complexes, including the imidazole ligand, and have concluded that hydrogen bonding involving this group influences the geometry around the metal atom and the crystallization mechanism [Ren, et al. (2007, 2009 and literature cited therein); Shang et al. (2009)]. We describe herewith the synthesis and crystal structure of the title compound, (Fig. 1), namely bib.TA.4H₂O (I) (bib = 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene, TA = terephthalate), which exhibits a three-dimensional hydrogen-bonded molecular architecture.

The crystal lattice contains two bib, two TA and eight lattice water molecules in the solid. The bib and TA in a trans, trans configuration are in a face-to-face orientation and the dihedral angle between acid TA and base bib components is 9.5°. And the bib and TA ligands are joined together by two water molecules through hydrogen bonds between the carboxy oxygen atom in TA and the nitrogen atom of –C=N– in bib to give a macrocycle O1W–H1WB···O2W, O2W—H2WB···O1, O1W—H1WA···O2, N2—H2C···O1W and O2–H2D···N1 with the hydrogen bond geometry given in Table 1, and a face-to-face intracyclic \<i>p-\<i>p interaction at 3.69 Å (Fig. 1). Each bib group also features another macrocycles, resulting in 1-D chains running along the a axis. As illustrated in Fig. 2, the adjacent TA ligands are furthermore linked in the antiparallel alignment with offset along the ab plane by hydrogen bonds between the water molecules and the oxygen of TA groups (O2W—H2WA···O1, O1W—H1WA···O2, O2W—H2WB···O1, and O1W—H1WB···O2W (see Table 1). These ab planes are packed and stabilized by the hydrogen bonds between the lattice water and oxygen atom of TA ligands (O2w—H2wa···O1 = 2.82 Å) into a 3-D structure. Weak intermolecular C—H···O contacts contribute to the stability of the layered structure (Table 1).

Related literature top

For general background, see: Jeffrey (1997). For hydrogen bonding in molecular complexes of disubstituted biphenyls, see: Thaimattam et al. (1998). For the synthesis of the title compound, see: Ren et al. (2007). For related structures, see: Ren et al. (2007, 2009 and literature cited therein); Shang et al. (2009). For experimental refinement details, see: Nardelli, (1999).

Experimental top

All the reagents and solvents employed were commercially available and used as received without further purification.

Syntheses of bib 1,4-Benzenedicarboxylic acid (2.31 g, 13.9 mmol), ethylenediamine (3.70 ml, 50 mmol), ethylenediamine dihydrochloride(6.64 g, 50 mmol) and toluene-p-sulfonic acid (0.208 g, 1.09 mmol) were added to the solvent of ethyleneglycol (20 ml), and the mixture solution was refluxed for 3 hr. About half of the ethylene glycol solvent was then slowly removed by distillation. The residue was dissolved in a mixture of water (40 ml) and concentrated HCl (11 M, 3 ml). The addition of 50% aqueous NaOH gave a yellow precipitate that was purified by recrystallization. The ligand bib was obtained in 83% based on 1,4-benzenedicarboxylic acid (ca 2.50 g). Found: C 66.98; H 6.92; N 26.08%. Calc. for C12H14N4: C 67.27; H 6.59; N 26.15%. Main IR bonds (KBr, cm^-1): 3188m, 2936m, 2866m, 1606 s, 1532 s, 1466 s, 1345m, 1270 s, 1191w, 1080w, 981m, 907w, 767w, 687m.

Syntheses of bib.TA.4H₂O (I) To a solution of bib (0.043 g, 0.2 mmol) in MeOH (15 ml), an aqueous solution (5 ml) of TA (0.034 g, 0.2 mmol) was added. The solution was allowed at room temperature in air for 48 hr by slow evaporation. Large colourless prismatic crystals of bib.TA.4H₂O were obtained, which were collected by filtration, washed with water and dried in vacuum desiccator over silica gel (0.052 g, 56%). Found: C 53.02; H 6.20; N 12.31%. Calc. for C10H14N2O4: C 53.09; H 6.24; N 12.38%. Main IR bonds (KBr,cm^-1): 3351m, 3142m, 2985m, 1626 s, 1601 s, 1582 s, 1516w, 1366 s, 1351 s, 1281m, 1040w, 864w, 822m, 752w, 689m.

Structure description top

For general background, see: Jeffrey (1997). For hydrogen bonding in molecular complexes of disubstituted biphenyls, see: Thaimattam et al. (1998). For the synthesis of the title compound, see: Ren et al. (2007). For related structures, see: Ren et al. (2007, 2009 and literature cited therein); Shang et al. (2009). For experimental refinement details, see: Nardelli, (1999).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Symmetry-related atoms shown labelled A and B. [symmetry codes A: (-x + 1, -y + 2, -z); B: (-x + 1, -y + 1, -z).
	Fig. 2. A partial packing diagram for the title compound. Hydrogen bonds are shown as dashed lines.

1,4-Bis(4,5-dihydro-1H-imidazol-2-yl)benzene–terephthalic acid–water (1/1/4) top

Crystal data top

C₁₂H₁₄N₄·C₈H₆O₄·4H₂O	F(000) = 480
M_r = 452.46	D_x = 1.407 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.9929 (13) Å	Cell parameters from 978 reflections
b = 16.847 (3) Å	θ = 2.4–22.2°
c = 7.9615 (12) Å	µ = 0.11 mm⁻¹
β = 94.899 (3)°	T = 273 K
V = 1068.2 (3) Å³	Block, colorless
Z = 2	0.50 × 0.35 × 0.30 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2300 independent reflections
Radiation source: fine-focus sealed tube	832 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.075
φ and ω scans	θ_max = 27.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
T_min = 0.947, T_max = 0.968	k = −21→21
5588 measured reflections	l = −5→10

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)] = 0.090	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.257	w = 1/[σ²(F_o²) + (0.1628P)²] where P = (F_o² + 2F_c²)/3
S = 0.79	(Δ/σ)_max < 0.001
2300 reflections	Δρ_max = 0.71 e Å⁻³
158 parameters	Δρ_min = −0.43 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: 0.12 (2)

Crystal data top

C₁₂H₁₄N₄·C₈H₆O₄·4H₂O	V = 1068.2 (3) Å³
M_r = 452.46	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.9929 (13) Å	µ = 0.11 mm⁻¹
b = 16.847 (3) Å	T = 273 K
c = 7.9615 (12) Å	0.50 × 0.35 × 0.30 mm
β = 94.899 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2300 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	832 reflections with I > 2σ(I)
T_min = 0.947, T_max = 0.968	R_int = 0.075
5588 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.090	6 restraints
wR(F²) = 0.257	H atoms treated by a mixture of independent and constrained refinement
S = 0.79	Δρ_max = 0.71 e Å⁻³
2300 reflections	Δρ_min = −0.43 e Å⁻³
158 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	0.2209 (4)	0.83842 (17)	0.1428 (4)	0.0622 (10)
N2	0.0932 (4)	0.95122 (17)	0.1837 (4)	0.0621 (10)
H2C	0.0744	1.0015	0.1797	0.074*
C1	−0.0182 (6)	0.8931 (2)	0.2516 (6)	0.0704 (13)
H1A	−0.1318	0.8981	0.1991	0.085*
H1B	−0.0199	0.8989	0.3726	0.085*
C2	0.0597 (6)	0.8138 (2)	0.2069 (6)	0.0692 (13)
H2A	0.0785	0.7800	0.3053	0.083*
H2B	−0.0109	0.7860	0.1208	0.083*
C3	0.2264 (5)	0.9167 (2)	0.1292 (4)	0.0558 (11)
C4	0.3678 (5)	0.9588 (2)	0.0625 (4)	0.0541 (11)
C5	0.4927 (6)	0.9183 (2)	−0.0102 (5)	0.0684 (13)
H5	0.4886	0.8632	−0.0177	0.082*
O1	0.4731 (4)	0.71811 (16)	0.0453 (4)	0.0702 (9)
O2	0.2324 (5)	0.66542 (18)	0.1033 (4)	0.0915 (11)
H2D	0.2110	0.7124	0.1183	0.137*
C6	0.3758 (6)	1.0410 (2)	0.0723 (5)	0.0659 (12)
H6	0.2921	1.0689	0.1212	0.079*
C7	0.3793 (7)	0.6590 (2)	0.0620 (5)	0.0649 (12)
C8	0.4386 (5)	0.5771 (2)	0.0299 (5)	0.0570 (11)
C9	0.6008 (6)	0.5648 (2)	−0.0226 (5)	0.0647 (12)
H9	0.6694	0.6082	−0.0391	0.078*
C10	0.3416 (6)	0.5107 (2)	0.0509 (5)	0.0644 (12)
H10	0.2339	0.5170	0.0849	0.077*
O1W	0.9737 (5)	0.61448 (19)	0.2736 (5)	0.0901 (12)
H1WA	1.053 (4)	0.627 (2)	0.212 (5)	0.11 (2)*
H1WB	0.904 (5)	0.6509 (19)	0.296 (6)	0.10 (2)*
O2W	0.7204 (4)	0.76340 (18)	0.8161 (5)	0.0821 (11)
H2WA	0.6459	0.7691	0.7341	0.098*
H2WB	0.700 (6)	0.776 (7)	0.916 (3)	0.31 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.076 (2)	0.0398 (17)	0.073 (2)	−0.0058 (16)	0.0184 (18)	0.0054 (15)
N2	0.074 (2)	0.0401 (18)	0.074 (2)	0.0037 (17)	0.0201 (19)	0.0008 (15)
C1	0.082 (3)	0.050 (2)	0.082 (3)	−0.003 (2)	0.021 (2)	0.002 (2)
C2	0.087 (3)	0.047 (2)	0.076 (3)	−0.002 (2)	0.022 (2)	0.0008 (19)
C3	0.078 (3)	0.040 (2)	0.050 (2)	0.000 (2)	0.007 (2)	0.0006 (16)
C4	0.072 (3)	0.043 (2)	0.048 (2)	−0.0032 (19)	0.015 (2)	0.0032 (16)
C5	0.094 (3)	0.039 (2)	0.077 (3)	0.003 (2)	0.033 (3)	−0.003 (2)
O1	0.089 (2)	0.0440 (15)	0.080 (2)	0.0001 (15)	0.0227 (16)	−0.0008 (13)
O2	0.099 (3)	0.0495 (17)	0.132 (3)	0.0123 (16)	0.046 (2)	−0.0028 (16)
C6	0.079 (3)	0.042 (2)	0.081 (3)	0.004 (2)	0.029 (2)	0.0007 (19)
C7	0.080 (3)	0.050 (2)	0.067 (3)	0.003 (2)	0.018 (2)	0.0043 (19)
C8	0.069 (3)	0.047 (2)	0.056 (2)	0.0062 (19)	0.012 (2)	0.0006 (17)
C9	0.082 (3)	0.042 (2)	0.071 (3)	−0.007 (2)	0.011 (2)	−0.0018 (19)
C10	0.080 (3)	0.040 (2)	0.075 (3)	−0.0062 (19)	0.020 (2)	−0.0006 (18)
O1W	0.100 (3)	0.0528 (19)	0.123 (3)	−0.0071 (19)	0.038 (2)	0.0076 (17)
O2W	0.076 (2)	0.077 (2)	0.094 (3)	0.0043 (16)	0.0140 (17)	0.0025 (18)

Geometric parameters (Å, º) top

N1—C3	1.324 (5)	O2—C7	1.251 (5)
N1—C2	1.485 (5)	O2—H2D	0.8200
N2—C3	1.319 (5)	C6—C5ⁱ	1.381 (5)
N2—C1	1.458 (5)	C6—H6	0.9300
N2—H2C	0.8600	C7—C8	1.487 (6)
C1—C2	1.528 (5)	C8—C10	1.379 (5)
C1—H1A	0.9700	C8—C9	1.412 (6)
C1—H1B	0.9700	C9—C10ⁱⁱ	1.377 (5)
C2—H2A	0.9700	C9—H9	0.9300
C2—H2B	0.9700	C10—C9ⁱⁱ	1.377 (5)
C3—C4	1.472 (6)	C10—H10	0.9300
C4—C5	1.377 (5)	O1W—H1WA	0.86 (3)
C4—C6	1.389 (5)	O1W—H1WB	0.86 (4)
C5—C6ⁱ	1.381 (5)	O2W—H2WA	0.85
C5—H5	0.9299	O2W—H2WB	0.85 (4)
O1—C7	1.260 (5)

C3—N1—C2	110.0 (3)	C4—C5—C6ⁱ	120.4 (3)
C3—N2—C1	111.2 (3)	C4—C5—H5	119.9
C3—N2—H2C	124.4	C6ⁱ—C5—H5	119.7
C1—N2—H2C	124.4	C7—O2—H2D	109.5
N2—C1—C2	103.1 (3)	C5ⁱ—C6—C4	120.5 (4)
N2—C1—H1A	111.1	C5ⁱ—C6—H6	119.7
C2—C1—H1A	111.1	C4—C6—H6	119.8
N2—C1—H1B	111.1	O2—C7—O1	122.7 (4)
C2—C1—H1B	111.1	O2—C7—C8	116.4 (4)
H1A—C1—H1B	109.1	O1—C7—C8	120.9 (4)
N1—C2—C1	102.7 (3)	C10—C8—C9	117.1 (3)
N1—C2—H2A	111.2	C10—C8—C7	122.8 (4)
C1—C2—H2A	111.2	C9—C8—C7	120.1 (4)
N1—C2—H2B	111.2	C10ⁱⁱ—C9—C8	120.9 (4)
C1—C2—H2B	111.2	C10ⁱⁱ—C9—H9	119.6
H2A—C2—H2B	109.1	C8—C9—H9	119.5
N2—C3—N1	112.3 (4)	C9ⁱⁱ—C10—C8	122.0 (4)
N2—C3—C4	124.9 (3)	C9ⁱⁱ—C10—H10	118.8
N1—C3—C4	122.8 (4)	C8—C10—H10	119.1
C5—C4—C6	119.1 (4)	H1WA—O1W—H1WB	118 (2)
C5—C4—C3	121.3 (3)	H2WA—O2W—H2WB	120.8
C6—C4—C3	119.6 (4)

C3—N2—C1—C2	−7.5 (4)	C3—C4—C5—C6ⁱ	179.9 (4)
C3—N1—C2—C1	−7.6 (4)	C5—C4—C6—C5ⁱ	−0.1 (7)
N2—C1—C2—N1	8.6 (4)	C3—C4—C6—C5ⁱ	−179.9 (4)
C1—N2—C3—N1	2.9 (5)	O2—C7—C8—C10	−2.8 (6)
C1—N2—C3—C4	−176.3 (4)	O1—C7—C8—C10	178.3 (4)
C2—N1—C3—N2	3.3 (5)	O2—C7—C8—C9	177.9 (4)
C2—N1—C3—C4	−177.5 (3)	O1—C7—C8—C9	−1.0 (6)
N2—C3—C4—C5	−172.2 (4)	C10—C8—C9—C10ⁱⁱ	−0.1 (6)
N1—C3—C4—C5	8.6 (6)	C7—C8—C9—C10ⁱⁱ	179.2 (4)
N2—C3—C4—C6	7.6 (6)	C9—C8—C10—C9ⁱⁱ	0.1 (6)
N1—C3—C4—C6	−171.6 (4)	C7—C8—C10—C9ⁱⁱ	−179.2 (4)
C6—C4—C5—C6ⁱ	0.1 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WB···O1ⁱⁱⁱ	0.85 (4)	2.37 (6)	2.904 (5)	121 (7)
O2W—H2WA···O1^iv	0.85	1.96	2.815 (5)	180
O1W—H1WB···O2W^v	0.85 (4)	2.08 (4)	2.926 (5)	172 (5)
O1W—H1WA···O2^vi	0.86 (3)	1.85 (2)	2.707 (5)	172 (3)
O2—H2D···N1	0.82	2.13	2.934 (4)	165
N2—H2C···O1W^vii	0.86	1.98	2.828 (4)	167
C5—H5···O1	0.93	2.50	3.407 (4)	165
C6—H6···O1W^vii	0.93	2.47	3.380 (6)	166

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₄N₄·C₈H₆O₄·4H₂O
M_r	452.46
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	7.9929 (13), 16.847 (3), 7.9615 (12)
β (°)	94.899 (3)
V (Å³)	1068.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.50 × 0.35 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.947, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	5588, 2300, 832
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.090, 0.257, 0.79
No. of reflections	2300
No. of parameters	158
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)	0.71, −0.43

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2WB···O1ⁱ	0.85 (4)	2.37 (6)	2.904 (5)	121 (7)
O2W—H2WA···O1ⁱⁱ	0.85	1.96	2.815 (5)	179.7
O1W—H1WB···O2Wⁱⁱⁱ	0.85 (4)	2.08 (4)	2.926 (5)	172 (5)
O1W—H1WA···O2^iv	0.86 (3)	1.851 (15)	2.707 (5)	172 (3)
O2—H2D···N1	0.82	2.13	2.934 (4)	165.2
N2—H2C···O1W^v	0.86	1.98	2.828 (4)	166.9
C5—H5···O1	0.93	2.50	3.407 (4)	165
C6—H6···O1W^v	0.93	2.47	3.380 (6)	166

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

Acknowledgements

This work was generously supported by the National Natural Science Foundation of China (No. 20701016).

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