Aqua­(4-nitro­phthalato)bis­[2-(1H-pyrazol-3-yl)pyridine]­zinc(II) hemihydrate

Ni, L.; Zhao, J.-L.; Wei, H.

doi:10.1107/S1600536810051949

metal-organic compounds

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Volume 67| Part 1| January 2011| Page m105

https://doi.org/10.1107/S1600536810051949

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Aqua(4-nitrophthalato)bis[2-(1H-pyrazol-3-yl)pyridine]zinc(II) hemihydrate

Lei Ni,^a ^* Ji-Li Zhao ^a and Hong Wei ^a

^aCollege of Chemistry and Biology, Beihua University, Jilin 132013, People's Republic of China
^*Correspondence e-mail: nilei_bh@163.com

(Received 28 August 2010; accepted 11 December 2010; online 24 December 2010)

In the title compound, [Zn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O, the Zn^II atom shows a distorted octahedral ZnN₄O₂ coordination environment and is bonded to two 3-(2-pyridyl)-1H-pyrazole ligands via the N atoms, one monodentate 4-nitrophthalate ligand and one associated water molecule. Additionally, one water of crystallization, with a site-occupation factor of 0.5, is present. The two 3-(2-pyridyl)-1H-pyrazole ligands are planar [r.m.s. deviations = 0.03 (1) and 0.35 (1) Å] and the dihedral angle between the two planar 3-(2-pyridyl)-1H-pyrazole ligands is 67.31 (4)°. Intermolecular π–π stacking interactions between 3-(2-pyridyl)-1H-pyrazole ligands with a face-to-face separation of 3.64 (1) Å are observed. Moreover, the crystal structure is stabilized by O—H⋯O and N—H⋯O hydrogen bonds between the water of crystallization, the associated water molecule and the 3-(2-pyridyl)-1H-pyrazole ligands.

Related literature

For background to metal-organic frameworks, see: Hagrman et al. (1999 ); Kitagawa et al. (2004 ).

Experimental

Crystal data

[Zn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O
M_r = 591.84
Triclinic, $[P \overline 1]$
a = 10.4284 (6) Å
b = 11.1844 (7) Å
c = 11.9656 (8) Å
α = 96.508 (3)°
β = 112.091 (3)°
γ = 96.366 (3)°
V = 1266.84 (14) Å³
Z = 2
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 294 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.886, T_max = 0.922
9062 measured reflections
4258 independent reflections
3825 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.104
S = 1.00
4258 reflections
364 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H2W⋯O5ⁱ	0.82 (3)	1.81 (3)	2.627 (3)	174 (3)
N5—H5A⋯O4ⁱ	0.86	1.95	2.788 (3)	166
N2—H2A⋯O2	0.86	1.82	2.606 (4)	150
Symmetry code: (i) -x+2, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); 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); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810051949/im2226sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051949/im2226Isup2.hkl

checkCIF report

Comment top

The synthesis of entangled metal-organic frameworks (MOFs) has attracted continuous research interest not only because of their appealing structural and topological novelty, but also due to their unusual optical, electronic, magnetic, and catalytic properties, as well as their potential medical application (Hagrman et al. (1999); Kitagawa et al. (2004)). Here, we describe the synthesis and structural characterization of the title compound resulting from an attempted MOF synthesis in which Zn and Gd complex building blocks were expected to be the constituents.

Single crystal X-ray diffraction analyses revealed that the asymmetric unit of the title compound, [(Zn(C₈H₇N₃)₂(C₈NH₃O₆)(H₂O)].(H₂O)_0.5, consists of one Zn²⁺ ion, two 3-(2-pyridyl)-1H-pyrazole ligands, one 4-Nitrophthalato ligand, one associated water molecule, and half water of crystallization. As shown in Figure 1, the Zn²⁺ ion is hexacoordinated by four N atoms from 3-(2-pyridyl)-1H-pyrazole ligands and two oxygen atoms from 4-Nitrophthalato ligand and one associated water molecule, exhibiting a distorted octahedral arrangement of ZnN₄O₂. Moreover, the Rms deviations of the two 3-(2-pyridyl)-1H-pyrazole groups from planarity are 0.03 (1) and 0.35 (1) Å, respectively. The dihedral angle between the two 3-(2-pyridyl)-1H-pyrazole planars is 67.31 (4) Å. Interestingly, between the molecules, there is π-π stacking interactions with the face-to-face separation (ca 3.64 (1) Å) between the 3-(2-pyridyl)-1H-pyrazole planars. Meantime, there are extensive hydrogen bonds between water of crystallization, associated water molecule, and 3-(2-pyridyl)-1H-pyrazole, and leads to a consolidation of the structure (Figure 2).

Related literature top

For background to metal-organic frameworks, see: Hagrman et al. (1999); Kitagawa et al. (2004).

Experimental top

A mixture of zinc oxalate dihydrate (0.26 mmol, 0.050 g), 3-(2-pyridyl)-1H-pyrazole (0.32 mmoL, 0.05 g), 4-nitrophthalic acid (0.24 mmoL, 0.05 g), gadolinium(III) nitrate pentahydrate (0.12 mmoL, 0.05 g), and 14 ml H₂O was sealed in a 25 ml Teflon-lined stainless steel autoclave at 433 K for three days. Pink crystals suitable for the X-ray experiment were obtained. The yield is 60% based on the zinc salt. Anal. Calc. for C₄₈H₄₀N₁₄O₁₅Zn₂: C 48.65, H 3.38, N 16.55%; Found: C 48.32, H 3.15, N 16.39%.

Structure description top

For background to metal-organic frameworks, see: Hagrman et al. (1999); Kitagawa et al. (2004).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius.
	Fig. 2. Crystal packing of the title compound, displayed with hydrogen bonds as dashed lines.

Aqua(4-nitrophthalato)bis[2-(1H-pyrazol-3-yl)pyridine]zinc(II) hemihydrate top

Crystal data top

[Zn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O	Z = 2
M_r = 591.84	F(000) = 604
Triclinic, P1	D_x = 1.552 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4284 (6) Å	Cell parameters from 4528 reflections
b = 11.1844 (7) Å	θ = 2.4–27.3°
c = 11.9656 (8) Å	µ = 1.03 mm⁻¹
α = 96.508 (3)°	T = 294 K
β = 112.091 (3)°	Block, colorless
γ = 96.366 (3)°	0.12 × 0.10 × 0.08 mm
V = 1266.84 (14) Å³

Data collection top

Bruker APEXII CCD diffractometer	4258 independent reflections
Radiation source: fine-focus sealed tube	3825 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
phi and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
T_min = 0.886, T_max = 0.922	k = −13→13
9062 measured reflections	l = −14→13

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.066P)² + 0.7068P] where P = (F_o² + 2F_c²)/3
4258 reflections	(Δ/σ)_max = 0.001
364 parameters	Δρ_max = 0.65 e Å⁻³
3 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Zn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O	γ = 96.366 (3)°
M_r = 591.84	V = 1266.84 (14) Å³
Triclinic, P1	Z = 2
a = 10.4284 (6) Å	Mo Kα radiation
b = 11.1844 (7) Å	µ = 1.03 mm⁻¹
c = 11.9656 (8) Å	T = 294 K
α = 96.508 (3)°	0.12 × 0.10 × 0.08 mm
β = 112.091 (3)°

Data collection top

Bruker APEXII CCD diffractometer	4258 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3825 reflections with I > 2σ(I)
T_min = 0.886, T_max = 0.922	R_int = 0.020
9062 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	3 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.65 e Å⁻³
4258 reflections	Δρ_min = −0.42 e Å⁻³
364 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
C1	0.7155 (4)	0.7772 (3)	0.9195 (3)	0.0652 (9)
H1	0.6311	0.7613	0.9291	0.078*
C2	0.8440 (4)	0.8158 (3)	1.0110 (3)	0.0618 (9)
H2	0.8654	0.8318	1.0946	0.074*
C3	0.9371 (3)	0.8262 (2)	0.9526 (3)	0.0471 (7)
C4	1.0889 (3)	0.8628 (2)	0.9968 (3)	0.0476 (7)
C5	1.1747 (4)	0.9022 (3)	1.1197 (3)	0.0610 (8)
H5	1.1367	0.9060	1.1788	0.073*
C6	1.3160 (4)	0.9354 (3)	1.1522 (3)	0.0719 (10)
H6	1.3755	0.9618	1.2339	0.086*
C7	1.3695 (4)	0.9292 (3)	1.0618 (3)	0.0708 (10)
H7	1.4651	0.9517	1.0817	0.085*
C8	1.2775 (4)	0.8889 (3)	0.9417 (3)	0.0589 (8)
H8	1.3136	0.8841	0.8814	0.071*
C9	1.2913 (3)	0.7454 (3)	0.5661 (3)	0.0594 (8)
H9	1.3580	0.7702	0.5356	0.071*
C10	1.2595 (3)	0.6312 (3)	0.5882 (3)	0.0576 (8)
H10	1.2987	0.5629	0.5755	0.069*
C11	1.1556 (3)	0.6392 (2)	0.6339 (2)	0.0381 (5)
C12	1.0801 (3)	0.5491 (2)	0.6763 (2)	0.0369 (5)
C13	1.0886 (3)	0.4254 (2)	0.6620 (3)	0.0493 (7)
H13	1.1427	0.3953	0.6223	0.059*
C14	1.0159 (4)	0.3486 (3)	0.7075 (3)	0.0621 (9)
H14	1.0200	0.2656	0.6988	0.075*
C15	0.9378 (4)	0.3948 (3)	0.7654 (4)	0.0680 (9)
H15	0.8888	0.3442	0.7977	0.082*
C16	0.9322 (4)	0.5181 (3)	0.7755 (3)	0.0606 (8)
H16	0.8783	0.5491	0.8150	0.073*
C17	0.6685 (3)	0.7186 (3)	0.5137 (3)	0.0499 (7)
C18	0.5894 (3)	0.6933 (2)	0.3769 (2)	0.0403 (6)
C19	0.4792 (3)	0.5955 (3)	0.3277 (3)	0.0539 (7)
H19	0.4518	0.5534	0.3799	0.065*
C20	0.4097 (3)	0.5596 (3)	0.2034 (3)	0.0586 (8)
H20	0.3366	0.4936	0.1711	0.070*
C21	0.4512 (3)	0.6235 (3)	0.1282 (3)	0.0496 (7)
C22	0.5606 (3)	0.7203 (2)	0.1733 (2)	0.0431 (6)
H22	0.5887	0.7600	0.1200	0.052*
C23	0.6285 (2)	0.7579 (2)	0.2984 (2)	0.0371 (5)
C24	0.7389 (3)	0.8724 (2)	0.3428 (3)	0.0442 (6)
Zn1	0.97417 (3)	0.78410 (2)	0.71551 (3)	0.03624 (12)
N1	0.3763 (3)	0.5867 (3)	−0.0053 (3)	0.0720 (8)
N2	0.7314 (3)	0.7660 (2)	0.8127 (2)	0.0519 (6)
H2A	0.6641	0.7428	0.7420	0.062*
N3	0.8669 (3)	0.7961 (2)	0.8318 (2)	0.0452 (5)
N4	1.1400 (3)	0.8564 (2)	0.9082 (2)	0.0477 (6)
N5	1.2091 (2)	0.8153 (2)	0.5964 (2)	0.0442 (5)
H5A	1.2100	0.8911	0.5895	0.053*
N6	1.1256 (2)	0.75232 (18)	0.63868 (19)	0.0374 (5)
N7	1.0006 (2)	0.59453 (19)	0.7312 (2)	0.0423 (5)
O1	0.95913 (19)	0.95872 (16)	0.67148 (17)	0.0420 (4)
O2	0.5984 (3)	0.7250 (6)	0.5755 (3)	0.165 (2)
O3	0.79649 (18)	0.72281 (17)	0.55259 (17)	0.0433 (4)
O4	0.7478 (3)	0.94256 (18)	0.43546 (19)	0.0594 (6)
O5	0.8072 (3)	0.8910 (2)	0.2798 (3)	0.0751 (7)
O6	0.4156 (3)	0.6389 (3)	−0.0729 (2)	0.0957 (10)
O7	0.2773 (4)	0.5050 (4)	−0.0427 (3)	0.1448 (18)
O1W	0.5000	0.0000	0.5000	0.198 (4)
H1W	0.901 (2)	0.943 (3)	0.6007 (10)	0.080*
H2W	1.031 (2)	1.004 (3)	0.681 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.086 (3)	0.066 (2)	0.074 (2)	0.0190 (18)	0.061 (2)	0.0210 (17)
C2	0.092 (3)	0.0636 (19)	0.0523 (18)	0.0227 (18)	0.0484 (19)	0.0194 (15)
C3	0.0754 (19)	0.0368 (13)	0.0434 (15)	0.0165 (13)	0.0361 (14)	0.0114 (11)
C4	0.0715 (19)	0.0345 (13)	0.0434 (15)	0.0159 (13)	0.0270 (14)	0.0103 (11)
C5	0.091 (3)	0.0509 (17)	0.0440 (16)	0.0205 (17)	0.0269 (17)	0.0116 (13)
C6	0.088 (3)	0.062 (2)	0.0500 (19)	0.0151 (18)	0.0103 (18)	0.0082 (15)
C7	0.066 (2)	0.065 (2)	0.069 (2)	0.0092 (17)	0.0149 (18)	0.0103 (17)
C8	0.0617 (19)	0.0566 (18)	0.0591 (19)	0.0092 (15)	0.0251 (16)	0.0092 (15)
C9	0.0543 (18)	0.072 (2)	0.075 (2)	0.0182 (15)	0.0457 (17)	0.0238 (17)
C10	0.0617 (18)	0.0580 (18)	0.075 (2)	0.0287 (15)	0.0436 (17)	0.0208 (16)
C11	0.0386 (13)	0.0403 (13)	0.0372 (13)	0.0119 (10)	0.0157 (11)	0.0063 (10)
C12	0.0373 (12)	0.0372 (12)	0.0346 (12)	0.0100 (10)	0.0112 (10)	0.0072 (10)
C13	0.0568 (16)	0.0407 (14)	0.0500 (16)	0.0176 (13)	0.0181 (13)	0.0071 (12)
C14	0.073 (2)	0.0354 (14)	0.074 (2)	0.0138 (14)	0.0228 (18)	0.0132 (14)
C15	0.078 (2)	0.0462 (17)	0.097 (3)	0.0088 (16)	0.049 (2)	0.0330 (17)
C16	0.067 (2)	0.0456 (16)	0.090 (2)	0.0122 (14)	0.0504 (19)	0.0229 (16)
C17	0.0393 (15)	0.0692 (19)	0.0479 (15)	0.0069 (13)	0.0247 (13)	0.0119 (14)
C18	0.0305 (12)	0.0452 (14)	0.0499 (15)	0.0083 (10)	0.0196 (11)	0.0111 (11)
C19	0.0434 (15)	0.0562 (17)	0.0664 (19)	−0.0021 (13)	0.0262 (14)	0.0210 (15)
C20	0.0389 (15)	0.0493 (16)	0.077 (2)	−0.0103 (12)	0.0170 (15)	0.0051 (15)
C21	0.0367 (13)	0.0525 (16)	0.0486 (16)	0.0028 (12)	0.0087 (12)	−0.0012 (13)
C22	0.0384 (13)	0.0467 (14)	0.0441 (14)	0.0028 (11)	0.0165 (12)	0.0102 (12)
C23	0.0314 (12)	0.0347 (12)	0.0455 (14)	0.0047 (10)	0.0160 (11)	0.0061 (10)
C24	0.0407 (14)	0.0352 (13)	0.0491 (15)	0.0008 (11)	0.0104 (12)	0.0079 (12)
Zn1	0.04219 (19)	0.03371 (17)	0.04103 (19)	0.00763 (12)	0.02487 (14)	0.00712 (12)
N1	0.0539 (16)	0.077 (2)	0.0604 (18)	−0.0016 (15)	0.0026 (14)	−0.0046 (15)
N2	0.0599 (15)	0.0532 (14)	0.0574 (15)	0.0075 (12)	0.0395 (13)	0.0110 (11)
N3	0.0587 (14)	0.0411 (12)	0.0493 (13)	0.0113 (10)	0.0346 (11)	0.0102 (10)
N4	0.0606 (15)	0.0407 (12)	0.0460 (13)	0.0110 (11)	0.0254 (11)	0.0056 (10)
N5	0.0450 (12)	0.0422 (12)	0.0544 (13)	0.0050 (10)	0.0288 (11)	0.0124 (10)
N6	0.0392 (11)	0.0351 (10)	0.0414 (11)	0.0058 (9)	0.0202 (9)	0.0059 (9)
N7	0.0463 (12)	0.0344 (11)	0.0526 (13)	0.0084 (9)	0.0252 (11)	0.0104 (9)
O1	0.0434 (10)	0.0361 (9)	0.0475 (10)	0.0010 (7)	0.0204 (8)	0.0079 (8)
O2	0.0457 (15)	0.393 (7)	0.0555 (17)	0.021 (3)	0.0304 (13)	0.017 (3)
O3	0.0376 (10)	0.0464 (10)	0.0458 (10)	0.0068 (8)	0.0176 (8)	0.0030 (8)
O4	0.0814 (15)	0.0387 (10)	0.0495 (12)	−0.0046 (10)	0.0213 (11)	0.0036 (9)
O5	0.0723 (15)	0.0643 (14)	0.0923 (18)	−0.0264 (12)	0.0529 (15)	−0.0085 (13)
O6	0.0778 (18)	0.140 (3)	0.0511 (14)	−0.0108 (18)	0.0169 (14)	0.0024 (16)
O7	0.124 (3)	0.145 (3)	0.082 (2)	−0.076 (3)	−0.021 (2)	0.003 (2)
O1W	0.196 (7)	0.229 (8)	0.280 (10)	0.104 (7)	0.185 (8)	0.091 (8)

Geometric parameters (Å, º) top

C1—N2	1.343 (4)	C16—N7	1.333 (4)
C1—C2	1.357 (5)	C16—H16	0.9300
C1—H1	0.9300	C17—O2	1.221 (4)
C2—C3	1.396 (4)	C17—O3	1.231 (3)
C2—H2	0.9300	C17—C18	1.506 (4)
C3—N3	1.334 (4)	C18—C19	1.390 (4)
C3—C4	1.460 (4)	C18—C23	1.396 (4)
C4—N4	1.352 (4)	C19—C20	1.374 (5)
C4—C5	1.390 (4)	C19—H19	0.9300
C5—C6	1.369 (5)	C20—C21	1.371 (5)
C5—H5	0.9300	C20—H20	0.9300
C6—C7	1.390 (6)	C21—C22	1.376 (4)
C6—H6	0.9300	C21—N1	1.474 (4)
C7—C8	1.382 (5)	C22—C23	1.383 (4)
C7—H7	0.9300	C22—H22	0.9300
C8—N4	1.330 (4)	C23—C24	1.518 (3)
C8—H8	0.9300	C24—O5	1.235 (4)
C9—N5	1.341 (4)	C24—O4	1.250 (4)
C9—C10	1.363 (5)	Zn1—O1	2.0871 (18)
C9—H9	0.9300	Zn1—N3	2.089 (2)
C10—C11	1.393 (4)	Zn1—O3	2.0981 (18)
C10—H10	0.9300	Zn1—N6	2.147 (2)
C11—N6	1.336 (3)	Zn1—N7	2.188 (2)
C11—C12	1.460 (4)	Zn1—N4	2.287 (2)
C12—N7	1.342 (3)	N1—O7	1.204 (4)
C12—C13	1.391 (4)	N1—O6	1.211 (4)
C13—C14	1.371 (5)	N2—N3	1.341 (3)
C13—H13	0.9300	N2—H2A	0.8600
C14—C15	1.359 (5)	N5—N6	1.337 (3)
C14—H14	0.9300	N5—H5A	0.8600
C15—C16	1.379 (4)	O1—H1W	0.820 (13)
C15—H15	0.9300	O1—H2W	0.82 (3)

N2—C1—C2	108.1 (3)	C18—C19—H19	119.3
N2—C1—H1	126.0	C21—C20—C19	118.3 (3)
C2—C1—H1	126.0	C21—C20—H20	120.9
C1—C2—C3	105.1 (3)	C19—C20—H20	120.9
C1—C2—H2	127.4	C20—C21—C22	122.1 (3)
C3—C2—H2	127.4	C20—C21—N1	118.7 (3)
N3—C3—C2	109.9 (3)	C22—C21—N1	119.2 (3)
N3—C3—C4	116.7 (2)	C21—C22—C23	119.5 (3)
C2—C3—C4	133.4 (3)	C21—C22—H22	120.2
N4—C4—C5	122.4 (3)	C23—C22—H22	120.2
N4—C4—C3	114.5 (2)	C22—C23—C18	119.3 (2)
C5—C4—C3	123.1 (3)	C22—C23—C24	117.3 (2)
C6—C5—C4	118.8 (3)	C18—C23—C24	123.3 (2)
C6—C5—H5	120.6	O5—C24—O4	125.7 (3)
C4—C5—H5	120.6	O5—C24—C23	116.6 (2)
C5—C6—C7	119.3 (3)	O4—C24—C23	117.6 (3)
C5—C6—H6	120.4	O1—Zn1—N3	96.46 (8)
C7—C6—H6	120.4	O1—Zn1—O3	86.38 (7)
C8—C7—C6	118.5 (4)	N3—Zn1—O3	96.57 (9)
C8—C7—H7	120.8	O1—Zn1—N6	94.67 (8)
C6—C7—H7	120.8	N3—Zn1—N6	163.63 (9)
N4—C8—C7	123.2 (3)	O3—Zn1—N6	96.08 (7)
N4—C8—H8	118.4	O1—Zn1—N7	168.95 (8)
C7—C8—H8	118.4	N3—Zn1—N7	94.18 (9)
N5—C9—C10	107.6 (3)	O3—Zn1—N7	89.49 (8)
N5—C9—H9	126.2	N6—Zn1—N7	75.57 (8)
C10—C9—H9	126.2	O1—Zn1—N4	93.00 (8)
C9—C10—C11	105.1 (3)	N3—Zn1—N4	73.48 (9)
C9—C10—H10	127.5	O3—Zn1—N4	169.91 (8)
C11—C10—H10	127.5	N6—Zn1—N4	94.01 (8)
N6—C11—C10	110.3 (2)	N7—Zn1—N4	92.85 (8)
N6—C11—C12	118.0 (2)	O7—N1—O6	122.6 (3)
C10—C11—C12	131.8 (2)	O7—N1—C21	118.0 (4)
N7—C12—C13	121.8 (3)	O6—N1—C21	119.4 (3)
N7—C12—C11	114.8 (2)	N3—N2—C1	110.5 (3)
C13—C12—C11	123.4 (2)	N3—N2—H2A	124.7
C14—C13—C12	118.9 (3)	C1—N2—H2A	124.7
C14—C13—H13	120.6	C3—N3—N2	106.3 (2)
C12—C13—H13	120.6	C3—N3—Zn1	120.6 (2)
C15—C14—C13	119.5 (3)	N2—N3—Zn1	132.65 (19)
C15—C14—H14	120.3	C8—N4—C4	117.9 (3)
C13—C14—H14	120.3	C8—N4—Zn1	127.8 (2)
C14—C15—C16	119.0 (3)	C4—N4—Zn1	114.3 (2)
C14—C15—H15	120.5	N6—N5—C9	111.4 (2)
C16—C15—H15	120.5	N6—N5—H5A	124.3
N7—C16—C15	122.8 (3)	C9—N5—H5A	124.3
N7—C16—H16	118.6	C11—N6—N5	105.7 (2)
C15—C16—H16	118.6	C11—N6—Zn1	115.52 (17)
O2—C17—O3	126.1 (3)	N5—N6—Zn1	138.68 (16)
O2—C17—C18	116.8 (3)	C16—N7—C12	118.1 (2)
O3—C17—C18	117.0 (2)	C16—N7—Zn1	126.03 (19)
C19—C18—C23	119.3 (3)	C12—N7—Zn1	115.32 (17)
C19—C18—C17	117.7 (3)	Zn1—O1—H1W	101 (3)
C23—C18—C17	122.8 (2)	Zn1—O1—H2W	119 (3)
C20—C19—C18	121.4 (3)	H1W—O1—H2W	114 (3)
C20—C19—H19	119.3	C17—O3—Zn1	139.12 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2W···O5ⁱ	0.82 (3)	1.81 (3)	2.627 (3)	174 (3)
N5—H5A···O4ⁱ	0.86	1.95	2.788 (3)	166
N2—H2A···O2	0.86	1.82	2.606 (4)	150

Symmetry code: (i) −x+2, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₃NO₆)(C₈H₇N₃)₂(H₂O)]·0.5H₂O
M_r	591.84
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	10.4284 (6), 11.1844 (7), 11.9656 (8)
α, β, γ (°)	96.508 (3), 112.091 (3), 96.366 (3)
V (Å³)	1266.84 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.03
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.886, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	9062, 4258, 3825
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.104, 1.00
No. of reflections	4258
No. of parameters	364
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.42

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2W···O5ⁱ	0.82 (3)	1.81 (3)	2.627 (3)	174 (3)
N5—H5A···O4ⁱ	0.86	1.95	2.788 (3)	166
N2—H2A···O2	0.86	1.82	2.606 (4)	150

Symmetry code: (i) −x+2, −y+2, −z+1.

Acknowledgements

The authors acknowledge financial support from the Science Foundation of Beihua University.

References

Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hagrman, P. J., Hagrman, D. & Zubieta, J. (1999). Angew. Chem. Int. Ed. 111, 2798–2848. CrossRef Google Scholar
Kitagawa, S., Kitaura, R. & Noro, S. I. (2004). Angew. Chem. Int. Ed. 116, 2388–2430. CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar