Diaqua­(5-carb­oxy­benzene-1,3-dicarboxyl­ato-κO1)[8-ethyl-5-oxo-2-(piperazin-4-ium-1-yl)-5,8-dihydro­pyrido[2,3-d]pyrimidine-6-carboxyl­ato-κ2O5,O6]zinc monohydrate

Ye, Z.-L.; Xin, G.-H.; Zhang, F.-T.; Xiao, D.-R.

doi:10.1107/S1600536813002122

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page m127

doi:10.1107/S1600536813002122

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Diaqua(5-carboxybenzene-1,3-dicarboxylato-κO¹)[8-ethyl-5-oxo-2-(piperazin-4-ium-1-yl)-5,8-dihydropyrido[2,3-d]pyrimidine-6-carboxylato-κ²O⁵,O⁶]zinc monohydrate

Zhong-Li Ye,^a Guang-Hua Xin,^a Fu-Tian Zhang ^a and Dong-Rong Xiao ^a ^*

^aCollege of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China
^*Correspondence e-mail: xiaodr98@yahoo.com.cn

(Received 9 January 2013; accepted 22 January 2013; online 31 January 2013)

In the title compound, [Zn(C₁₄H₁₇N₅O₃)(C₉H₄O₆)(H₂O)₂]·H₂O, the complex molecule exists in a zwitterionic form. The Zn^II ion exhibits a distorted tetragonal-pyramidal geometry, being coordinated by two O atoms from the zwitterionic 8-ethyl-5-oxo-2-(piperazin-4-ium-1-yl)-5,8-dihydropyrido[2,3-d]pyrimidine-6-carboxylate (L) ligand, one O atom from the 5-carboxybenzene-1,3-dicarboxylate dianion, [Hbtc]²⁻, and two O atoms from two aqua ligands. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds link the components into a three-dimensional structure. The crystal packing exhibits π–π interactions between the aromatic rings, with centroid–centroid distances in the range 3.466 (3)–3.667 (3) Å.

Related literature

For general background to the use of quinolones in the treatment of infections, see: Mizuki et al. (1996 ). For the crystal structure of a related compound, see: Zhang et al. (2011 ).

Experimental

Crystal data

[Zn(C₁₄H₁₇N₅O₃)(C₉H₄O₆)(H₂O)₂]·H₂O
M_r = 630.87
Monoclinic, P 2₁ /c
a = 13.5019 (11) Å
b = 12.5743 (10) Å
c = 17.7314 (10) Å
β = 125.575 (4)°
V = 2448.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 293 K
0.42 × 0.38 × 0.35 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.659, T_max = 0.703
12140 measured reflections
4299 independent reflections
3894 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.105
S = 0.86
4299 reflections
370 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.90	1.96	2.821 (2)	160
N1—H1B⋯O8ⁱⁱ	0.90	2.20	2.930 (2)	138
O9—H9A⋯O7ⁱⁱⁱ	0.85	1.76	2.5722 (19)	158
OW1—HW1A⋯O5ⁱⁱ	0.82	1.83	2.647 (2)	176
OW2—HW2A⋯O6ⁱⁱ	0.82	1.85	2.674 (2)	174
OW3—HW3A⋯O3^iv	0.84	2.27	2.977 (2)	142
OW3—HW3B⋯OW1^v	0.84	2.37	3.159 (2)	156
OW2—HW2B⋯O2^vi	0.83	1.89	2.715 (2)	169
Symmetry codes: (i) x+1, y, z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x-1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813002122/cv5383sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813002122/cv5383Isup2.hkl

checkCIF report

Comment top

Pipemidic acid (8-ethyl-5-oxo-2-piperazin-1-yl-5,8-dihydropyrido[2,3-d]pyrimidine-6- carboxylic acid), L, is a member of quinolones used to treat various infections (Mizuki et al., 1996). The complexes of the L ligand and [Hbtc]^2- anion have not been reported till now. In this paper, we report the crystal structure of the title compound.

The asymmetric unit of the title compound is composed of one Zn^II ion, one L ligand , one [Hbtc]^2- anion (H₃btc = benzene-1,3,5-tricarboxylic acid), two coordinated and one lattice water molecules (Fig. 1). All bond lengths in L are normal, though slightly different from those reported for base molecule L earlier by Zhang et al. (2011). So, the C1—O2, C3—O3 and C1—O1 bond lengths are 1.255 (2), 1.275 (2) and 1.255 (2) Å, respectively, versus 1.219 (2), 1.268 (3) and 1.319 (3) Å reported by Zhang et al. (2011).

In the crystal, intermolecular N—H···O and O—H···O hydrogen bonds (Table 1) link all moieties into three-dimensional supramolecular structure. The crystal packing exhibits π–π interactions between the aromatic rings with the intercentroids distances covering the range 3.466 (3) – 3.667 (3) Å.

Related literature top

For general background to the use of quinolones in the treatment of infections, see: Mizuki et al. (1996). For the crystal structure of a related compound, see: Zhang et al. (2011).

Experimental top

A mixture of Zn(OAC)₂^.3H₂O (0.546 g, 0.25 mmol), L (0.758 g, 0.25 mmol), H₃btc(0.526 g, 0.25 mmol) and distilled water (8 mL) was stirred for 20 min in air. The mixture was then transferred to a 23 ml Teflon-lined hydrothermal bomb. The bomb was kept at 423 K for 96 h under autogenous pressure. Upon cooling, colorless block of 1 was obtained from the reaction mixture.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound showing the atomic numbering and 30% probability displacement ellipsoids. H atoms have been omitted for clarity.

Diaqua(5-carboxybenzene-1,3-dicarboxylato-κO¹)[8-ethyl-5-oxo-2-(piperazin-4-ium-1-yl)-5,8-dihydropyrido[2,3-d]pyrimidine-6-carboxylato-κ²O⁵,O⁶]zinc monohydrate top

Crystal data top

[Zn(C₁₄H₁₇N₅O₃)(C₉H₄O₆)(H₂O)₂]·H₂O	F(000) = 1304
M_r = 630.87	D_x = 1.711 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12140 reflections
a = 13.5019 (11) Å	θ = 1.9–25.0°
b = 12.5743 (10) Å	µ = 1.08 mm⁻¹
c = 17.7314 (10) Å	T = 293 K
β = 125.575 (4)°	Block, colourless
V = 2448.5 (3) Å³	0.42 × 0.38 × 0.35 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	4299 independent reflections
Radiation source: fine-focus sealed tube	3894 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
phi and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→13
T_min = 0.659, T_max = 0.703	k = −14→10
12140 measured reflections	l = −19→21

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 0.86	w = 1/[σ²(F_o²) + (0.105P)²] where P = (F_o² + 2F_c²)/3
4299 reflections	(Δ/σ)_max = 0.001
370 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Zn(C₁₄H₁₇N₅O₃)(C₉H₄O₆)(H₂O)₂]·H₂O	V = 2448.5 (3) Å³
M_r = 630.87	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.5019 (11) Å	µ = 1.08 mm⁻¹
b = 12.5743 (10) Å	T = 293 K
c = 17.7314 (10) Å	0.42 × 0.38 × 0.35 mm
β = 125.575 (4)°

Data collection top

Bruker APEX CCD area-detector diffractometer	4299 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3894 reflections with I > 2σ(I)
T_min = 0.659, T_max = 0.703	R_int = 0.019
12140 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 0.86	Δρ_max = 0.30 e Å⁻³
4299 reflections	Δρ_min = −0.29 e Å⁻³
370 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
Zn1	−0.032037 (19)	0.542603 (16)	0.212780 (15)	0.02453 (12)
O1	−0.00857 (14)	0.45417 (12)	0.31957 (11)	0.0390 (4)
OW1	−0.14163 (14)	0.42573 (12)	0.12210 (10)	0.0334 (3)
HW1A	−0.1043	0.3693	0.1375	0.040*
HW1B	−0.1824	0.4383	0.0659	0.040*
N1	0.82562 (16)	0.33637 (14)	0.38179 (12)	0.0336 (4)
H1A	0.8906	0.3303	0.3799	0.040*
H1B	0.7758	0.2812	0.3501	0.040*
C1	0.07412 (17)	0.39071 (15)	0.37520 (13)	0.0248 (4)
OW2	−0.03717 (14)	0.61280 (11)	0.10620 (10)	0.0345 (3)
HW2A	0.0169	0.5959	0.1002	0.041*
HW2B	−0.0530	0.6774	0.0963	0.041*
O2	0.06097 (13)	0.32612 (11)	0.42274 (10)	0.0340 (3)
N2	0.68419 (14)	0.42975 (13)	0.42967 (11)	0.0244 (4)
C2	0.19476 (16)	0.39307 (14)	0.38844 (12)	0.0219 (4)
C2O	−0.37837 (16)	0.76072 (14)	0.26753 (12)	0.0220 (4)
OW3	0.77949 (16)	0.23797 (14)	0.71317 (12)	0.0509 (4)
HW3A	0.8273	0.2843	0.7177	0.061*
HW3B	0.7854	0.1827	0.6896	0.061*
O3	0.15171 (13)	0.53636 (10)	0.28385 (10)	0.0284 (3)
N3	0.50374 (15)	0.52444 (12)	0.35526 (11)	0.0248 (4)
C3	0.28179 (17)	0.32237 (15)	0.45016 (13)	0.0249 (4)
H3A	0.2610	0.2759	0.4797	0.030*
O4	−0.13831 (13)	0.64086 (11)	0.21967 (10)	0.0324 (3)
N4	0.54190 (14)	0.37213 (12)	0.45188 (10)	0.0220 (3)
C4	0.42950 (16)	0.38277 (14)	0.42995 (12)	0.0197 (4)
O5	0.01241 (12)	0.74802 (11)	0.31946 (10)	0.0309 (3)
N5	0.39455 (14)	0.31466 (12)	0.47158 (10)	0.0239 (3)
C5	0.57379 (17)	0.44147 (14)	0.41227 (12)	0.0210 (4)
O6	−0.12766 (16)	1.06302 (13)	0.42602 (13)	0.0456 (4)
C6	0.39329 (18)	0.53030 (14)	0.33426 (13)	0.0226 (4)
H6A	0.3426	0.5842	0.2943	0.027*
O7	−0.28043 (13)	1.03074 (11)	0.43593 (10)	0.0290 (3)
C7	0.34660 (17)	0.46027 (13)	0.36832 (12)	0.0196 (4)
O8	−0.58074 (13)	0.74380 (12)	0.22537 (10)	0.0338 (3)
C8	0.22443 (18)	0.46717 (14)	0.34316 (13)	0.0212 (4)
O9	−0.51412 (13)	0.62674 (12)	0.16984 (10)	0.0361 (4)
H9A	−0.5883	0.6067	0.1402	0.054*
C9	0.76274 (19)	0.34109 (17)	0.48758 (14)	0.0303 (4)
H9B	0.7156	0.2759	0.4681	0.036*
H9C	0.7943	0.3543	0.5518	0.036*
C10	0.86758 (18)	0.32865 (19)	0.47921 (14)	0.0346 (5)
H10A	0.9277	0.3835	0.5154	0.042*
H10B	0.9062	0.2602	0.5042	0.042*
C11	0.7598 (2)	0.43770 (19)	0.33365 (17)	0.0377 (5)
H11A	0.6851	0.4210	0.2739	0.045*
H11B	0.8102	0.4807	0.3231	0.045*
C12	0.73005 (19)	0.49977 (17)	0.39075 (16)	0.0329 (5)
H12A	0.8026	0.5359	0.4406	0.040*
H12B	0.6692	0.5532	0.3522	0.040*
C13	0.48182 (19)	0.23716 (16)	0.54400 (14)	0.0321 (5)
H13A	0.5642	0.2582	0.5676	0.039*
H13B	0.4743	0.2393	0.5951	0.039*
C14	0.4609 (3)	0.1272 (2)	0.5085 (2)	0.0662 (9)
H14A	0.5191	0.0806	0.5575	0.099*
H14B	0.4700	0.1242	0.4588	0.099*
H14C	0.3801	0.1053	0.4862	0.099*
C15	−0.09348 (16)	0.71577 (14)	0.27897 (12)	0.0215 (4)
C16	−0.17983 (16)	0.76464 (14)	0.29685 (12)	0.0212 (4)
C17	−0.15124 (17)	0.85606 (15)	0.35071 (12)	0.0212 (4)
H17A	−0.0747	0.8870	0.3796	0.025*
C18	−0.23701 (16)	0.90140 (14)	0.36141 (12)	0.0212 (4)
C19	−0.34947 (17)	0.85178 (15)	0.32052 (12)	0.0234 (4)
H19A	−0.4060	0.8802	0.3289	0.028*
C21	−0.29326 (16)	0.71805 (15)	0.25523 (13)	0.0233 (4)
H21A	−0.3129	0.6577	0.2187	0.028*
C22	−0.50197 (17)	0.70998 (15)	0.21896 (12)	0.0244 (4)
C23	−0.21103 (17)	1.00653 (16)	0.41192 (13)	0.0249 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01950 (17)	0.02615 (18)	0.03055 (17)	0.00258 (8)	0.01604 (13)	−0.00079 (8)
O1	0.0278 (8)	0.0537 (10)	0.0451 (9)	0.0111 (6)	0.0268 (8)	0.0178 (7)
OW1	0.0390 (9)	0.0277 (7)	0.0291 (7)	−0.0004 (6)	0.0173 (7)	0.0011 (6)
N1	0.0305 (10)	0.0413 (10)	0.0381 (10)	0.0043 (8)	0.0251 (8)	−0.0010 (8)
C1	0.0241 (10)	0.0273 (10)	0.0284 (10)	−0.0039 (8)	0.0183 (9)	−0.0062 (8)
OW2	0.0375 (8)	0.0330 (8)	0.0440 (8)	0.0068 (6)	0.0300 (7)	0.0054 (6)
O2	0.0332 (8)	0.0350 (8)	0.0461 (9)	0.0001 (6)	0.0299 (7)	0.0057 (7)
N2	0.0200 (8)	0.0278 (8)	0.0292 (8)	0.0033 (7)	0.0165 (7)	0.0035 (7)
C2	0.0218 (9)	0.0231 (9)	0.0246 (9)	−0.0021 (7)	0.0156 (8)	−0.0042 (7)
C2O	0.0194 (9)	0.0243 (9)	0.0236 (9)	0.0008 (7)	0.0133 (8)	0.0039 (7)
OW3	0.0491 (11)	0.0523 (11)	0.0622 (11)	0.0057 (8)	0.0385 (9)	0.0089 (8)
O3	0.0205 (7)	0.0287 (8)	0.0363 (8)	0.0047 (5)	0.0166 (7)	0.0079 (6)
N3	0.0217 (9)	0.0237 (8)	0.0308 (9)	0.0016 (6)	0.0162 (7)	0.0034 (7)
C3	0.0257 (10)	0.0262 (10)	0.0272 (10)	−0.0032 (8)	0.0179 (8)	−0.0015 (8)
O4	0.0277 (8)	0.0298 (7)	0.0427 (8)	0.0010 (6)	0.0221 (7)	−0.0108 (6)
N4	0.0194 (8)	0.0240 (8)	0.0234 (8)	0.0011 (6)	0.0128 (7)	−0.0003 (6)
C4	0.0202 (9)	0.0204 (9)	0.0184 (8)	−0.0010 (7)	0.0111 (7)	−0.0027 (7)
O5	0.0215 (7)	0.0334 (8)	0.0406 (8)	−0.0005 (6)	0.0196 (7)	−0.0063 (6)
N5	0.0217 (8)	0.0249 (8)	0.0258 (8)	0.0011 (6)	0.0143 (7)	0.0030 (6)
C5	0.0198 (10)	0.0222 (9)	0.0217 (9)	−0.0009 (7)	0.0124 (8)	−0.0043 (7)
O6	0.0497 (11)	0.0391 (9)	0.0693 (12)	−0.0188 (8)	0.0467 (10)	−0.0230 (8)
C6	0.0214 (10)	0.0214 (9)	0.0252 (9)	0.0008 (7)	0.0137 (8)	0.0007 (7)
O7	0.0244 (8)	0.0345 (8)	0.0291 (7)	0.0061 (6)	0.0161 (7)	−0.0030 (6)
C7	0.0183 (10)	0.0201 (9)	0.0200 (9)	−0.0011 (6)	0.0109 (8)	−0.0034 (6)
O8	0.0228 (7)	0.0394 (8)	0.0424 (8)	0.0011 (6)	0.0208 (7)	−0.0019 (7)
C8	0.0201 (10)	0.0210 (9)	0.0232 (9)	−0.0016 (7)	0.0130 (8)	−0.0049 (7)
O9	0.0242 (8)	0.0423 (9)	0.0443 (9)	−0.0121 (6)	0.0213 (7)	−0.0137 (7)
C9	0.0251 (10)	0.0382 (12)	0.0309 (10)	0.0078 (8)	0.0182 (9)	0.0057 (9)
C10	0.0248 (11)	0.0461 (13)	0.0335 (11)	0.0086 (9)	0.0173 (9)	0.0055 (9)
C11	0.0343 (12)	0.0461 (13)	0.0431 (13)	0.0048 (10)	0.0284 (11)	0.0065 (10)
C12	0.0284 (11)	0.0321 (11)	0.0469 (12)	0.0013 (9)	0.0268 (10)	0.0054 (10)
C13	0.0305 (11)	0.0338 (11)	0.0332 (11)	0.0074 (9)	0.0192 (9)	0.0138 (9)
C14	0.096 (2)	0.0375 (14)	0.0573 (17)	0.0229 (15)	0.0402 (17)	0.0114 (13)
C15	0.0228 (10)	0.0189 (9)	0.0234 (9)	0.0048 (7)	0.0139 (8)	0.0058 (7)
C16	0.0182 (9)	0.0237 (9)	0.0228 (9)	0.0042 (7)	0.0125 (8)	0.0045 (7)
C17	0.0175 (9)	0.0233 (9)	0.0211 (9)	0.0025 (7)	0.0104 (7)	0.0034 (7)
C18	0.0219 (9)	0.0234 (9)	0.0201 (9)	0.0030 (7)	0.0132 (8)	0.0035 (7)
C19	0.0218 (9)	0.0283 (10)	0.0242 (9)	0.0049 (8)	0.0157 (8)	0.0039 (7)
C21	0.0230 (9)	0.0216 (9)	0.0263 (9)	−0.0005 (7)	0.0150 (8)	−0.0010 (7)
C22	0.0209 (9)	0.0284 (10)	0.0250 (9)	−0.0001 (8)	0.0139 (8)	0.0041 (8)
C23	0.0233 (10)	0.0261 (10)	0.0248 (9)	0.0042 (8)	0.0137 (8)	0.0028 (8)

Geometric parameters (Å, º) top

Zn1—O4	1.9505 (13)	O5—C15	1.237 (2)
Zn1—O3	2.0277 (14)	N5—C13	1.492 (2)
Zn1—OW1	2.0412 (14)	O6—C23	1.228 (3)
Zn1—OW2	2.0501 (14)	C6—C7	1.407 (3)
Zn1—O1	2.0553 (15)	C6—H6A	0.9300
O1—C1	1.255 (2)	O7—C23	1.271 (2)
OW1—HW1A	0.8193	C7—C8	1.439 (3)
OW1—HW1B	0.8271	O8—C22	1.210 (2)
N1—C10	1.475 (3)	O9—C22	1.310 (2)
N1—C11	1.503 (3)	O9—H9A	0.8547
N1—H1A	0.9000	C9—C10	1.515 (3)
N1—H1B	0.8999	C9—H9B	0.9700
C1—O2	1.255 (2)	C9—H9C	0.9700
C1—C2	1.505 (3)	C10—H10A	0.9700
OW2—HW2A	0.8247	C10—H10B	0.9700
OW2—HW2B	0.8319	C11—C12	1.506 (3)
N2—C5	1.343 (2)	C11—H11A	0.9700
N2—C12	1.460 (3)	C11—H11B	0.9700
N2—C9	1.468 (3)	C12—H12A	0.9700
C2—C3	1.368 (3)	C12—H12B	0.9700
C2—C8	1.431 (3)	C13—C14	1.477 (3)
C2O—C19	1.386 (3)	C13—H13A	0.9700
C2O—C21	1.396 (3)	C13—H13B	0.9700
C2O—C22	1.504 (3)	C14—H14A	0.9600
OW3—HW3A	0.8383	C14—H14B	0.9600
OW3—HW3B	0.8382	C14—H14C	0.9600
O3—C8	1.275 (2)	C15—C16	1.506 (2)
N3—C6	1.312 (3)	C16—C21	1.385 (3)
N3—C5	1.376 (2)	C16—C17	1.398 (3)
C3—N5	1.341 (2)	C17—C18	1.399 (3)
C3—H3A	0.9300	C17—H17A	0.9300
O4—C15	1.272 (2)	C18—C19	1.393 (3)
N4—C4	1.336 (2)	C18—C23	1.519 (3)
N4—C5	1.338 (2)	C19—H19A	0.9300
C4—N5	1.381 (2)	C21—H21A	0.9300
C4—C7	1.405 (3)

O4—Zn1—O3	131.63 (6)	C22—O9—H9A	107.1
O4—Zn1—OW1	106.43 (6)	N2—C9—C10	110.23 (17)
O3—Zn1—OW1	121.73 (6)	N2—C9—H9B	109.6
O4—Zn1—OW2	98.83 (6)	C10—C9—H9B	109.6
O3—Zn1—OW2	87.86 (6)	N2—C9—H9C	109.6
OW1—Zn1—OW2	87.92 (6)	C10—C9—H9C	109.6
O4—Zn1—O1	90.56 (6)	H9B—C9—H9C	108.1
O3—Zn1—O1	85.95 (6)	N1—C10—C9	111.33 (16)
OW1—Zn1—O1	89.35 (6)	N1—C10—H10A	109.4
OW2—Zn1—O1	170.62 (6)	C9—C10—H10A	109.4
C1—O1—Zn1	131.15 (13)	N1—C10—H10B	109.4
Zn1—OW1—HW1A	109.7	C9—C10—H10B	109.4
Zn1—OW1—HW1B	118.8	H10A—C10—H10B	108.0
HW1A—OW1—HW1B	114.6	N1—C11—C12	111.01 (18)
C10—N1—C11	114.71 (17)	N1—C11—H11A	109.4
C10—N1—H1A	108.6	C12—C11—H11A	109.4
C11—N1—H1A	108.5	N1—C11—H11B	109.4
C10—N1—H1B	108.6	C12—C11—H11B	109.4
C11—N1—H1B	108.6	H11A—C11—H11B	108.0
H1A—N1—H1B	107.6	N2—C12—C11	110.94 (18)
O1—C1—O2	122.04 (18)	N2—C12—H12A	109.5
O1—C1—C2	119.83 (17)	C11—C12—H12A	109.5
O2—C1—C2	118.10 (17)	N2—C12—H12B	109.5
Zn1—OW2—HW2A	116.8	C11—C12—H12B	109.5
Zn1—OW2—HW2B	118.8	H12A—C12—H12B	108.0
HW2A—OW2—HW2B	111.3	C14—C13—N5	112.67 (19)
C5—N2—C12	122.99 (16)	C14—C13—H13A	109.1
C5—N2—C9	119.84 (16)	N5—C13—H13A	109.1
C12—N2—C9	117.14 (16)	C14—C13—H13B	109.1
C3—C2—C8	118.77 (17)	N5—C13—H13B	109.1
C3—C2—C1	117.39 (16)	H13A—C13—H13B	107.8
C8—C2—C1	123.80 (16)	C13—C14—H14A	109.5
C19—C2O—C21	119.41 (17)	C13—C14—H14B	109.5
C19—C2O—C22	121.32 (16)	H14A—C14—H14B	109.5
C21—C2O—C22	119.19 (17)	C13—C14—H14C	109.5
HW3A—OW3—HW3B	109.4	H14A—C14—H14C	109.5
C8—O3—Zn1	128.01 (13)	H14B—C14—H14C	109.5
C6—N3—C5	115.66 (16)	O5—C15—O4	123.77 (17)
N5—C3—C2	125.35 (17)	O5—C15—C16	121.28 (16)
N5—C3—H3A	117.3	O4—C15—C16	114.94 (16)
C2—C3—H3A	117.3	C21—C16—C17	119.49 (17)
C15—O4—Zn1	120.47 (12)	C21—C16—C15	117.82 (17)
C4—N4—C5	116.09 (16)	C17—C16—C15	122.66 (17)
N4—C4—N5	117.77 (16)	C16—C17—C18	120.43 (17)
N4—C4—C7	123.49 (17)	C16—C17—H17A	119.8
N5—C4—C7	118.74 (16)	C18—C17—H17A	119.8
C3—N5—C4	119.24 (15)	C19—C18—C17	118.99 (17)
C3—N5—C13	119.27 (16)	C19—C18—C23	120.31 (16)
C4—N5—C13	121.39 (16)	C17—C18—C23	120.61 (16)
N4—C5—N2	117.45 (17)	C2O—C19—C18	120.99 (17)
N4—C5—N3	125.89 (17)	C2O—C19—H19A	119.5
N2—C5—N3	116.65 (17)	C18—C19—H19A	119.5
N3—C6—C7	124.19 (17)	C16—C21—C2O	120.65 (17)
N3—C6—H6A	117.9	C16—C21—H21A	119.7
C7—C6—H6A	117.9	C2O—C21—H21A	119.7
C4—C7—C6	114.51 (17)	O8—C22—O9	124.50 (18)
C4—C7—C8	122.25 (17)	O8—C22—C2O	122.69 (18)
C6—C7—C8	123.24 (17)	O9—C22—C2O	112.82 (16)
O3—C8—C2	125.06 (18)	O6—C23—O7	124.09 (19)
O3—C8—C7	119.38 (17)	O6—C23—C18	119.57 (17)
C2—C8—C7	115.56 (16)	O7—C23—C18	116.33 (17)

O4—Zn1—O1—C1	−157.90 (19)	C3—C2—C8—O3	179.39 (18)
O3—Zn1—O1—C1	−26.19 (18)	C1—C2—C8—O3	−3.1 (3)
OW1—Zn1—O1—C1	95.68 (19)	C3—C2—C8—C7	−0.5 (2)
OW2—Zn1—O1—C1	22.6 (5)	C1—C2—C8—C7	176.99 (16)
Zn1—O1—C1—O2	−163.93 (14)	C4—C7—C8—O3	−177.04 (17)
Zn1—O1—C1—C2	17.9 (3)	C6—C7—C8—O3	3.5 (3)
O1—C1—C2—C3	179.80 (18)	C4—C7—C8—C2	2.8 (2)
O2—C1—C2—C3	1.6 (3)	C6—C7—C8—C2	−176.66 (16)
O1—C1—C2—C8	2.3 (3)	C5—N2—C9—C10	166.77 (17)
O2—C1—C2—C8	−175.91 (17)	C12—N2—C9—C10	−11.2 (3)
O4—Zn1—O3—C8	111.22 (16)	C11—N1—C10—C9	56.9 (2)
OW1—Zn1—O3—C8	−62.65 (17)	N2—C9—C10—N1	−44.5 (2)
OW2—Zn1—O3—C8	−148.87 (16)	C10—N1—C11—C12	−11.1 (3)
O1—Zn1—O3—C8	24.08 (16)	C5—N2—C12—C11	−120.9 (2)
C8—C2—C3—N5	−1.2 (3)	C9—N2—C12—C11	57.0 (2)
C1—C2—C3—N5	−178.84 (17)	N1—C11—C12—N2	−43.3 (2)
O3—Zn1—O4—C15	−2.41 (18)	C3—N5—C13—C14	79.6 (2)
OW1—Zn1—O4—C15	172.16 (14)	C4—N5—C13—C14	−104.1 (2)
OW2—Zn1—O4—C15	−97.42 (14)	Zn1—O4—C15—O5	17.8 (2)
O1—Zn1—O4—C15	82.66 (15)	Zn1—O4—C15—C16	−162.60 (12)
C5—N4—C4—N5	−178.14 (15)	O5—C15—C16—C21	−174.32 (17)
C5—N4—C4—C7	0.8 (3)	O4—C15—C16—C21	6.1 (2)
C2—C3—N5—C4	0.5 (3)	O5—C15—C16—C17	7.8 (3)
C2—C3—N5—C13	176.88 (18)	O4—C15—C16—C17	−171.76 (16)
N4—C4—N5—C3	−179.16 (16)	C21—C16—C17—C18	−1.0 (3)
C7—C4—N5—C3	1.8 (2)	C15—C16—C17—C18	176.78 (16)
N4—C4—N5—C13	4.6 (2)	C16—C17—C18—C19	2.4 (3)
C7—C4—N5—C13	−174.43 (16)	C16—C17—C18—C23	−173.99 (16)
C4—N4—C5—N2	−177.05 (16)	C21—C2O—C19—C18	0.2 (3)
C4—N4—C5—N3	3.2 (3)	C22—C2O—C19—C18	−176.69 (16)
C12—N2—C5—N4	179.90 (17)	C17—C18—C19—C2O	−2.0 (3)
C9—N2—C5—N4	2.1 (3)	C23—C18—C19—C2O	174.44 (16)
C12—N2—C5—N3	−0.3 (3)	C17—C16—C21—C2O	−0.8 (3)
C9—N2—C5—N3	−178.13 (16)	C15—C16—C21—C2O	−178.74 (16)
C6—N3—C5—N4	−4.5 (3)	C19—C2O—C21—C16	1.3 (3)
C6—N3—C5—N2	175.71 (17)	C22—C2O—C21—C16	178.18 (16)
C5—N3—C6—C7	1.9 (3)	C19—C2O—C22—O8	−2.0 (3)
N4—C4—C7—C6	−3.0 (3)	C21—C2O—C22—O8	−178.81 (18)
N5—C4—C7—C6	175.96 (16)	C19—C2O—C22—O9	177.94 (16)
N4—C4—C7—C8	177.49 (16)	C21—C2O—C22—O9	1.1 (2)
N5—C4—C7—C8	−3.6 (3)	C19—C18—C23—O6	−160.80 (19)
N3—C6—C7—C4	1.5 (3)	C17—C18—C23—O6	15.6 (3)
N3—C6—C7—C8	−178.97 (17)	C19—C18—C23—O7	18.2 (3)
Zn1—O3—C8—C2	−15.8 (3)	C17—C18—C23—O7	−165.44 (16)
Zn1—O3—C8—C7	164.05 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.90	1.96	2.821 (2)	160
N1—H1B···O8ⁱⁱ	0.90	2.20	2.930 (2)	138
O9—H9A···O7ⁱⁱⁱ	0.85	1.76	2.5722 (19)	158
OW1—HW1A···O5ⁱⁱ	0.82	1.83	2.647 (2)	176
OW2—HW2A···O6ⁱⁱ	0.82	1.85	2.674 (2)	174
OW3—HW3A···O3^iv	0.84	2.27	2.977 (2)	142
OW3—HW3B···OW1^v	0.84	2.37	3.159 (2)	156
OW2—HW2B···O2^vi	0.83	1.89	2.715 (2)	169

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

Experimental details

Crystal data
Chemical formula	[Zn(C₁₄H₁₇N₅O₃)(C₉H₄O₆)(H₂O)₂]·H₂O
M_r	630.87
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	13.5019 (11), 12.5743 (10), 17.7314 (10)
β (°)	125.575 (4)
V (Å³)	2448.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.42 × 0.38 × 0.35

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.659, 0.703
No. of measured, independent and observed [I > 2σ(I)] reflections	12140, 4299, 3894
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.105, 0.86
No. of reflections	4299
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.29

Computer programs: SMART (Bruker, 2001), SAINT (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
N1—H1A···O2ⁱ	0.90	1.96	2.821 (2)	159.7
N1—H1B···O8ⁱⁱ	0.90	2.20	2.930 (2)	137.7
O9—H9A···O7ⁱⁱⁱ	0.85	1.76	2.5722 (19)	158.4
OW1—HW1A···O5ⁱⁱ	0.82	1.83	2.647 (2)	175.6
OW2—HW2A···O6ⁱⁱ	0.82	1.85	2.674 (2)	174.0
OW3—HW3A···O3^iv	0.84	2.27	2.977 (2)	141.5
OW3—HW3B···OW1^v	0.84	2.37	3.159 (2)	156.2
OW2—HW2B···O2^vi	0.83	1.89	2.715 (2)	169.4

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

Acknowledgements

This work was supported financially by the Science and Technology Foundation of Southwest University (grant No. SWUB2007035) and the Science and Technology Innovation Foundation for Students of Southwest University.

References

Bruker (2001). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mizuki, Y., Fujiwara, I. & Yamaguchi, T. (1996). J. Antimicrob. Chemother. 37, Suppl. A, 41–45. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, G.-J., He, J.-H., Yan, S.-W., Ye, Z.-L. & Xin, G.-H. (2011). Acta Cryst. E67, o1011–o1012. Web of Science CSD CrossRef IUCr Journals Google Scholar

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