Poly[[diaqua­bis­{μ-4-[6-(4-carboxyphenyl)-4,4′-bipyridin-2-yl]benzoato-κ2O:N4′}zinc] dimethyl­formamide tetra­solvate]

Ge, X.; Song, S.

doi:10.1107/S1600536812043838

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 11| November 2012| Page m1413

doi:10.1107/S1600536812043838

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Poly[[diaquabis{μ-4-[6-(4-carboxyphenyl)-4,4′-bipyridin-2-yl]benzoato-κ²O:N^4′}zinc] dimethylformamide tetrasolvate]

Xin Ge ^a and Shuyan Song ^a ^*

^aState Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China
^*Correspondence e-mail: songsy@ciac.jl.cn

(Received 15 October 2012; accepted 23 October 2012; online 27 October 2012)

In the title compound, {[Zn(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO}_n, the Zn^II ion is located on an inversion center and is six-coordinated by two N atoms from two ligands, two carboxylate O atoms from two other symmetry-related ligands and two O atoms from two water molecules, furnishing a slightly distorted octahedral geometry. The Zn^II atoms are connected by the bridging ligands into a layer parallel to (101). O—H⋯O hydrogen bonds link the layers and the dimethylformamide solvent molecules. π–π interactions between the pyridine and benzene rings [centroid–centroid distances = 3.7428 (17) and 3.7619 (17) Å] and intralayer O—H⋯O hydrogen bonds are also present.

Related literature

For the design of transition metal complexes with supramolecular structures, see: Li et al. (2011 ); Wang et al. (2010 ); Yang et al. (2007 ). For related structures, see: Song et al. (2012 ).

Experimental

Crystal data

[Zn(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO
M_r = 1184.57
Monoclinic, P 2₁ /n
a = 7.4744 (5) Å
b = 17.7122 (13) Å
c = 21.4993 (15) Å
β = 95.075 (1)°
V = 2835.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 293 K
0.25 × 0.22 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.839, T_max = 0.915
15534 measured reflections
5606 independent reflections
3804 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.158
S = 1.05
5606 reflections
385 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O6ⁱ	0.85 (1)	1.93 (2)	2.750 (4)	164 (4)
O1W—H1B⋯O2	0.85 (1)	1.98 (2)	2.718 (3)	145 (4)
O3—H3A⋯O2ⁱⁱ	0.86 (1)	1.77 (2)	2.592 (3)	161 (5)
Symmetry codes: (i) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812043838/hy2597sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812043838/hy2597Isup2.hkl

checkCIF report

Comment top

The coordination chemistry of transition metal complexes is a rapidly growing area due to the ability of the resulting complexes to find applications in materials science with luminescent, magnetic, catalytic, and gas absorption and separation properties (Li et al., 2011; Yang et al., 2007). Multifunctional ligands can link metal ions into one-, two- or three-dimensional structures (Wang et al., 2010). In order to extend the investigations in this field, we used a multifunctional ligand, 4,4'-(4,4'-bipyridine-2,6-diyl)dibenzoic acid (bpydbH₂), to design and synthesize the title zinc(II) complex and its structure is reported here.

The asymmetric unit of the title complex contains a half Zn^II ion, one (bpydbH)^- ligand, one aqua ligand and two lattice dimethylformamide (DMF) molecules. As shown in Fig. 1, the Zn^II ion, lying on an inversion center, is six-coordinated by two N atoms from two (bpydbH)^- ligands, two deprotonated carboxylate O atoms from the other two (bpydbH)^- ligands and two aqua ligands, furnishing a slightly distorted octahedral geometry. The bond distances and angles are in the normal range (Song et al., 2012). The Zn nodes are extended by the (bpydbH)^- linkers in four directions, forming a layer parallel to (101) (Fig. 2). Intralayer O—H···O hydrogen bonds stabilize the layer. O—H···O hydrogen bonds link the layers and the dimethylformamide solvent molecules. π–π interactions between the pyridine and benzene rings [centroid–centroid distances = 3.7428 (17) and 3.7619 (17) Å] are also present.

Related literature top

For the design of supramolecular structures of transition metal complexes, see: Li et al. (2011); Wang et al. (2010); Yang et al. (2007). For related structures, see: Song et al. (2012).

Experimental top

Zn(NO₃)₂.6H₂O (0.008 g, 0.025 mmol) and bpydbH₂ (0.010 g, 0.025 mmol) were suspended in a mixed solution of DMF (4 ml) and H₂O (0.5 ml). The mixture was heated in a 15 ml Teflon-lined stainless-steel autoclave at 90°C for 3 days. After it was cooled to room temperature slowly, colorless crystals were collected by filtration, washed with DMF and dried in air, with a yield of 59% based on bpydbH₂.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 3/2-x, 1/2+y, 1/2-z; (ii) 1/2+x, 1/2-y, -1/2+z; (iii) 2-x, 1-y, -z.]
	Fig. 2. View of the layer structure in the title compound.

Poly[[diaquabis{µ-4-[6-(4-carboxyphenyl)-4,4'-bipyridin-2-yl]benzoato- κ²O:N^4'}zinc] dimethylformamide tetrasolvate] top

Crystal data top

[Zn(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO	F(000) = 1240
M_r = 1184.57	D_x = 1.388 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5607 reflections
a = 7.4744 (5) Å	θ = 1.0–26.1°
b = 17.7122 (13) Å	µ = 0.51 mm⁻¹
c = 21.4993 (15) Å	T = 293 K
β = 95.075 (1)°	Block, colorless
V = 2835.1 (3) Å³	0.25 × 0.22 × 0.19 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	5606 independent reflections
Radiation source: fine-focus sealed tube	3804 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 26.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→9
T_min = 0.839, T_max = 0.915	k = −16→21
15534 measured reflections	l = −26→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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.078P)² + 1.0747P] where P = (F_o² + 2F_c²)/3
5606 reflections	(Δ/σ)_max < 0.001
385 parameters	Δρ_max = 0.40 e Å⁻³
3 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

[Zn(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO	V = 2835.1 (3) Å³
M_r = 1184.57	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4744 (5) Å	µ = 0.51 mm⁻¹
b = 17.7122 (13) Å	T = 293 K
c = 21.4993 (15) Å	0.25 × 0.22 × 0.19 mm
β = 95.075 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5606 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3804 reflections with I > 2σ(I)
T_min = 0.839, T_max = 0.915	R_int = 0.044
15534 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	3 restraints
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.40 e Å⁻³
5606 reflections	Δρ_min = −0.35 e Å⁻³
385 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
Zn1	1.0000	0.5000	0.0000	0.03205 (18)
C1	0.6503 (5)	0.73356 (19)	0.63443 (16)	0.0392 (8)
C2	0.6897 (4)	0.66640 (18)	0.59720 (14)	0.0331 (7)
C3	0.6424 (4)	0.59554 (18)	0.61726 (15)	0.0347 (8)
H3	0.5935	0.5901	0.6553	0.042*
C4	0.6676 (4)	0.53241 (19)	0.58068 (14)	0.0318 (7)
H4	0.6355	0.4850	0.5945	0.038*
C5	0.7403 (4)	0.53927 (17)	0.52353 (13)	0.0266 (6)
C6	0.7865 (4)	0.61109 (18)	0.50425 (15)	0.0317 (7)
H6	0.8333	0.6170	0.4659	0.038*
C7	0.7642 (4)	0.67359 (18)	0.54074 (15)	0.0336 (7)
H7	0.7993	0.7209	0.5275	0.040*
C8	0.7645 (4)	0.47318 (18)	0.48218 (14)	0.0275 (7)
C9	0.7387 (4)	0.39894 (17)	0.50138 (14)	0.0275 (7)
H9	0.7094	0.3891	0.5417	0.033*
C10	0.7572 (4)	0.33962 (17)	0.45977 (13)	0.0264 (6)
C11	0.8034 (4)	0.35839 (17)	0.40001 (13)	0.0288 (7)
H11	0.8162	0.3207	0.3706	0.035*
C12	0.8302 (4)	0.43340 (17)	0.38481 (13)	0.0263 (6)
C13	0.8806 (4)	0.45519 (17)	0.32174 (13)	0.0278 (7)
C14	0.8268 (4)	0.41227 (18)	0.26902 (14)	0.0329 (7)
H14	0.7549	0.3700	0.2729	0.039*
C15	0.8791 (4)	0.43189 (18)	0.21099 (14)	0.0326 (7)
H15	0.8420	0.4028	0.1762	0.039*
C16	0.9868 (4)	0.49489 (17)	0.20442 (14)	0.0283 (7)
C17	1.0387 (4)	0.53839 (18)	0.25678 (14)	0.0321 (7)
H17	1.1100	0.5809	0.2528	0.038*
C18	0.9856 (4)	0.51921 (18)	0.31450 (14)	0.0324 (7)
H18	1.0202	0.5492	0.3490	0.039*
C19	1.0453 (5)	0.51556 (17)	0.14145 (15)	0.0333 (8)
C20	0.7223 (4)	0.26062 (17)	0.47603 (13)	0.0266 (6)
C21	0.7949 (4)	0.19986 (18)	0.44509 (14)	0.0344 (8)
H21	0.8797	0.2085	0.4168	0.041*
C22	0.7410 (4)	0.12758 (18)	0.45651 (14)	0.0348 (7)
H22	0.7923	0.0882	0.4357	0.042*
C23	0.5550 (4)	0.16840 (18)	0.52842 (14)	0.0326 (7)
H23	0.4745	0.1578	0.5578	0.039*
C24	0.6034 (4)	0.24235 (17)	0.52010 (13)	0.0292 (7)
H24	0.5568	0.2802	0.5439	0.035*
C25	0.5183 (11)	0.7258 (3)	0.2575 (3)	0.128 (3)
H25A	0.5527	0.7407	0.2173	0.192*
H25B	0.5922	0.7515	0.2896	0.192*
H25C	0.3947	0.7387	0.2606	0.192*
C26	0.5986 (7)	0.6048 (3)	0.2118 (2)	0.0877 (17)
H26A	0.6200	0.6397	0.1791	0.132*
H26B	0.5067	0.5697	0.1970	0.132*
H26C	0.7073	0.5778	0.2243	0.132*
C27	0.5016 (7)	0.6134 (3)	0.3160 (2)	0.0726 (13)
H27	0.5261	0.5620	0.3197	0.087*
C28	0.8396 (6)	0.1388 (3)	0.6757 (2)	0.0836 (16)
H28A	0.8060	0.1752	0.7056	0.125*
H28B	0.8962	0.0964	0.6971	0.125*
H28C	0.7344	0.1222	0.6506	0.125*
C29	1.0019 (7)	0.2524 (3)	0.6437 (2)	0.0759 (14)
H29A	0.9434	0.2711	0.6786	0.114*
H29B	0.9580	0.2792	0.6066	0.114*
H29C	1.1291	0.2599	0.6513	0.114*
C30	1.0301 (5)	0.1338 (2)	0.59015 (18)	0.0506 (10)
H30	0.9951	0.0835	0.5854	0.061*
N1	0.8119 (3)	0.49033 (14)	0.42511 (11)	0.0278 (6)
N2	0.6181 (3)	0.11067 (14)	0.49621 (11)	0.0313 (6)
N3	0.5410 (4)	0.64597 (18)	0.26498 (14)	0.0501 (8)
N4	0.9645 (4)	0.1733 (2)	0.63570 (15)	0.0520 (8)
O1	0.9686 (3)	0.48245 (12)	0.09483 (9)	0.0361 (6)
O2	1.1689 (3)	0.56380 (13)	0.13980 (10)	0.0432 (6)
O3	0.7257 (4)	0.79565 (15)	0.61423 (13)	0.0569 (7)
H3A	0.683 (6)	0.8386 (13)	0.624 (2)	0.085*
O4	0.5576 (4)	0.73346 (15)	0.67822 (12)	0.0544 (7)
O5	0.4357 (5)	0.64314 (19)	0.35968 (14)	0.0839 (11)
O6	1.1334 (4)	0.15890 (17)	0.55402 (13)	0.0590 (8)
O1W	1.2630 (3)	0.54461 (14)	0.02156 (11)	0.0416 (6)
H1A	1.299 (5)	0.5844 (14)	0.0047 (18)	0.062*
H1B	1.278 (5)	0.559 (2)	0.0592 (8)	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0519 (3)	0.0240 (3)	0.0219 (3)	0.0006 (2)	0.0128 (2)	0.0000 (2)
C1	0.050 (2)	0.033 (2)	0.0353 (19)	0.0030 (16)	0.0075 (16)	−0.0027 (15)
C2	0.0362 (17)	0.0336 (18)	0.0293 (17)	0.0046 (14)	0.0013 (14)	−0.0048 (14)
C3	0.0421 (18)	0.0354 (19)	0.0278 (17)	0.0034 (15)	0.0100 (14)	0.0005 (14)
C4	0.0413 (18)	0.0293 (17)	0.0254 (16)	0.0013 (14)	0.0066 (14)	0.0021 (13)
C5	0.0270 (15)	0.0278 (17)	0.0248 (16)	0.0007 (13)	0.0013 (12)	0.0009 (12)
C6	0.0361 (17)	0.0308 (18)	0.0291 (17)	−0.0009 (14)	0.0081 (14)	−0.0001 (13)
C7	0.0378 (18)	0.0275 (17)	0.0360 (18)	−0.0006 (14)	0.0060 (15)	0.0006 (14)
C8	0.0272 (15)	0.0292 (16)	0.0266 (16)	−0.0020 (13)	0.0054 (13)	−0.0014 (13)
C9	0.0295 (16)	0.0309 (17)	0.0228 (15)	−0.0004 (13)	0.0057 (13)	0.0016 (12)
C10	0.0298 (15)	0.0284 (16)	0.0214 (15)	0.0015 (13)	0.0046 (12)	0.0016 (12)
C11	0.0371 (17)	0.0282 (17)	0.0217 (15)	0.0012 (13)	0.0063 (13)	−0.0005 (12)
C12	0.0317 (16)	0.0287 (17)	0.0187 (14)	−0.0002 (13)	0.0039 (12)	0.0017 (12)
C13	0.0338 (16)	0.0274 (17)	0.0229 (15)	0.0020 (13)	0.0074 (13)	0.0034 (12)
C14	0.0452 (19)	0.0290 (17)	0.0261 (16)	−0.0059 (14)	0.0118 (14)	0.0008 (13)
C15	0.0480 (19)	0.0296 (18)	0.0211 (15)	0.0010 (14)	0.0075 (14)	0.0008 (13)
C16	0.0390 (17)	0.0244 (16)	0.0226 (15)	0.0038 (13)	0.0102 (13)	0.0026 (12)
C17	0.0437 (18)	0.0272 (17)	0.0263 (16)	−0.0049 (14)	0.0081 (14)	0.0032 (13)
C18	0.0448 (18)	0.0322 (18)	0.0209 (16)	−0.0038 (14)	0.0065 (14)	−0.0012 (12)
C19	0.0482 (19)	0.0265 (18)	0.0268 (17)	0.0052 (15)	0.0115 (15)	0.0043 (13)
C20	0.0333 (16)	0.0241 (16)	0.0229 (15)	0.0006 (13)	0.0054 (12)	0.0001 (12)
C21	0.0439 (19)	0.0327 (18)	0.0286 (17)	−0.0002 (15)	0.0144 (15)	0.0001 (13)
C22	0.0481 (19)	0.0285 (17)	0.0296 (17)	0.0029 (15)	0.0132 (15)	−0.0025 (13)
C23	0.0461 (19)	0.0294 (17)	0.0240 (16)	0.0000 (14)	0.0124 (14)	0.0014 (13)
C24	0.0406 (17)	0.0264 (16)	0.0213 (15)	−0.0009 (13)	0.0063 (13)	−0.0003 (12)
C25	0.226 (8)	0.052 (4)	0.107 (5)	0.005 (4)	0.016 (5)	0.023 (3)
C26	0.084 (3)	0.127 (5)	0.055 (3)	0.038 (3)	0.025 (3)	0.002 (3)
C27	0.103 (4)	0.055 (3)	0.064 (3)	0.011 (3)	0.032 (3)	0.009 (2)
C28	0.078 (3)	0.116 (5)	0.061 (3)	−0.027 (3)	0.031 (3)	−0.016 (3)
C29	0.092 (3)	0.065 (3)	0.073 (3)	0.005 (3)	0.020 (3)	−0.018 (2)
C30	0.054 (2)	0.051 (2)	0.047 (2)	0.0043 (19)	0.0038 (19)	−0.0033 (18)
N1	0.0320 (13)	0.0289 (15)	0.0235 (13)	−0.0014 (11)	0.0069 (11)	0.0025 (10)
N2	0.0468 (16)	0.0251 (14)	0.0232 (13)	−0.0013 (12)	0.0103 (12)	0.0005 (10)
N3	0.059 (2)	0.051 (2)	0.0425 (18)	0.0119 (16)	0.0188 (15)	0.0105 (15)
N4	0.0484 (18)	0.063 (2)	0.0460 (19)	0.0022 (16)	0.0137 (15)	−0.0078 (16)
O1	0.0617 (15)	0.0290 (13)	0.0190 (11)	−0.0026 (10)	0.0118 (11)	−0.0013 (9)
O2	0.0644 (16)	0.0364 (14)	0.0311 (12)	−0.0112 (12)	0.0170 (11)	0.0010 (10)
O3	0.0751 (19)	0.0377 (16)	0.0612 (17)	0.0008 (14)	0.0256 (15)	−0.0095 (13)
O4	0.0735 (18)	0.0479 (17)	0.0439 (15)	0.0008 (14)	0.0177 (14)	−0.0080 (12)
O5	0.134 (3)	0.071 (2)	0.0527 (18)	0.008 (2)	0.044 (2)	−0.0085 (16)
O6	0.0602 (17)	0.065 (2)	0.0548 (17)	0.0113 (14)	0.0242 (14)	−0.0028 (14)
O1W	0.0544 (15)	0.0381 (15)	0.0345 (13)	−0.0061 (12)	0.0165 (12)	−0.0018 (11)

Geometric parameters (Å, º) top

Zn1—O1	2.096 (2)	C18—H18	0.9300
Zn1—O1ⁱ	2.096 (2)	C19—O1	1.255 (4)
Zn1—O1W	2.131 (3)	C19—O2	1.261 (4)
Zn1—O1Wⁱ	2.131 (3)	C20—C24	1.393 (4)
Zn1—N2ⁱⁱ	2.154 (3)	C20—C21	1.400 (4)
Zn1—N2ⁱⁱⁱ	2.154 (3)	C21—C22	1.371 (4)
C1—O4	1.217 (4)	C21—H21	0.9300
C1—O3	1.326 (4)	C22—N2	1.342 (4)
C1—C2	1.478 (4)	C22—H22	0.9300
C2—C3	1.383 (5)	C23—N2	1.344 (4)
C2—C7	1.385 (4)	C23—C24	1.375 (4)
C3—C4	1.389 (4)	C23—H23	0.9300
C3—H3	0.9300	C24—H24	0.9300
C4—C5	1.392 (4)	C25—N3	1.431 (6)
C4—H4	0.9300	C25—H25A	0.9600
C5—C6	1.391 (4)	C25—H25B	0.9600
C5—C8	1.490 (4)	C25—H25C	0.9600
C6—C7	1.375 (4)	C26—N3	1.453 (5)
C6—H6	0.9300	C26—H26A	0.9600
C7—H7	0.9300	C26—H26B	0.9600
C8—N1	1.342 (4)	C26—H26C	0.9600
C8—C9	1.397 (4)	C27—O5	1.217 (5)
C9—C10	1.395 (4)	C27—N3	1.297 (5)
C9—H9	0.9300	C27—H27	0.9300
C10—C11	1.400 (4)	C28—N4	1.458 (5)
C10—C20	1.471 (4)	C28—H28A	0.9600
C11—C12	1.387 (4)	C28—H28B	0.9600
C11—H11	0.9300	C28—H28C	0.9600
C12—N1	1.344 (4)	C29—N4	1.436 (5)
C12—C13	1.490 (4)	C29—H29A	0.9600
C13—C14	1.394 (4)	C29—H29B	0.9600
C13—C18	1.396 (4)	C29—H29C	0.9600
C14—C15	1.384 (4)	C30—O6	1.226 (4)
C14—H14	0.9300	C30—N4	1.333 (5)
C15—C16	1.390 (4)	C30—H30	0.9300
C15—H15	0.9300	N2—Zn1^iv	2.154 (3)
C16—C17	1.391 (4)	O3—H3A	0.86 (1)
C16—C19	1.504 (4)	O1W—H1A	0.85 (1)
C17—C18	1.378 (4)	O1W—H1B	0.85 (1)
C17—H17	0.9300

O1—Zn1—O1ⁱ	180.0	C17—C18—C13	120.7 (3)
O1—Zn1—O1W	91.38 (9)	C17—C18—H18	119.7
O1ⁱ—Zn1—O1W	88.62 (9)	C13—C18—H18	119.7
O1—Zn1—O1Wⁱ	88.62 (9)	O1—C19—O2	125.3 (3)
O1ⁱ—Zn1—O1Wⁱ	91.38 (9)	O1—C19—C16	117.1 (3)
O1W—Zn1—O1Wⁱ	180.0	O2—C19—C16	117.5 (3)
O1—Zn1—N2ⁱⁱ	89.05 (9)	C24—C20—C21	116.2 (3)
O1ⁱ—Zn1—N2ⁱⁱ	90.95 (9)	C24—C20—C10	121.3 (3)
O1W—Zn1—N2ⁱⁱ	88.43 (10)	C21—C20—C10	122.3 (3)
O1Wⁱ—Zn1—N2ⁱⁱ	91.57 (10)	C22—C21—C20	120.1 (3)
O1—Zn1—N2ⁱⁱⁱ	90.95 (9)	C22—C21—H21	120.0
O1ⁱ—Zn1—N2ⁱⁱⁱ	89.05 (9)	C20—C21—H21	120.0
O1W—Zn1—N2ⁱⁱⁱ	91.57 (10)	N2—C22—C21	123.4 (3)
O1Wⁱ—Zn1—N2ⁱⁱⁱ	88.43 (10)	N2—C22—H22	118.3
N2ⁱⁱ—Zn1—N2ⁱⁱⁱ	180.0	C21—C22—H22	118.3
O4—C1—O3	122.8 (3)	N2—C23—C24	123.3 (3)
O4—C1—C2	124.9 (3)	N2—C23—H23	118.3
O3—C1—C2	112.3 (3)	C24—C23—H23	118.3
C3—C2—C7	119.4 (3)	C23—C24—C20	120.1 (3)
C3—C2—C1	119.5 (3)	C23—C24—H24	120.0
C7—C2—C1	121.0 (3)	C20—C24—H24	120.0
C2—C3—C4	120.2 (3)	N3—C25—H25A	109.5
C2—C3—H3	119.9	N3—C25—H25B	109.5
C4—C3—H3	119.9	H25A—C25—H25B	109.5
C3—C4—C5	120.8 (3)	N3—C25—H25C	109.5
C3—C4—H4	119.6	H25A—C25—H25C	109.5
C5—C4—H4	119.6	H25B—C25—H25C	109.5
C6—C5—C4	118.0 (3)	N3—C26—H26A	109.5
C6—C5—C8	119.6 (3)	N3—C26—H26B	109.5
C4—C5—C8	122.4 (3)	H26A—C26—H26B	109.5
C7—C6—C5	121.4 (3)	N3—C26—H26C	109.5
C7—C6—H6	119.3	H26A—C26—H26C	109.5
C5—C6—H6	119.3	H26B—C26—H26C	109.5
C6—C7—C2	120.3 (3)	O5—C27—N3	126.7 (5)
C6—C7—H7	119.9	O5—C27—H27	116.6
C2—C7—H7	119.9	N3—C27—H27	116.6
N1—C8—C9	122.5 (3)	N4—C28—H28A	109.5
N1—C8—C5	115.0 (3)	N4—C28—H28B	109.5
C9—C8—C5	122.4 (3)	H28A—C28—H28B	109.5
C10—C9—C8	119.7 (3)	N4—C28—H28C	109.5
C10—C9—H9	120.1	H28A—C28—H28C	109.5
C8—C9—H9	120.1	H28B—C28—H28C	109.5
C9—C10—C11	117.1 (3)	N4—C29—H29A	109.5
C9—C10—C20	122.3 (3)	N4—C29—H29B	109.5
C11—C10—C20	120.5 (3)	H29A—C29—H29B	109.5
C12—C11—C10	119.8 (3)	N4—C29—H29C	109.5
C12—C11—H11	120.1	H29A—C29—H29C	109.5
C10—C11—H11	120.1	H29B—C29—H29C	109.5
N1—C12—C11	122.8 (3)	O6—C30—N4	124.6 (4)
N1—C12—C13	116.1 (3)	O6—C30—H30	117.7
C11—C12—C13	121.1 (3)	N4—C30—H30	117.7
C14—C13—C18	118.5 (3)	C8—N1—C12	118.0 (3)
C14—C13—C12	121.4 (3)	C22—N2—C23	116.7 (3)
C18—C13—C12	120.1 (3)	C22—N2—Zn1^iv	122.2 (2)
C15—C14—C13	120.8 (3)	C23—N2—Zn1^iv	120.6 (2)
C15—C14—H14	119.6	C27—N3—C25	120.0 (4)
C13—C14—H14	119.6	C27—N3—C26	123.2 (4)
C14—C15—C16	120.3 (3)	C25—N3—C26	116.6 (4)
C14—C15—H15	119.8	C30—N4—C29	121.4 (4)
C16—C15—H15	119.8	C30—N4—C28	120.6 (4)
C15—C16—C17	119.0 (3)	C29—N4—C28	117.8 (4)
C15—C16—C19	120.3 (3)	C19—O1—Zn1	128.7 (2)
C17—C16—C19	120.7 (3)	C1—O3—H3A	119 (3)
C18—C17—C16	120.7 (3)	Zn1—O1W—H1A	122 (3)
C18—C17—H17	119.7	Zn1—O1W—H1B	111 (3)
C16—C17—H17	119.7	H1A—O1W—H1B	98 (4)

O4—C1—C2—C3	−9.9 (5)	C19—C16—C17—C18	−179.7 (3)
O3—C1—C2—C3	171.1 (3)	C16—C17—C18—C13	0.8 (5)
O4—C1—C2—C7	166.5 (3)	C14—C13—C18—C17	−1.7 (5)
O3—C1—C2—C7	−12.6 (5)	C12—C13—C18—C17	177.6 (3)
C7—C2—C3—C4	−0.7 (5)	C15—C16—C19—O1	12.2 (4)
C1—C2—C3—C4	175.7 (3)	C17—C16—C19—O1	−167.6 (3)
C2—C3—C4—C5	−0.1 (5)	C15—C16—C19—O2	−166.8 (3)
C3—C4—C5—C6	−0.1 (5)	C17—C16—C19—O2	13.4 (5)
C3—C4—C5—C8	−178.2 (3)	C9—C10—C20—C24	26.9 (4)
C4—C5—C6—C7	1.1 (4)	C11—C10—C20—C24	−150.4 (3)
C8—C5—C6—C7	179.3 (3)	C9—C10—C20—C21	−158.1 (3)
C5—C6—C7—C2	−1.9 (5)	C11—C10—C20—C21	24.6 (4)
C3—C2—C7—C6	1.7 (5)	C24—C20—C21—C22	3.3 (4)
C1—C2—C7—C6	−174.6 (3)	C10—C20—C21—C22	−171.9 (3)
C6—C5—C8—N1	−7.2 (4)	C20—C21—C22—N2	0.7 (5)
C4—C5—C8—N1	170.9 (3)	N2—C23—C24—C20	0.6 (5)
C6—C5—C8—C9	173.1 (3)	C21—C20—C24—C23	−3.9 (4)
C4—C5—C8—C9	−8.8 (4)	C10—C20—C24—C23	171.3 (3)
N1—C8—C9—C10	−1.9 (4)	C9—C8—N1—C12	1.8 (4)
C5—C8—C9—C10	177.7 (3)	C5—C8—N1—C12	−177.9 (2)
C8—C9—C10—C11	0.7 (4)	C11—C12—N1—C8	−0.4 (4)
C8—C9—C10—C20	−176.6 (3)	C13—C12—N1—C8	179.2 (2)
C9—C10—C11—C12	0.5 (4)	C21—C22—N2—C23	−4.0 (5)
C20—C10—C11—C12	177.9 (3)	C21—C22—N2—Zn1^iv	168.0 (2)
C10—C11—C12—N1	−0.7 (5)	C24—C23—N2—C22	3.4 (5)
C10—C11—C12—C13	179.6 (3)	C24—C23—N2—Zn1^iv	−168.8 (2)
N1—C12—C13—C14	−150.2 (3)	O5—C27—N3—C25	4.1 (8)
C11—C12—C13—C14	29.5 (4)	O5—C27—N3—C26	−172.1 (5)
N1—C12—C13—C18	30.6 (4)	O6—C30—N4—C29	4.2 (6)
C11—C12—C13—C18	−149.7 (3)	O6—C30—N4—C28	178.8 (4)
C18—C13—C14—C15	1.2 (5)	O2—C19—O1—Zn1	−5.2 (5)
C12—C13—C14—C15	−178.1 (3)	C16—C19—O1—Zn1	175.85 (19)
C13—C14—C15—C16	0.1 (5)	O1W—Zn1—O1—C19	24.7 (3)
C14—C15—C16—C17	−1.0 (5)	O1Wⁱ—Zn1—O1—C19	−155.3 (3)
C14—C15—C16—C19	179.3 (3)	N2ⁱⁱ—Zn1—O1—C19	113.1 (3)
C15—C16—C17—C18	0.5 (5)	N2ⁱⁱⁱ—Zn1—O1—C19	−66.9 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O6^v	0.85 (1)	1.93 (2)	2.750 (4)	164 (4)
O1W—H1B···O2	0.85 (1)	1.98 (2)	2.718 (3)	145 (4)
O3—H3A···O2^vi	0.86 (1)	1.77 (2)	2.592 (3)	161 (5)

Symmetry codes: (v) −x+5/2, y+1/2, −z+1/2; (vi) x−1/2, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₂₄H₁₅N₂O₄)₂(H₂O)₂]·4C₃H₇NO
M_r	1184.57
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	7.4744 (5), 17.7122 (13), 21.4993 (15)
β (°)	95.075 (1)
V (Å³)	2835.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.25 × 0.22 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.839, 0.915
No. of measured, independent and observed [I > 2σ(I)] reflections	15534, 5606, 3804
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.158, 1.05
No. of reflections	5606
No. of parameters	385
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)	0.40, −0.35

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O6ⁱ	0.85 (1)	1.93 (2)	2.750 (4)	164 (4)
O1W—H1B···O2	0.85 (1)	1.98 (2)	2.718 (3)	145 (4)
O3—H3A···O2ⁱⁱ	0.86 (1)	1.77 (2)	2.592 (3)	161 (5)

Symmetry codes: (i) −x+5/2, y+1/2, −z+1/2; (ii) x−1/2, −y+3/2, z+1/2.

Acknowledgements

The authors are grateful for financial aid from the National Natural Science Foundation of China (grant No. 21001101).

References

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