Poly[tetra-n-butyl­ammonium [(μ5-benzene-1,3,5-tricarboxyl­ato)(μ4-benzene-1,3,5-tricarboxyl­ato)-μ3-hydroxido-trizincate] 0.25-hydrate]

Zhu, X.-H.; Cheng, X.-C.

doi:10.1107/S1600536811044485

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1641

doi:10.1107/S1600536811044485

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Poly[tetra-n-butylammonium [(μ₅-benzene-1,3,5-tricarboxylato)(μ₄-benzene-1,3,5-tricarboxylato)-μ₃-hydroxido-trizincate] 0.25-hydrate]

Xiao-Hong Zhu ^a ^* and Xiao-Chun Cheng ^a

^aFaculty of Life Science and Chemical Engineering, Huaiyin Institute of Technology, Huaian 223003, People's Republic of China
^*Correspondence e-mail: hgzhuxh@yeah.net

(Received 4 October 2011; accepted 25 October 2011; online 29 October 2011)

In the asymmetric unit of title coordination polymer, {(C₁₆H₃₆N)[Zn₃(C₉H₃O₆)₂(OH)]·0.25H₂O}_n, there are three independent Zn²⁺ cations, two benzene-1,3,5-tricarboxylate ligands and a μ₃-bridging hydroxide group, together with a tetra-n-butylammonium counter-cation and a partially occupied water molecule of solvation (occupancy 0.25). Each Zn ion is coordinated by three carboxylate O atoms and one O atom from the bridging hydroxide ion, displaying a slightly distorted tetrahedral stereochemistry [overall Zn—O range = 1.875 (3)–1.987 (2) Å]. An intramolecular hydrogen bond involving the hydroxide H atom and a carboxylate O-atom acceptor is also present in the complex unit. The bridging benzene-1,3,5-tricarboxylate anions generate a three-dimensional framework structure.

Related literature

For a related structure, see: Su et al. (2009 ).

Experimental

Crystal data

(C₁₆H₃₆N)[Zn₃(C₉H₃O₆)₂(OH)]·0.25H₂O
M_r = 873.86
Orthorhombic, P b c a
a = 16.295 (5) Å
b = 16.295 (5) Å
c = 28.946 (5) Å
V = 7686 (4) Å³
Z = 8
Mo Kα radiation
μ = 1.92 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.18 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.700, T_max = 0.724
46890 measured reflections
9492 independent reflections
6072 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.099
S = 0.93
9492 reflections
443 parameters
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −1.35 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H7⋯O8	0.93	1.73	2.609 (3)	158

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811044485/zs2153sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811044485/zs2153Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811044485/zs2153Isup4.cdx

checkCIF report

Comment top

benzene-1,3,5-tricarboxylic acid is often used as organic ligand in the synthesis of metal complexes because of its abundant and variable coordination modes (Su et al., 2009). Herein, we report the crystal structure of the title coordination polymer, [[(C₁₆H₃₆N) Zn₃(C₉H₃O₃)₂(OH)].0.25(H₂O)]_n (Fig. 1). In the asymmetric unit there are three independent Zn cations, two benzene-1,3,5-tricarboxylate ligands and a µ₃-bridging hydroxide group, together with a tetra-n-butylammonium counter-cation and a partial water molecule of solvation. The coordination sphere about each ZnO₄ centre comprises three carboxylate O atoms from separate benzene-1,3,5-tricarboxylate anions and one O atom from the bridging hydroxide anion, giving in each a slightly distorted tetrahedral stereochemistry [Zn—O ranges: 1.875 (3)–1.958 (2) Å (Zn1); 1.914 (2)–1.987 (2) Å (Zn2); 1.921 (2)–1.968 (2) Å (Zn3)]. An intramolecular hydrogen bond involving the hydroxo ligand H-donor and a carboxylate O-acceptor is also present in the complex unit (Table 1). The bridging benzene-1,3,5-tricarboxylate anions generate a three-dimensional framework structure (Fig. 2).

Related literature top

For a related structure, see: Su et al. (2009).

Experimental top

The reaction mixture of zinc nitrate hexahydrate (59.4 mg, 0.2 mmol), benzene-1,3,5-tricarboxylic acid (21.0 mg, 0.1 mmol), and 1 ml of aqueous tetra-n-butylammonium hydroxide solution (10%, w/w) in 12 ml of water was sealed in a 16 ml Teflon-lined stainless steel container and heated to 453 K for 3 days. After cooling to room temperature, colorless block crystals of the title complex were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. : The coordination environment of the Zn ions in the title complex together with the tetra-n-butylammonium counter-cation and the partial water molecule of solvation, with the ellipsoids drawn at the 30% probability level. The hydrogen atoms are omitted. Symmetry code: (A) x + 1/2, -y + 1/2, -z + 1; (B) -x + 3/2, y - 1/2, z; (C) -x + 2, y + 1/2, -z + 3/2; (D) x + 1/2, y, -z + 3/2.
	Fig. 2. : The packing diagram of title coordination polymer complex. The tetra-n-butylammonium counter-cation and the partial water molecule of solvation are omitted for clarity.

Poly[tetra-n-butylammonium [(µ₅-benzene-1,3,5-tricarboxylato)(µ₄- benzene-1,3,5-tricarboxylato)-µ₃-hydroxido-trizincate] 0.25-hydrate] top

Crystal data top

(C₁₆H₃₆N)[Zn₃(C₉H₃O₆)₂(OH)]·0.25H₂O	F(000) = 3600
M_r = 873.86	D_x = 1.510 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6690 reflections
a = 16.295 (5) Å	θ = 2.3–25.4°
b = 16.295 (5) Å	µ = 1.92 mm⁻¹
c = 28.946 (5) Å	T = 293 K
V = 7686 (4) Å³	Block, colorless
Z = 8	0.20 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	9492 independent reflections
Radiation source: fine-focus sealed tube	6072 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ϕ and ω scans	θ_max = 28.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→16
T_min = 0.700, T_max = 0.724	k = −16→21
46890 measured reflections	l = −38→37

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.040P)²] where P = (F_o² + 2F_c²)/3
9492 reflections	(Δ/σ)_max = 0.002
443 parameters	Δρ_max = 1.24 e Å⁻³
0 restraints	Δρ_min = −1.35 e Å⁻³

Crystal data top

(C₁₆H₃₆N)[Zn₃(C₉H₃O₆)₂(OH)]·0.25H₂O	V = 7686 (4) Å³
M_r = 873.86	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 16.295 (5) Å	µ = 1.92 mm⁻¹
b = 16.295 (5) Å	T = 293 K
c = 28.946 (5) Å	0.20 × 0.20 × 0.18 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	9492 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	6072 reflections with I > 2σ(I)
T_min = 0.700, T_max = 0.724	R_int = 0.060
46890 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.099	H-atom parameters constrained
S = 0.93	Δρ_max = 1.24 e Å⁻³
9492 reflections	Δρ_min = −1.35 e Å⁻³
443 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 > 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	Occ. (<1)
C1	0.76518 (19)	0.3324 (2)	0.57153 (11)	0.0241 (8)
C2	0.72626 (19)	0.2998 (2)	0.53324 (11)	0.0250 (8)
H1	0.7475	0.2534	0.5188	0.030*
C3	0.65577 (19)	0.3364 (2)	0.51636 (11)	0.0224 (7)
C4	0.62623 (19)	0.4065 (2)	0.53724 (11)	0.0235 (7)
H2	0.5783	0.4305	0.5262	0.028*
C5	0.6665 (2)	0.4418 (2)	0.57412 (11)	0.0240 (8)
C6	0.7354 (2)	0.4038 (2)	0.59158 (11)	0.0265 (8)
H3	0.7621	0.4262	0.6170	0.032*
C11	0.8392 (2)	0.2900 (2)	0.59169 (12)	0.0252 (8)
C31	0.6116 (2)	0.3057 (2)	0.47464 (11)	0.0230 (7)
C51	0.6355 (2)	0.5218 (2)	0.59296 (13)	0.0332 (9)
C101	0.9004 (2)	0.0957 (2)	0.76805 (11)	0.0231 (7)
C102	0.92903 (19)	0.0206 (2)	0.78223 (11)	0.0247 (8)
H4	0.9737	−0.0029	0.7672	0.030*
C103	0.89223 (19)	−0.0204 (2)	0.81857 (11)	0.0225 (7)
C104	0.82612 (19)	0.0157 (2)	0.84119 (11)	0.0256 (8)
H5	0.8012	−0.0113	0.8658	0.031*
C105	0.79740 (19)	0.0912 (2)	0.82739 (11)	0.0244 (8)
C106	0.83441 (19)	0.1305 (2)	0.79074 (11)	0.0240 (8)
H6	0.8146	0.1813	0.7811	0.029*
C111	0.9409 (2)	0.1396 (2)	0.72901 (12)	0.0274 (8)
C131	0.9225 (2)	−0.1027 (2)	0.83342 (11)	0.0246 (8)
C151	0.7268 (2)	0.1304 (2)	0.85213 (12)	0.0279 (8)
C211	0.8723 (2)	0.3453 (3)	0.82377 (14)	0.0455 (11)
H9	0.8856	0.3017	0.8022	0.055*
H8	0.8161	0.3366	0.8337	0.055*
C212	0.8758 (3)	0.4257 (3)	0.79796 (15)	0.0527 (12)
H10	0.8596	0.4701	0.8183	0.063*
H11	0.9316	0.4360	0.7878	0.063*
C213	0.81928 (19)	0.4232 (2)	0.75671 (12)	0.0639 (14)
H13	0.7634	0.4147	0.7672	0.077*
H12	0.8342	0.3772	0.7371	0.077*
C214	0.82376 (19)	0.5032 (2)	0.72833 (12)	0.0888 (19)
H14	0.8231	0.5494	0.7489	0.133*
H16	0.7775	0.5062	0.7079	0.133*
H15	0.8735	0.5038	0.7106	0.133*
C221	1.0164 (2)	0.3513 (3)	0.85266 (15)	0.0587 (14)
H18	1.0504	0.3435	0.8798	0.070*
H17	1.0220	0.4082	0.8432	0.070*
C222	1.0494 (3)	0.2962 (4)	0.81374 (18)	0.0782 (17)
H19	1.0380	0.2393	0.8212	0.094*
H20	1.0209	0.3092	0.7853	0.094*
C223	1.1379 (2)	0.3062 (3)	0.80653 (17)	0.108 (2)
H22	1.1662	0.2968	0.8356	0.129*
H21	1.1489	0.3622	0.7970	0.129*
C224	1.1714 (2)	0.2487 (3)	0.77085 (17)	0.137 (3)
H25	1.1587	0.1932	0.7793	0.205*
H24	1.2299	0.2552	0.7689	0.205*
H23	1.1472	0.2609	0.7414	0.205*
C231	0.9169 (3)	0.2499 (3)	0.88305 (16)	0.0545 (12)
H27	0.9338	0.2125	0.8588	0.065*
H26	0.8589	0.2408	0.8886	0.065*
C232	0.9637 (3)	0.2281 (3)	0.92683 (17)	0.0724 (16)
H28	1.0222	0.2279	0.9208	0.087*
H29	0.9525	0.2683	0.9507	0.087*
C233	0.9361 (3)	0.1441 (3)	0.94246 (19)	0.132
H30	0.9478	0.1044	0.9184	0.158*
H31	0.8772	0.1446	0.9475	0.158*
C234	0.9790 (3)	0.1180 (3)	0.98675 (19)	0.172 (4)
H32	1.0347	0.1371	0.9864	0.258*
H33	0.9785	0.0592	0.9891	0.258*
H34	0.9508	0.1411	1.0128	0.258*
C241	0.9052 (2)	0.3982 (3)	0.90251 (14)	0.0472 (11)
H35	0.9461	0.3962	0.9268	0.057*
H36	0.9072	0.4526	0.8889	0.057*
C242	0.8221 (2)	0.3864 (3)	0.92395 (14)	0.0449 (11)
H38	0.8185	0.3318	0.9372	0.054*
H37	0.7800	0.3913	0.9004	0.054*
C243	0.8077 (2)	0.4499 (2)	0.96125 (11)	0.0593 (13)
H39	0.8159	0.5041	0.9482	0.071*
H40	0.8481	0.4423	0.9855	0.071*
C244	0.7220 (2)	0.4457 (2)	0.98250 (11)	0.0803 (17)
H42	0.6815	0.4491	0.9585	0.120*
H43	0.7148	0.4906	1.0036	0.120*
H41	0.7158	0.3948	0.9988	0.120*
N1	0.92799 (19)	0.3363 (2)	0.86590 (11)	0.0427 (9)
O1	0.87184 (14)	0.23552 (16)	0.56768 (8)	0.0362 (6)
O2	0.86264 (14)	0.31397 (16)	0.63058 (8)	0.0355 (6)
O3	0.64976 (14)	0.25944 (15)	0.44788 (8)	0.0305 (6)
O4	0.53918 (13)	0.32934 (16)	0.46956 (8)	0.0337 (6)
O5	0.57056 (17)	0.54736 (18)	0.57447 (10)	0.0531 (6)
O6	0.67374 (17)	0.55794 (17)	0.62306 (10)	0.0531 (6)
O7	0.91524 (14)	0.21258 (14)	0.72211 (8)	0.0295 (6)
O8	0.99505 (16)	0.10514 (16)	0.70684 (9)	0.0431 (7)
O9	0.98565 (14)	−0.12995 (15)	0.81338 (8)	0.0315 (6)
O10	0.88317 (14)	−0.13893 (14)	0.86430 (8)	0.0316 (6)
O11	0.71941 (14)	0.20737 (15)	0.84644 (8)	0.0329 (6)
O12	0.68018 (16)	0.09061 (16)	0.87645 (9)	0.0468 (8)
O13	1.02002 (12)	0.19730 (13)	0.63449 (7)	0.0184 (5)
H7	1.0246	0.1607	0.6588	0.022*
Zn1	0.95951 (2)	0.15787 (2)	0.580582 (13)	0.02168 (10)
Zn2	0.95001 (2)	0.27515 (2)	0.669671 (12)	0.01930 (10)
Zn3	1.12713 (2)	0.24495 (2)	0.618089 (13)	0.02092 (10)
O1W	0.1549 (8)	0.1219 (9)	0.8850 (4)	0.083	0.25

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0221 (17)	0.025 (2)	0.0250 (18)	0.0056 (15)	−0.0026 (14)	0.0001 (15)
C2	0.0276 (19)	0.024 (2)	0.0238 (18)	0.0059 (15)	−0.0031 (15)	−0.0047 (15)
C3	0.0214 (17)	0.0221 (19)	0.0237 (18)	0.0008 (14)	−0.0029 (14)	−0.0010 (15)
C4	0.0193 (17)	0.025 (2)	0.0261 (18)	0.0038 (15)	−0.0005 (14)	0.0023 (15)
C5	0.0257 (18)	0.024 (2)	0.0222 (18)	0.0044 (15)	−0.0021 (14)	−0.0034 (15)
C6	0.0288 (19)	0.029 (2)	0.0223 (18)	0.0036 (16)	−0.0047 (15)	−0.0051 (16)
C11	0.0239 (18)	0.025 (2)	0.0265 (19)	0.0037 (15)	−0.0032 (15)	0.0027 (16)
C31	0.0271 (19)	0.0205 (19)	0.0212 (18)	−0.0002 (15)	−0.0043 (14)	0.0029 (15)
C51	0.039 (2)	0.025 (2)	0.036 (2)	0.0037 (17)	−0.0047 (17)	−0.0082 (17)
C101	0.0270 (18)	0.0190 (19)	0.0233 (18)	0.0021 (14)	0.0033 (14)	0.0050 (15)
C102	0.0234 (18)	0.024 (2)	0.0265 (19)	0.0051 (15)	0.0067 (14)	0.0038 (15)
C103	0.0229 (18)	0.0184 (19)	0.0262 (19)	0.0025 (14)	0.0007 (14)	0.0027 (15)
C104	0.0266 (19)	0.022 (2)	0.028 (2)	0.0014 (15)	0.0049 (15)	0.0054 (15)
C105	0.0234 (18)	0.022 (2)	0.0283 (19)	0.0026 (14)	0.0033 (14)	0.0021 (16)
C106	0.0269 (18)	0.0178 (19)	0.0272 (19)	0.0031 (14)	0.0007 (15)	0.0044 (15)
C111	0.030 (2)	0.023 (2)	0.029 (2)	0.0045 (15)	0.0035 (16)	0.0059 (16)
C131	0.0287 (19)	0.0195 (19)	0.0256 (19)	−0.0021 (15)	−0.0025 (15)	0.0001 (15)
C151	0.0264 (19)	0.024 (2)	0.033 (2)	0.0042 (16)	0.0007 (16)	0.0012 (17)
C211	0.041 (2)	0.049 (3)	0.047 (3)	−0.009 (2)	−0.005 (2)	−0.014 (2)
C212	0.047 (3)	0.052 (3)	0.059 (3)	−0.008 (2)	0.004 (2)	−0.005 (2)
C213	0.058 (3)	0.073 (4)	0.061 (3)	0.006 (3)	−0.001 (3)	−0.013 (3)
C214	0.091 (4)	0.103 (5)	0.072 (4)	0.023 (4)	0.002 (3)	0.019 (4)
C221	0.037 (3)	0.076 (4)	0.064 (3)	−0.011 (2)	−0.005 (2)	−0.023 (3)
C222	0.049 (3)	0.099 (5)	0.087 (4)	−0.002 (3)	0.003 (3)	−0.042 (4)
C223	0.062 (4)	0.137 (7)	0.124 (5)	−0.019 (4)	0.031 (4)	−0.057 (5)
C224	0.101 (5)	0.134 (7)	0.175 (7)	−0.015 (5)	0.060 (5)	−0.084 (6)
C231	0.060 (3)	0.039 (3)	0.064 (3)	−0.002 (2)	−0.015 (2)	−0.010 (2)
C232	0.079 (4)	0.052 (3)	0.087 (4)	0.003 (3)	−0.035 (3)	−0.011 (3)
C233	0.202	0.067	0.127	0.015	−0.102	−0.027
C234	0.229 (9)	0.096 (7)	0.191 (9)	0.001 (6)	−0.073 (7)	0.030 (6)
C241	0.055 (3)	0.042 (3)	0.044 (3)	−0.008 (2)	−0.008 (2)	−0.014 (2)
C242	0.047 (3)	0.040 (3)	0.048 (3)	0.001 (2)	−0.004 (2)	−0.004 (2)
C243	0.078 (3)	0.054 (3)	0.045 (3)	−0.005 (3)	−0.002 (2)	−0.009 (2)
C244	0.088 (4)	0.081 (5)	0.072 (4)	0.007 (3)	0.017 (3)	−0.017 (3)
N1	0.0382 (19)	0.041 (2)	0.049 (2)	−0.0068 (16)	−0.0052 (16)	−0.0132 (18)
O1	0.0314 (14)	0.0412 (17)	0.0361 (14)	0.0195 (12)	−0.0088 (11)	−0.0106 (13)
O2	0.0377 (15)	0.0389 (17)	0.0298 (14)	0.0149 (12)	−0.0170 (11)	−0.0074 (12)
O3	0.0377 (14)	0.0286 (15)	0.0252 (13)	0.0103 (11)	−0.0107 (11)	−0.0093 (11)
O4	0.0231 (13)	0.0478 (18)	0.0303 (14)	0.0050 (12)	−0.0091 (11)	−0.0062 (12)
O5	0.0554 (13)	0.0365 (13)	0.0674 (14)	0.0197 (10)	−0.0221 (11)	−0.0241 (11)
O6	0.0554 (13)	0.0365 (13)	0.0674 (14)	0.0197 (10)	−0.0221 (11)	−0.0241 (11)
O7	0.0387 (14)	0.0203 (14)	0.0295 (14)	0.0043 (11)	0.0108 (11)	0.0088 (11)
O8	0.0517 (17)	0.0348 (17)	0.0428 (16)	0.0208 (13)	0.0261 (13)	0.0201 (13)
O9	0.0312 (14)	0.0268 (15)	0.0367 (15)	0.0121 (11)	0.0079 (11)	0.0098 (12)
O10	0.0410 (15)	0.0190 (14)	0.0348 (14)	0.0014 (11)	0.0127 (12)	0.0104 (11)
O11	0.0316 (14)	0.0227 (15)	0.0445 (16)	0.0056 (11)	0.0121 (11)	0.0060 (12)
O12	0.0440 (16)	0.0316 (17)	0.065 (2)	0.0041 (13)	0.0315 (14)	0.0127 (15)
O13	0.0187 (11)	0.0167 (12)	0.0199 (11)	0.0021 (9)	−0.0016 (9)	0.0023 (10)
Zn1	0.01888 (19)	0.0196 (2)	0.0266 (2)	−0.00071 (16)	0.00158 (16)	−0.00610 (17)
Zn2	0.02036 (19)	0.0173 (2)	0.0202 (2)	0.00008 (16)	−0.00066 (15)	0.00052 (16)
Zn3	0.01865 (19)	0.0210 (2)	0.0231 (2)	0.00059 (16)	−0.00087 (16)	−0.00463 (17)
O1W	0.083	0.087	0.079	0.064	−0.013	−0.012

Geometric parameters (Å, º) top

C1—C2	1.383 (4)	C222—H19	0.9700
C1—C6	1.388 (4)	C222—H20	0.9700
C1—C11	1.507 (4)	C223—C224	1.4970
C2—C3	1.383 (4)	C223—H22	0.9700
C2—H1	0.9300	C223—H21	0.9700
C3—C4	1.380 (4)	C224—H25	0.9600
C3—C31	1.492 (4)	C224—H24	0.9600
C4—C5	1.378 (4)	C224—H23	0.9600
C4—H2	0.9300	C231—N1	1.502 (5)
C5—C6	1.378 (4)	C231—C232	1.521 (6)
C5—C51	1.501 (5)	C231—H27	0.9700
C6—H3	0.9300	C231—H26	0.9700
C11—O1	1.247 (4)	C232—C233	1.511 (7)
C11—O2	1.251 (4)	C232—H28	0.9700
C31—O3	1.247 (4)	C232—H29	0.9700
C31—O4	1.251 (4)	C233—C234	1.5206
C51—O6	1.222 (4)	C233—H30	0.9700
C51—O5	1.257 (4)	C233—H31	0.9700
C101—C102	1.373 (4)	C234—H32	0.9600
C101—C106	1.382 (4)	C234—H33	0.9600
C101—C111	1.491 (4)	C234—H34	0.9600
C102—C103	1.383 (4)	C241—C242	1.502 (5)
C102—H4	0.9300	C241—N1	1.510 (5)
C103—C104	1.391 (4)	C241—H35	0.9700
C103—C131	1.492 (5)	C241—H36	0.9700
C104—C105	1.375 (4)	C242—C243	1.514 (5)
C104—H5	0.9300	C242—H38	0.9700
C105—C106	1.378 (4)	C242—H37	0.9700
C105—C151	1.498 (4)	C243—C244	1.5272
C106—H6	0.9300	C243—H39	0.9700
C111—O8	1.227 (4)	C243—H40	0.9700
C111—O7	1.277 (4)	C244—H42	0.9600
C131—O10	1.248 (4)	C244—H43	0.9600
C131—O9	1.262 (4)	C244—H41	0.9600
C151—O12	1.221 (4)	O1—Zn1	1.945 (2)
C151—O11	1.271 (4)	O2—Zn2	1.926 (2)
C211—C212	1.510 (6)	O3—Zn3ⁱ	1.946 (2)
C211—N1	1.527 (5)	O4—Zn1ⁱ	1.958 (2)
C211—H9	0.9700	O5—Zn1ⁱⁱ	1.875 (3)
C211—H8	0.9700	O7—Zn2	1.914 (2)
C212—C213	1.509 (5)	O9—Zn2ⁱⁱⁱ	1.932 (2)
C212—H10	0.9700	O10—Zn3ⁱⁱⁱ	1.967 (2)
C212—H11	0.9700	O11—Zn3^iv	1.921 (2)
C213—C214	1.5431	O13—Zn1	1.954 (2)
C213—H13	0.9700	O13—Zn3	1.968 (2)
C213—H12	0.9700	O13—Zn2	1.987 (2)
C214—H14	0.9600	O13—H7	0.9259
C214—H16	0.9600	Zn1—O5^v	1.875 (3)
C214—H15	0.9600	Zn1—O4^vi	1.958 (2)
C221—N1	1.511 (5)	Zn2—O9^vii	1.932 (2)
C221—C222	1.538 (6)	Zn3—O11^viii	1.921 (2)
C221—H18	0.9700	Zn3—O3^vi	1.946 (2)
C221—H17	0.9700	Zn3—O10^vii	1.967 (2)
C222—C223	1.466 (5)

C2—C1—C6	119.7 (3)	H22—C223—H21	107.8
C2—C1—C11	120.1 (3)	C223—C224—H25	109.5
C6—C1—C11	120.1 (3)	C223—C224—H24	109.5
C1—C2—C3	120.0 (3)	H25—C224—H24	109.5
C1—C2—H1	120.0	C223—C224—H23	109.5
C3—C2—H1	120.0	H25—C224—H23	109.5
C4—C3—C2	119.4 (3)	H24—C224—H23	109.5
C4—C3—C31	117.6 (3)	N1—C231—C232	115.7 (4)
C2—C3—C31	122.9 (3)	N1—C231—H27	108.3
C5—C4—C3	121.2 (3)	C232—C231—H27	108.3
C5—C4—H2	119.4	N1—C231—H26	108.3
C3—C4—H2	119.4	C232—C231—H26	108.3
C6—C5—C4	119.0 (3)	H27—C231—H26	107.4
C6—C5—C51	122.1 (3)	C233—C232—C231	108.2 (4)
C4—C5—C51	118.9 (3)	C233—C232—H28	110.1
C5—C6—C1	120.5 (3)	C231—C232—H28	110.1
C5—C6—H3	119.7	C233—C232—H29	110.1
C1—C6—H3	119.7	C231—C232—H29	110.1
O1—C11—O2	126.4 (3)	H28—C232—H29	108.4
O1—C11—C1	116.9 (3)	C232—C233—C234	111.7 (3)
O2—C11—C1	116.7 (3)	C232—C233—H30	109.3
O3—C31—O4	125.7 (3)	C234—C233—H30	109.3
O3—C31—C3	117.7 (3)	C232—C233—H31	109.3
O4—C31—C3	116.6 (3)	C234—C233—H31	109.3
O6—C51—O5	125.0 (4)	H30—C233—H31	107.9
O6—C51—C5	120.4 (3)	C233—C234—H32	109.5
O5—C51—C5	114.6 (3)	C233—C234—H33	109.5
C102—C101—C106	119.2 (3)	H32—C234—H33	109.5
C102—C101—C111	120.2 (3)	C233—C234—H34	109.5
C106—C101—C111	120.6 (3)	H32—C234—H34	109.5
C101—C102—C103	120.7 (3)	H33—C234—H34	109.5
C101—C102—H4	119.6	C242—C241—N1	115.2 (3)
C103—C102—H4	119.6	C242—C241—H35	108.5
C102—C103—C104	119.3 (3)	N1—C241—H35	108.5
C102—C103—C131	120.7 (3)	C242—C241—H36	108.5
C104—C103—C131	120.0 (3)	N1—C241—H36	108.5
C105—C104—C103	120.3 (3)	H35—C241—H36	107.5
C105—C104—H5	119.8	C241—C242—C243	110.3 (3)
C103—C104—H5	119.8	C241—C242—H38	109.6
C104—C105—C106	119.4 (3)	C243—C242—H38	109.6
C104—C105—C151	120.2 (3)	C241—C242—H37	109.6
C106—C105—C151	120.4 (3)	C243—C242—H37	109.6
C105—C106—C101	121.1 (3)	H38—C242—H37	108.1
C105—C106—H6	119.5	C242—C243—C244	113.5 (2)
C101—C106—H6	119.5	C242—C243—H39	108.9
O8—C111—O7	125.4 (3)	C244—C243—H39	108.9
O8—C111—C101	119.7 (3)	C242—C243—H40	108.9
O7—C111—C101	114.8 (3)	C244—C243—H40	108.9
O10—C131—O9	125.5 (3)	H39—C243—H40	107.7
O10—C131—C103	117.5 (3)	C243—C244—H42	109.5
O9—C131—C103	116.9 (3)	C243—C244—H43	109.5
O12—C151—O11	122.6 (3)	H42—C244—H43	109.5
O12—C151—C105	121.8 (3)	C243—C244—H41	109.5
O11—C151—C105	115.5 (3)	H42—C244—H41	109.5
C212—C211—N1	117.1 (3)	H43—C244—H41	109.5
C212—C211—H9	108.0	C231—N1—C241	111.4 (3)
N1—C211—H9	108.0	C231—N1—C221	110.5 (3)
C212—C211—H8	108.0	C241—N1—C221	107.7 (3)
N1—C211—H8	108.0	C231—N1—C211	106.4 (3)
H9—C211—H8	107.3	C241—N1—C211	110.5 (3)
C213—C212—C211	110.2 (3)	C221—N1—C211	110.4 (3)
C213—C212—H10	109.6	C11—O1—Zn1	132.1 (2)
C211—C212—H10	109.6	C11—O2—Zn2	130.7 (2)
C213—C212—H11	109.6	C31—O3—Zn3ⁱ	122.5 (2)
C211—C212—H11	109.6	C31—O4—Zn1ⁱ	138.2 (2)
H10—C212—H11	108.1	C51—O5—Zn1ⁱⁱ	119.9 (2)
C212—C213—C214	111.7 (2)	C111—O7—Zn2	121.6 (2)
C212—C213—H13	109.3	C131—O9—Zn2ⁱⁱⁱ	127.4 (2)
C214—C213—H13	109.3	C131—O10—Zn3ⁱⁱⁱ	133.2 (2)
C212—C213—H12	109.3	C151—O11—Zn3^iv	108.6 (2)
C214—C213—H12	109.3	Zn1—O13—Zn3	112.61 (10)
H13—C213—H12	107.9	Zn1—O13—Zn2	109.24 (9)
C213—C214—H14	109.5	Zn3—O13—Zn2	112.38 (10)
C213—C214—H16	109.5	Zn1—O13—H7	115.8
H14—C214—H16	109.5	Zn3—O13—H7	111.5
C213—C214—H15	109.5	Zn2—O13—H7	93.9
H14—C214—H15	109.5	O5^v—Zn1—O1	114.51 (12)
H16—C214—H15	109.5	O5^v—Zn1—O13	121.54 (11)
N1—C221—C222	115.1 (3)	O1—Zn1—O13	108.06 (10)
N1—C221—H18	108.5	O5^v—Zn1—O4^vi	101.86 (11)
C222—C221—H18	108.5	O1—Zn1—O4^vi	105.99 (11)
N1—C221—H17	108.5	O13—Zn1—O4^vi	102.85 (9)
C222—C221—H17	108.5	O7—Zn2—O2	114.97 (11)
H18—C221—H17	107.5	O7—Zn2—O9^vii	112.68 (10)
C223—C222—C221	112.6 (4)	O2—Zn2—O9^vii	106.72 (11)
C223—C222—H19	109.1	O7—Zn2—O13	103.67 (9)
C221—C222—H19	109.1	O2—Zn2—O13	109.45 (9)
C223—C222—H20	109.1	O9^vii—Zn2—O13	109.25 (9)
C221—C222—H20	109.1	O11^viii—Zn3—O3^vi	111.37 (10)
H19—C222—H20	107.8	O11^viii—Zn3—O10^vii	103.59 (10)
C222—C223—C224	112.8 (3)	O3^vi—Zn3—O10^vii	107.81 (10)
C222—C223—H22	109.0	O11^viii—Zn3—O13	116.07 (10)
C224—C223—H22	109.0	O3^vi—Zn3—O13	112.96 (9)
C222—C223—H21	109.0	O10^vii—Zn3—O13	103.96 (9)
C224—C223—H21	109.0

C6—C1—C2—C3	−2.9 (5)	C232—C231—N1—C221	63.2 (5)
C11—C1—C2—C3	176.5 (3)	C232—C231—N1—C211	−176.9 (4)
C1—C2—C3—C4	1.8 (5)	C242—C241—N1—C231	−51.9 (5)
C1—C2—C3—C31	178.7 (3)	C242—C241—N1—C221	−173.2 (4)
C2—C3—C4—C5	1.2 (5)	C242—C241—N1—C211	66.2 (5)
C31—C3—C4—C5	−175.8 (3)	C222—C221—N1—C231	61.0 (5)
C3—C4—C5—C6	−3.0 (5)	C222—C221—N1—C241	−177.2 (4)
C3—C4—C5—C51	175.0 (3)	C222—C221—N1—C211	−56.5 (5)
C4—C5—C6—C1	1.8 (5)	C212—C211—N1—C231	−176.3 (4)
C51—C5—C6—C1	−176.1 (3)	C212—C211—N1—C241	62.6 (5)
C2—C1—C6—C5	1.1 (5)	C212—C211—N1—C221	−56.4 (5)
C11—C1—C6—C5	−178.3 (3)	O2—C11—O1—Zn1	8.2 (6)
C2—C1—C11—O1	13.4 (5)	C1—C11—O1—Zn1	−173.1 (2)
C6—C1—C11—O1	−167.2 (3)	O1—C11—O2—Zn2	−4.1 (6)
C2—C1—C11—O2	−167.9 (3)	C1—C11—O2—Zn2	177.2 (2)
C6—C1—C11—O2	11.5 (5)	O4—C31—O3—Zn3ⁱ	29.4 (5)
C4—C3—C31—O3	158.8 (3)	C3—C31—O3—Zn3ⁱ	−150.2 (2)
C2—C3—C31—O3	−18.1 (5)	O3—C31—O4—Zn1ⁱ	−22.1 (6)
C4—C3—C31—O4	−20.8 (5)	C3—C31—O4—Zn1ⁱ	157.5 (3)
C2—C3—C31—O4	162.3 (3)	O6—C51—O5—Zn1ⁱⁱ	16.2 (6)
C6—C5—C51—O6	4.0 (6)	C5—C51—O5—Zn1ⁱⁱ	−161.9 (2)
C4—C5—C51—O6	−173.9 (3)	O8—C111—O7—Zn2	8.0 (5)
C6—C5—C51—O5	−177.8 (3)	C101—C111—O7—Zn2	−172.9 (2)
C4—C5—C51—O5	4.3 (5)	O10—C131—O9—Zn2ⁱⁱⁱ	−10.7 (5)
C106—C101—C102—C103	0.5 (5)	C103—C131—O9—Zn2ⁱⁱⁱ	169.7 (2)
C111—C101—C102—C103	179.7 (3)	O9—C131—O10—Zn3ⁱⁱⁱ	−22.6 (5)
C101—C102—C103—C104	−0.8 (5)	C103—C131—O10—Zn3ⁱⁱⁱ	156.9 (2)
C101—C102—C103—C131	178.9 (3)	O12—C151—O11—Zn3^iv	0.4 (4)
C102—C103—C104—C105	0.4 (5)	C105—C151—O11—Zn3^iv	−178.8 (2)
C131—C103—C104—C105	−179.4 (3)	C11—O1—Zn1—O5^v	120.9 (3)
C103—C104—C105—C106	0.4 (5)	C11—O1—Zn1—O13	−18.0 (4)
C103—C104—C105—C151	−179.4 (3)	C11—O1—Zn1—O4^vi	−127.6 (3)
C104—C105—C106—C101	−0.8 (5)	Zn3—O13—Zn1—O5^v	119.45 (13)
C151—C105—C106—C101	179.0 (3)	Zn2—O13—Zn1—O5^v	−114.94 (13)
C102—C101—C106—C105	0.3 (5)	Zn3—O13—Zn1—O1	−105.14 (12)
C111—C101—C106—C105	−178.9 (3)	Zn2—O13—Zn1—O1	20.47 (13)
C102—C101—C111—O8	6.6 (5)	Zn3—O13—Zn1—O4^vi	6.67 (13)
C106—C101—C111—O8	−174.2 (3)	Zn2—O13—Zn1—O4^vi	132.28 (11)
C102—C101—C111—O7	−172.5 (3)	C111—O7—Zn2—O2	122.9 (3)
C106—C101—C111—O7	6.7 (5)	C111—O7—Zn2—O9^vii	−114.6 (3)
C102—C103—C131—O10	−175.2 (3)	C111—O7—Zn2—O13	3.4 (3)
C104—C103—C131—O10	4.5 (5)	C11—O2—Zn2—O7	−105.3 (3)
C102—C103—C131—O9	4.4 (5)	C11—O2—Zn2—O9^vii	129.0 (3)
C104—C103—C131—O9	−175.9 (3)	C11—O2—Zn2—O13	10.9 (3)
C104—C105—C151—O12	−18.6 (5)	Zn1—O13—Zn2—O7	104.57 (11)
C106—C105—C151—O12	161.6 (3)	Zn3—O13—Zn2—O7	−129.69 (11)
C104—C105—C151—O11	160.6 (3)	Zn1—O13—Zn2—O2	−18.56 (14)
C106—C105—C151—O11	−19.1 (5)	Zn3—O13—Zn2—O2	107.18 (12)
N1—C211—C212—C213	178.2 (3)	Zn1—O13—Zn2—O9^vii	−135.08 (11)
C211—C212—C213—C214	−177.8 (2)	Zn3—O13—Zn2—O9^vii	−9.34 (13)
N1—C221—C222—C223	−172.6 (4)	Zn1—O13—Zn3—O11^viii	−131.35 (11)
C221—C222—C223—C224	176.2 (3)	Zn2—O13—Zn3—O11^viii	104.76 (12)
N1—C231—C232—C233	172.1 (4)	Zn1—O13—Zn3—O3^vi	−0.97 (14)
C231—C232—C233—C234	−179.0 (3)	Zn2—O13—Zn3—O3^vi	−124.86 (11)
N1—C241—C242—C243	177.8 (3)	Zn1—O13—Zn3—O10^vii	115.62 (11)
C241—C242—C243—C244	176.0 (2)	Zn2—O13—Zn3—O10^vii	−8.27 (12)
C232—C231—N1—C241	−56.5 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H7···O8	0.93	1.73	2.609 (3)	158

Experimental details

Crystal data
Chemical formula	(C₁₆H₃₆N)[Zn₃(C₉H₃O₆)₂(OH)]·0.25H₂O
M_r	873.86
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	16.295 (5), 16.295 (5), 28.946 (5)
V (Å³)	7686 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.92
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.700, 0.724
No. of measured, independent and observed [I > 2σ(I)] reflections	46890, 9492, 6072
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.099, 0.93
No. of reflections	9492
No. of parameters	443
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.24, −1.35

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O13—H7···O8	0.93	1.73	2.609 (3)	158

Acknowledgements

The authors gratefully acknowledge the Natural Science Foundation of Jiangsu Province of China (BK2008195) for financial support of this work.

References

Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
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