Poly[(μ3-benzene-1,3,5-tricarboxyl­ato-κ3O1:O3:O5)(μ2-2-methyl­imidazolato-κ2N:N′)tris­(2-methyl­imidazole-κN)dizinc(II)]

Maniam, P.; Stock, N.

doi:10.1107/S1600536811015844

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Pages m669-m670

doi:10.1107/S1600536811015844

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Poly[(μ₃-benzene-1,3,5-tricarboxylato-κ³O¹:O³:O⁵)(μ₂-2-methylimidazolato-κ²N:N′)tris(2-methylimidazole-κN)dizinc(II)]

Palanikumar Maniam ^a and Norbert Stock ^a ^*

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Strasse 2, 24118 Kiel, Germany
^*Correspondence e-mail: stock@ac.uni-kiel.de

(Received 21 April 2011; accepted 26 April 2011; online 7 May 2011)

Hydrothermal reaction involving zinc nitrate hexahydrate, trisodium benzene-1,3,5-tricarboxylate (Na₃BTC) and 2-methylimidazole (2-MeImH) yielded the title compound, [Zn₂(C₉H₃O₆)(C₄H₅N₂)(C₄H₆N₂)₃]. In this mixed-ligand metal-organic compound, Zn²⁺ ions are coordinated by N atoms from 2-MeImH molecules and (2-MeIm)⁻ ions, as well as by O atoms from (BTC)³⁻ ions. This results in two different distorted tetrahedra, viz. ZnN₃O and ZnN₂O₂. These tetrahedra are interconnected via (BTC)³⁻ ions and N:N′-bridging (2-MeIm)⁻ ions, thus forming a layered structure in the bc plane. Hydrogen bonds between the O atoms of carboxylate ions and NH groups of 2-MeImH ligands link the layers into a three-dimensional structure.

Related literature

For metal-organic frameworks, see: Li et al. (1999 ); Kitagawa et al. (2004 ); Stock (2010 ); Maniam et al. (2010 ). For related structures, see: Cheng et al. (2001 ); Zheng et al. (2010 ); Huang et al. (2006 ); Martins et al. (2010 ); Park et al. (2006 ).

Experimental

Crystal data

[Zn₂(C₉H₃O₆)(C₄H₅N₂)(C₄H₆N₂)₃]
M_r = 665.28
Orthorhombic, P b c n
a = 18.9722 (6) Å
b = 18.2247 (4) Å
c = 16.5585 (4) Å
V = 5725.3 (3) Å³
Z = 8
Mo Kα radiation
μ = 1.73 mm⁻¹
T = 293 K
0.16 × 0.09 × 0.07 mm

Data collection

Stoe IPDS-1 diffractometer
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2008 ) T_min = 0.684, T_max = 0.814
38494 measured reflections
7732 independent reflections
6222 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.143
S = 1.13
7732 reflections
370 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn1—O4	1.942 (3)
Zn2—O6	1.968 (3)
Zn2—O1ⁱ	1.976 (2)
Zn1—N2Hⁱⁱ	1.971 (3)
Zn1—N1F	1.998 (3)
Zn1—N1G	2.015 (4)
Zn2—N1H	1.992 (3)
Zn2—N1E	2.027 (3)
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2E—H2EN⋯O3ⁱⁱⁱ	0.86	2.06	2.912 (5)	169
N2F—H2FN⋯O2^iv	0.86	1.84	2.693 (5)	172
N2G—H2GN⋯O5^v	0.86	1.94	2.798 (5)	175
Symmetry codes: (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iv) $[-x+1, y, -z-{\script{1\over 2}}]$ ; (v) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015844/bt5531sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811015844/bt5531Isup2.hkl

checkCIF report

Comment top

Metal-organic frameworks (MOF) are being investigated intensively, mainly for their high specific surface areas (Li et al., 1999; Kitagawa et al., 2004). In our workgroup, we are interested in using organic ligands containing multiple functional groups as the linkers for the MOFs. We employ high-throughput (HT) methods, which allow the rapid and systematic investigation of compound formation fields (Stock, 2010; Maniam et al., 2010). HT-screening of various first row transition metal ions with trisodium benzene-1,3,5-tricarboxylate (Na₃BTC) and 2-methylimidazole (2-MeImH) has yielded the colorless block crystals of (I). The asymmetric unit of compound (I) consists of two crystallographically independent Zn²⁺ ions, one fully deprotonated (BTC)^3-, one 2-methylimidazolate (2-MeIm)^- ion and three 2-MeImH ligands (Fig. 1). The Zn²⁺ ions are tetrahedrally coordinated by oxygen atoms originating from (BTC)^3- and nitrogen atoms from (2-MeIm)^- and 2-MeImH. The Zn···O bond distances lie between 1.942 (3)–1.976 (2) Å which are slightly shorter than Zn···N bonds of 1.971 (3)–2.027 (3) Å. The bond angles in ZnN₃O tetrahedra ranges between 100.42 (14)–116.61 (16)° while in ZnN₂O₂, the bond angles of 96.73 (13)–122.12 (11)° are observed (Tab. 1 & Tab. 2). It was also observed that Zn-(2-MeIm)^-—Zn angle lies at 146.8 (1)° which is close to 145° angles in zeolitic imidazolate frameworks and zeolite structures (Park et al.., 2006). The C=O and C—O bonds in the carboxylate groups can be clearly distinguished from each other by their bond lengths of 1.229 (5)–1.236 (5) Å and 1.266 (4)–1.275 (4) Å, respectively. Weak hydrogen bonds in the 2.6 < d(O···H—N) < 3.0 Å range are observed between the O atoms of the carboxylate ions and N—H groups of the 2-MeImH ligands (Fig. 2).

By considering the ZnN₃O and ZnN₂O₂ tetrahedra bridged by the (2-MeIm)^- as a Zn-(2-MeIm)-Zn dimer, this dimer is connected to three terminal 2-MeImH ligands and three (BTC)^3- ions. Each (BTC)^3- ion is then further connected to two Zn-(2-MeIm)-Zn dimers (Fig. 3) and layers in the bc plane are formed. Through extensive O···H—N hydrogen bonding, the layers are interconnected along the a-axis to form a dense three-dimensional crystal structure (Fig. 4, Tab. 2).

Related literature top

For metal-organic frameworks, see: Li et al. (1999); Kitagawa et al. (2004); Stock (2010); Maniam et al. (2010). For related structures, see: Cheng et al. (2001); Zheng et al. (2010); Huang et al. (2006); Martins et al. (2010); Park et al. (2006)

Experimental top

All reagents were of analytical grade (Aldrich and Fluka) and were used without further purification. High-throughput (HT) experiments in 300 ml Teflon-lined reactors yielded the crystals of compound (I). The reaction mixture consisted of zinc(II) nitrate hexahydrate (5.9 mg, 0.02 mmol), Na₃(BTC) (2.76 mg, 0.01 mmol), 2-methylimidazole (4.11 mg, 0.05 mmol) and deionized water (200 ml). The mixture was heated in a 300 µl Teflon-lined high-throughput reactor at 423 K for 48 h (Stock, 2010). The mixture was cooled to room temperature over a period of 12 h and colourless plate-like crystals were obtained.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are omitted for clarity.
	Fig. 2. The tetrahedral coordination environment of the Zn1 and Zn2 ions. Green broken lines indicate the weak hydrogen bonds between the carboxylate groups of the (BTC)^3- ions and H—N groups of the 2-MeImH ligands. [Symmetry codes: (i) -x + 3/2, y + 1/2, z; (ii) x, -y, z + 1/2; (iii) x, -y, z - 1/2; (iv) -x + 3/2, y - 1/2, z; (v) x + 1/2, -y + 1/2, -z; (vi) -x + 1, y, -z - 1/2; (vii) -x + 1, y, -z + 1/2; (viii) x - 1/2, -y + 1/2, -z.]
	Fig. 3. Ball-and-stick representation for (I) showing the interconnection of Zn-(2-MeIm)-Zn dimers (marked as differently colored polyhedra) by (BTC)^3- ions and thus forming a layered arrangement in the b,c plane. Zn: purple, O: grey, N: blue, C: black and H: green. Hydrogen atoms of (BTC)^3- are omitted for clarity.
	Fig. 4. Layer packing diagram of compound (I). All atoms of one layer are presented by the same colour. H-bonds (see Fig. 2) between the layers are depicted by black broken lines.

Poly[(µ₃-benzene-1,3,5-tricarboxylato- κ³O¹:O³:O⁵)(µ₂-2-methylimidazolato- κ²N:N')tris(2-methylimidazole-κN)dizinc(II)] top

Crystal data top

[Zn₂(C₉H₃O₆)(C₄H₅N₂)(C₄H₆N₂)₃]	F(000) = 2720
M_r = 665.28	D_x = 1.544 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 40409 reflections
a = 18.9722 (6) Å	θ = 1.6–29.7°
b = 18.2247 (4) Å	µ = 1.73 mm⁻¹
c = 16.5585 (4) Å	T = 293 K
V = 5725.3 (3) Å³	Block, colourless
Z = 8	0.16 × 0.09 × 0.07 mm

Data collection top

Stoe IPDS-1 diffractometer	7732 independent reflections
Radiation source: fine-focus sealed tube	6222 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ϕ scans	θ_max = 29.3°, θ_min = 1.6°
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2008)	h = −26→26
T_min = 0.684, T_max = 0.814	k = −24→23
38494 measured reflections	l = −16→22

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)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.143	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0602P)² + 8.9412P] where P = (F_o² + 2F_c²)/3
7732 reflections	(Δ/σ)_max < 0.001
370 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Zn₂(C₉H₃O₆)(C₄H₅N₂)(C₄H₆N₂)₃]	V = 5725.3 (3) Å³
M_r = 665.28	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 18.9722 (6) Å	µ = 1.73 mm⁻¹
b = 18.2247 (4) Å	T = 293 K
c = 16.5585 (4) Å	0.16 × 0.09 × 0.07 mm

Data collection top

Stoe IPDS-1 diffractometer	7732 independent reflections
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2008)	6222 reflections with I > 2σ(I)
T_min = 0.684, T_max = 0.814	R_int = 0.050
38494 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.143	H-atom parameters constrained
S = 1.13	Δρ_max = 0.47 e Å⁻³
7732 reflections	Δρ_min = −0.54 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	0.45797 (2)	0.21003 (2)	0.06434 (3)	0.03012 (11)
Zn2	0.86974 (2)	−0.02837 (2)	0.16875 (2)	0.02691 (11)
O1	0.82544 (13)	0.04108 (16)	−0.22416 (15)	0.0317 (6)
O2	0.75851 (19)	0.1297 (2)	−0.27156 (19)	0.0542 (9)
O3	0.54340 (16)	0.20240 (19)	−0.1090 (2)	0.0482 (8)
O4	0.53500 (14)	0.15579 (16)	0.01530 (17)	0.0372 (6)
O5	0.73489 (17)	0.0422 (2)	0.14383 (17)	0.0461 (8)
O6	0.81368 (14)	−0.01665 (16)	0.06956 (16)	0.0367 (6)
C1	0.73604 (17)	0.0869 (2)	−0.1391 (2)	0.0262 (6)
C2	0.67256 (19)	0.1251 (2)	−0.1327 (2)	0.0301 (7)
H2A	0.6548	0.1500	−0.1773	0.036*
C3	0.63563 (18)	0.1261 (2)	−0.0602 (2)	0.0299 (7)
C4	0.66398 (18)	0.0910 (2)	0.0066 (2)	0.0301 (7)
H4A	0.6397	0.0921	0.0554	0.036*
C5	0.72805 (18)	0.0544 (2)	0.0019 (2)	0.0271 (7)
C6	0.76310 (18)	0.0509 (2)	−0.0720 (2)	0.0276 (7)
H6A	0.8048	0.0243	−0.0763	0.033*
C7	0.77524 (18)	0.0865 (2)	−0.2179 (2)	0.0289 (7)
C8	0.56601 (18)	0.1652 (2)	−0.0522 (2)	0.0302 (7)
C9	0.76020 (19)	0.0245 (2)	0.0779 (2)	0.0296 (7)
C1E	0.9480 (2)	0.1157 (3)	0.1420 (3)	0.0398 (9)
C2E	0.9061 (3)	0.1880 (3)	0.2364 (3)	0.0512 (11)
H2E	0.8966	0.2290	0.2680	0.061*
C3E	0.8810 (2)	0.1201 (3)	0.2469 (3)	0.0423 (9)
H3E	0.8505	0.1058	0.2879	0.051*
C4E	0.9881 (3)	0.0916 (3)	0.0703 (3)	0.0579 (13)
H4E1	1.0137	0.1325	0.0484	0.070*
H4E2	0.9561	0.0730	0.0304	0.070*
H4E3	1.0206	0.0537	0.0856	0.070*
N1E	0.90718 (18)	0.07433 (19)	0.1879 (2)	0.0352 (7)
N2E	0.9484 (2)	0.1849 (2)	0.1696 (3)	0.0471 (9)
H2EN	0.9713	0.2210	0.1489	0.057*
C1F	0.3558 (2)	0.1785 (2)	−0.0669 (3)	0.0396 (9)
C2F	0.3373 (2)	0.2885 (3)	−0.0222 (3)	0.0427 (10)
H2F	0.3412	0.3314	0.0079	0.051*
C3F	0.2905 (2)	0.2767 (3)	−0.0822 (3)	0.0495 (11)
H3F	0.2565	0.3093	−0.1010	0.059*
C4F	0.3840 (3)	0.1032 (3)	−0.0801 (4)	0.0613 (15)
H4F1	0.3585	0.0800	−0.1232	0.074*
H4F2	0.3787	0.0749	−0.0315	0.074*
H4F3	0.4330	0.1060	−0.0941	0.074*
N1F	0.37830 (16)	0.22648 (19)	−0.0125 (2)	0.0353 (7)
N2F	0.30319 (19)	0.2075 (2)	−0.1096 (3)	0.0479 (9)
H2FN	0.2809	0.1861	−0.1482	0.057*
C1G	0.3665 (3)	0.1373 (3)	0.1915 (4)	0.0604 (14)
C2G	0.4502 (3)	0.0661 (3)	0.1528 (4)	0.0667 (16)
H2G	0.4899	0.0485	0.1260	0.080*
C3G	0.4119 (4)	0.0282 (4)	0.2072 (4)	0.0738 (17)
H3G	0.4194	−0.0198	0.2241	0.089*
C4G	0.3175 (5)	0.2000 (5)	0.1996 (7)	0.131 (4)
H4G1	0.2818	0.1883	0.2386	0.157*
H4G2	0.2958	0.2098	0.1484	0.157*
H4G3	0.3431	0.2426	0.2172	0.157*
N1G	0.4217 (2)	0.1347 (2)	0.1431 (2)	0.0444 (8)
N2G	0.3604 (3)	0.0740 (3)	0.2321 (3)	0.0631 (13)
H2GN	0.3290	0.0643	0.2680	0.076*
C1H	0.94630 (18)	−0.1645 (2)	0.1130 (2)	0.0328 (8)
C2H	1.01834 (19)	−0.0828 (2)	0.1579 (2)	0.0338 (8)
H2H	1.0369	−0.0393	0.1782	0.041*
C3H	1.05531 (18)	−0.1437 (2)	0.1393 (3)	0.0359 (8)
H3H	1.1038	−0.1493	0.1452	0.043*
C4H	0.8800 (2)	−0.2001 (3)	0.0853 (4)	0.0578 (15)
H4H1	0.8900	−0.2490	0.0671	0.069*
H4H2	0.8601	−0.1721	0.0418	0.069*
H4H3	0.8470	−0.2020	0.1293	0.069*
N1H	0.94875 (15)	−0.09609 (18)	0.14179 (19)	0.0302 (6)
N2H	1.01007 (16)	−0.19593 (18)	0.1103 (2)	0.0324 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.02406 (18)	0.0339 (2)	0.0324 (2)	−0.00044 (16)	0.00318 (16)	−0.00303 (18)
Zn2	0.02578 (18)	0.0330 (2)	0.02195 (18)	0.00254 (16)	0.00150 (15)	0.00171 (16)
O1	0.0277 (11)	0.0457 (15)	0.0218 (11)	0.0058 (10)	0.0038 (9)	−0.0020 (11)
O2	0.064 (2)	0.067 (2)	0.0317 (15)	0.0266 (17)	0.0106 (14)	0.0175 (16)
O3	0.0392 (15)	0.059 (2)	0.0460 (17)	0.0201 (14)	0.0056 (14)	0.0122 (16)
O4	0.0305 (13)	0.0449 (15)	0.0361 (15)	0.0112 (11)	0.0091 (11)	0.0009 (12)
O5	0.0490 (17)	0.066 (2)	0.0232 (12)	0.0188 (15)	0.0029 (12)	0.0022 (14)
O6	0.0354 (13)	0.0493 (17)	0.0254 (12)	0.0162 (12)	−0.0044 (10)	0.0017 (12)
C1	0.0248 (15)	0.0310 (17)	0.0228 (15)	−0.0002 (13)	0.0014 (12)	−0.0024 (13)
C2	0.0306 (16)	0.0342 (18)	0.0253 (16)	0.0060 (14)	−0.0006 (13)	0.0027 (15)
C3	0.0293 (16)	0.0323 (17)	0.0281 (17)	0.0038 (13)	0.0033 (14)	0.0000 (14)
C4	0.0268 (15)	0.0383 (19)	0.0252 (16)	0.0017 (14)	0.0035 (13)	0.0017 (15)
C5	0.0274 (15)	0.0325 (17)	0.0215 (15)	0.0023 (13)	−0.0009 (12)	−0.0003 (13)
C6	0.0255 (15)	0.0323 (17)	0.0250 (16)	0.0041 (12)	−0.0006 (12)	−0.0012 (14)
C7	0.0283 (15)	0.0357 (18)	0.0228 (15)	0.0002 (13)	0.0002 (12)	0.0002 (14)
C8	0.0256 (15)	0.0348 (18)	0.0300 (18)	0.0031 (13)	0.0010 (13)	−0.0009 (15)
C9	0.0301 (16)	0.0369 (18)	0.0217 (15)	0.0030 (14)	−0.0010 (12)	0.0014 (14)
C1E	0.037 (2)	0.044 (2)	0.038 (2)	−0.0042 (17)	0.0001 (16)	0.0052 (18)
C2E	0.058 (3)	0.041 (2)	0.054 (3)	−0.005 (2)	−0.004 (2)	−0.009 (2)
C3E	0.042 (2)	0.044 (2)	0.041 (2)	−0.0027 (17)	0.0055 (17)	−0.0072 (19)
C4E	0.061 (3)	0.065 (3)	0.048 (3)	−0.002 (3)	0.019 (2)	0.014 (3)
N1E	0.0395 (17)	0.0330 (17)	0.0330 (17)	−0.0053 (13)	0.0025 (13)	−0.0001 (13)
N2E	0.049 (2)	0.0393 (19)	0.053 (2)	−0.0128 (16)	−0.0061 (18)	0.0047 (18)
C1F	0.0324 (18)	0.042 (2)	0.045 (2)	−0.0075 (16)	−0.0023 (16)	−0.0096 (19)
C2F	0.0330 (18)	0.043 (2)	0.052 (3)	0.0046 (16)	−0.0054 (17)	−0.016 (2)
C3F	0.037 (2)	0.057 (3)	0.055 (3)	0.0069 (19)	−0.0136 (19)	−0.014 (2)
C4F	0.058 (3)	0.040 (3)	0.086 (4)	−0.003 (2)	−0.010 (3)	−0.021 (3)
N1F	0.0261 (14)	0.0379 (17)	0.0420 (18)	−0.0006 (12)	−0.0046 (13)	−0.0075 (14)
N2F	0.0368 (17)	0.057 (2)	0.049 (2)	−0.0025 (16)	−0.0129 (16)	−0.0165 (19)
C1G	0.066 (3)	0.054 (3)	0.061 (3)	−0.016 (2)	0.034 (3)	−0.003 (3)
C2G	0.063 (3)	0.061 (3)	0.076 (4)	0.006 (3)	0.016 (3)	0.024 (3)
C3G	0.080 (4)	0.067 (4)	0.074 (4)	−0.005 (3)	0.008 (3)	0.028 (3)
C4G	0.130 (7)	0.093 (6)	0.169 (10)	0.021 (5)	0.116 (7)	0.016 (6)
N1G	0.0441 (19)	0.049 (2)	0.0405 (19)	−0.0053 (16)	0.0117 (16)	0.0037 (17)
N2G	0.072 (3)	0.070 (3)	0.047 (2)	−0.027 (2)	0.020 (2)	0.004 (2)
C1H	0.0244 (16)	0.039 (2)	0.0348 (19)	0.0002 (14)	0.0025 (14)	−0.0037 (16)
C2H	0.0288 (16)	0.041 (2)	0.0317 (19)	0.0012 (15)	−0.0039 (14)	−0.0053 (16)
C3H	0.0219 (15)	0.048 (2)	0.038 (2)	0.0040 (14)	−0.0044 (14)	−0.0122 (18)
C4H	0.0225 (18)	0.058 (3)	0.092 (4)	0.0010 (18)	0.000 (2)	−0.024 (3)
N1H	0.0244 (13)	0.0361 (16)	0.0302 (15)	0.0039 (12)	0.0007 (11)	−0.0044 (13)
N2H	0.0257 (14)	0.0363 (17)	0.0350 (16)	0.0034 (12)	0.0002 (12)	−0.0051 (14)

Geometric parameters (Å, º) top

Zn1—O4	1.942 (3)	N2E—H2EN	0.8600
Zn2—O6	1.968 (3)	C1F—N1F	1.325 (5)
Zn2—O1ⁱ	1.976 (2)	C1F—N2F	1.333 (6)
Zn1—N2Hⁱⁱ	1.971 (3)	C1F—C4F	1.490 (7)
Zn1—N1F	1.998 (3)	C2F—C3F	1.349 (6)
Zn1—N1G	2.015 (4)	C2F—N1F	1.381 (5)
Zn2—N1H	1.992 (3)	C2F—H2F	0.9300
Zn2—N1E	2.027 (3)	C3F—N2F	1.361 (6)
O1—C7	1.265 (4)	C3F—H3F	0.9300
O2—C7	1.228 (5)	C4F—H4F1	0.9600
O3—C8	1.236 (5)	C4F—H4F2	0.9600
O4—C8	1.274 (5)	C4F—H4F3	0.9600
O5—C9	1.236 (5)	N2F—H2FN	0.8600
O6—C9	1.269 (4)	C1G—N1G	1.319 (6)
C1—C6	1.388 (5)	C1G—N2G	1.340 (7)
C1—C2	1.395 (5)	C1G—C4G	1.480 (10)
C1—C7	1.503 (5)	C2G—C3G	1.348 (8)
C2—C3	1.390 (5)	C2G—N1G	1.372 (7)
C2—H2A	0.9300	C2G—H2G	0.9300
C3—C4	1.386 (5)	C3G—N2G	1.349 (8)
C3—C8	1.507 (5)	C3G—H3G	0.9300
C4—C5	1.389 (5)	C4G—H4G1	0.9600
C4—H4A	0.9300	C4G—H4G2	0.9600
C5—C6	1.394 (5)	C4G—H4G3	0.9600
C5—C9	1.501 (5)	N2G—H2GN	0.8600
C6—H6A	0.9300	C1H—N1H	1.336 (5)
C1E—N1E	1.321 (5)	C1H—N2H	1.339 (4)
C1E—N2E	1.340 (6)	C1H—C4H	1.488 (5)
C1E—C4E	1.477 (7)	C2H—C3H	1.348 (6)
C2E—C3E	1.338 (7)	C2H—N1H	1.369 (4)
C2E—N2E	1.368 (7)	C2H—H2H	0.9300
C2E—H2E	0.9300	C3H—N2H	1.368 (5)
C3E—N1E	1.377 (5)	C3H—H3H	0.9300
C3E—H3E	0.9300	C4H—H4H1	0.9600
C4E—H4E1	0.9600	C4H—H4H2	0.9600
C4E—H4E2	0.9600	C4H—H4H3	0.9600
C4E—H4E3	0.9600

O4—Zn1—N2Hⁱⁱ	111.87 (13)	N1F—C1F—N2F	109.9 (4)
O4—Zn1—N1F	112.28 (13)	N1F—C1F—C4F	126.3 (4)
N2Hⁱⁱ—Zn1—N1F	110.38 (14)	N2F—C1F—C4F	123.8 (4)
O4—Zn1—N1G	100.42 (14)	C3F—C2F—N1F	109.0 (4)
N2Hⁱⁱ—Zn1—N1G	116.61 (16)	C3F—C2F—H2F	125.5
N1F—Zn1—N1G	104.81 (15)	N1F—C2F—H2F	125.5
O6—Zn2—O1ⁱ	122.12 (11)	C2F—C3F—N2F	106.1 (4)
O6—Zn2—N1H	106.66 (12)	C2F—C3F—H3F	127.0
O1ⁱ—Zn2—N1H	116.64 (13)	N2F—C3F—H3F	127.0
O6—Zn2—N1E	102.68 (13)	C1F—C4F—H4F1	109.5
O1ⁱ—Zn2—N1E	96.73 (13)	C1F—C4F—H4F2	109.5
N1H—Zn2—N1E	110.08 (13)	H4F1—C4F—H4F2	109.5
C7—O1—Zn2ⁱⁱⁱ	118.0 (2)	C1F—C4F—H4F3	109.5
C8—O4—Zn1	130.2 (3)	H4F1—C4F—H4F3	109.5
C9—O6—Zn2	113.9 (2)	H4F2—C4F—H4F3	109.5
C6—C1—C2	119.6 (3)	C1F—N1F—C2F	106.2 (3)
C6—C1—C7	120.7 (3)	C1F—N1F—Zn1	125.3 (3)
C2—C1—C7	119.7 (3)	C2F—N1F—Zn1	128.5 (3)
C3—C2—C1	120.5 (3)	C1F—N2F—C3F	108.8 (4)
C3—C2—H2A	119.8	C1F—N2F—H2FN	125.6
C1—C2—H2A	119.8	C3F—N2F—H2FN	125.6
C4—C3—C2	119.2 (3)	N1G—C1G—N2G	110.0 (5)
C4—C3—C8	119.2 (3)	N1G—C1G—C4G	125.6 (5)
C2—C3—C8	121.6 (3)	N2G—C1G—C4G	124.4 (5)
C3—C4—C5	121.1 (3)	C3G—C2G—N1G	109.4 (6)
C3—C4—H4A	119.5	C3G—C2G—H2G	125.3
C5—C4—H4A	119.5	N1G—C2G—H2G	125.3
C4—C5—C6	119.3 (3)	N2G—C3G—C2G	106.1 (6)
C4—C5—C9	118.9 (3)	N2G—C3G—H3G	126.9
C6—C5—C9	121.7 (3)	C2G—C3G—H3G	126.9
C1—C6—C5	120.3 (3)	C1G—C4G—H4G1	109.5
C1—C6—H6A	119.9	C1G—C4G—H4G2	109.5
C5—C6—H6A	119.9	H4G1—C4G—H4G2	109.5
O2—C7—O1	123.7 (3)	C1G—C4G—H4G3	109.5
O2—C7—C1	119.8 (3)	H4G1—C4G—H4G3	109.5
O1—C7—C1	116.5 (3)	H4G2—C4G—H4G3	109.5
O3—C8—O4	125.5 (3)	C1G—N1G—C2G	105.9 (4)
O3—C8—C3	119.8 (3)	C1G—N1G—Zn1	129.8 (4)
O4—C8—C3	114.7 (3)	C2G—N1G—Zn1	124.2 (3)
O5—C9—O6	124.1 (3)	C1G—N2G—C3G	108.5 (4)
O5—C9—C5	119.2 (3)	C1G—N2G—H2GN	125.8
O6—C9—C5	116.7 (3)	C3G—N2G—H2GN	125.8
N1E—C1E—N2E	110.2 (4)	N1H—C1H—N2H	112.3 (3)
N1E—C1E—C4E	126.4 (4)	N1H—C1H—C4H	123.1 (3)
N2E—C1E—C4E	123.4 (4)	N2H—C1H—C4H	124.6 (4)
C3E—C2E—N2E	105.9 (4)	C3H—C2H—N1H	108.2 (3)
C3E—C2E—H2E	127.0	C3H—C2H—H2H	125.9
N2E—C2E—H2E	127.0	N1H—C2H—H2H	125.9
C2E—C3E—N1E	109.9 (4)	C2H—C3H—N2H	109.1 (3)
C2E—C3E—H3E	125.1	C2H—C3H—H3H	125.5
N1E—C3E—H3E	125.1	N2H—C3H—H3H	125.5
C1E—C4E—H4E1	109.5	C1H—C4H—H4H1	109.5
C1E—C4E—H4E2	109.5	C1H—C4H—H4H2	109.5
H4E1—C4E—H4E2	109.5	H4H1—C4H—H4H2	109.5
C1E—C4E—H4E3	109.5	C1H—C4H—H4H3	109.5
H4E1—C4E—H4E3	109.5	H4H1—C4H—H4H3	109.5
H4E2—C4E—H4E3	109.5	H4H2—C4H—H4H3	109.5
C1E—N1E—C3E	105.8 (4)	C1H—N1H—C2H	105.6 (3)
C1E—N1E—Zn2	130.0 (3)	C1H—N1H—Zn2	129.2 (2)
C3E—N1E—Zn2	122.9 (3)	C2H—N1H—Zn2	124.9 (3)
C1E—N2E—C2E	108.2 (4)	C1H—N2H—C3H	104.9 (3)
C1E—N2E—H2EN	125.9	C1H—N2H—Zn1^iv	131.5 (3)
C2E—N2E—H2EN	125.9	C3H—N2H—Zn1^iv	123.2 (2)

N2Hⁱⁱ—Zn1—O4—C8	−76.9 (4)	N1F—C2F—C3F—N2F	−0.3 (6)
N1F—Zn1—O4—C8	47.9 (4)	N2F—C1F—N1F—C2F	0.0 (5)
N1G—Zn1—O4—C8	158.8 (4)	C4F—C1F—N1F—C2F	179.9 (5)
O1ⁱ—Zn2—O6—C9	41.1 (3)	N2F—C1F—N1F—Zn1	−178.4 (3)
N1H—Zn2—O6—C9	178.8 (3)	C4F—C1F—N1F—Zn1	1.5 (7)
N1E—Zn2—O6—C9	−65.4 (3)	C3F—C2F—N1F—C1F	0.2 (5)
C6—C1—C2—C3	−1.3 (6)	C3F—C2F—N1F—Zn1	178.5 (3)
C7—C1—C2—C3	−180.0 (3)	O4—Zn1—N1F—C1F	37.9 (4)
C1—C2—C3—C4	2.5 (6)	N2Hⁱⁱ—Zn1—N1F—C1F	163.5 (3)
C1—C2—C3—C8	−178.4 (3)	N1G—Zn1—N1F—C1F	−70.2 (4)
C2—C3—C4—C5	−0.7 (6)	O4—Zn1—N1F—C2F	−140.1 (4)
C8—C3—C4—C5	−179.9 (3)	N2Hⁱⁱ—Zn1—N1F—C2F	−14.6 (4)
C3—C4—C5—C6	−2.2 (6)	N1G—Zn1—N1F—C2F	111.8 (4)
C3—C4—C5—C9	173.4 (4)	N1F—C1F—N2F—C3F	−0.2 (6)
C2—C1—C6—C5	−1.7 (5)	C4F—C1F—N2F—C3F	179.9 (5)
C7—C1—C6—C5	177.0 (3)	C2F—C3F—N2F—C1F	0.3 (6)
C4—C5—C6—C1	3.4 (5)	N1G—C2G—C3G—N2G	−1.1 (8)
C9—C5—C6—C1	−172.1 (3)	N2G—C1G—N1G—C2G	1.3 (7)
Zn2ⁱⁱⁱ—O1—C7—O2	−9.8 (5)	C4G—C1G—N1G—C2G	−177.9 (8)
Zn2ⁱⁱⁱ—O1—C7—C1	171.5 (2)	N2G—C1G—N1G—Zn1	178.2 (4)
C6—C1—C7—O2	−165.6 (4)	C4G—C1G—N1G—Zn1	−1.0 (11)
C2—C1—C7—O2	13.0 (6)	C3G—C2G—N1G—C1G	−0.1 (8)
C6—C1—C7—O1	13.2 (5)	C3G—C2G—N1G—Zn1	−177.2 (5)
C2—C1—C7—O1	−168.2 (3)	O4—Zn1—N1G—C1G	−175.7 (5)
Zn1—O4—C8—O3	−16.3 (6)	N2Hⁱⁱ—Zn1—N1G—C1G	63.3 (5)
Zn1—O4—C8—C3	164.1 (3)	N1F—Zn1—N1G—C1G	−59.1 (5)
C4—C3—C8—O3	173.2 (4)	O4—Zn1—N1G—C2G	0.7 (5)
C2—C3—C8—O3	−5.9 (6)	N2Hⁱⁱ—Zn1—N1G—C2G	−120.3 (5)
C4—C3—C8—O4	−7.2 (5)	N1F—Zn1—N1G—C2G	117.3 (5)
C2—C3—C8—O4	173.7 (4)	N1G—C1G—N2G—C3G	−2.0 (7)
Zn2—O6—C9—O5	−16.2 (5)	C4G—C1G—N2G—C3G	177.2 (8)
Zn2—O6—C9—C5	161.9 (3)	C2G—C3G—N2G—C1G	1.9 (8)
C4—C5—C9—O5	−10.7 (6)	N1H—C2H—C3H—N2H	0.7 (5)
C6—C5—C9—O5	164.7 (4)	N2H—C1H—N1H—C2H	0.4 (5)
C4—C5—C9—O6	171.0 (3)	C4H—C1H—N1H—C2H	−178.0 (4)
C6—C5—C9—O6	−13.5 (5)	N2H—C1H—N1H—Zn2	−173.3 (3)
N2E—C2E—C3E—N1E	0.2 (6)	C4H—C1H—N1H—Zn2	8.2 (6)
N2E—C1E—N1E—C3E	−0.1 (5)	C3H—C2H—N1H—C1H	−0.7 (4)
C4E—C1E—N1E—C3E	−179.9 (5)	C3H—C2H—N1H—Zn2	173.4 (3)
N2E—C1E—N1E—Zn2	167.5 (3)	O6—Zn2—N1H—C1H	−57.7 (4)
C4E—C1E—N1E—Zn2	−12.4 (7)	O1ⁱ—Zn2—N1H—C1H	82.7 (4)
C2E—C3E—N1E—C1E	−0.1 (5)	N1E—Zn2—N1H—C1H	−168.4 (3)
C2E—C3E—N1E—Zn2	−168.8 (3)	O6—Zn2—N1H—C2H	129.6 (3)
O6—Zn2—N1E—C1E	−60.7 (4)	O1ⁱ—Zn2—N1H—C2H	−89.9 (3)
O1ⁱ—Zn2—N1E—C1E	174.2 (4)	N1E—Zn2—N1H—C2H	18.9 (4)
N1H—Zn2—N1E—C1E	52.6 (4)	N1H—C1H—N2H—C3H	0.0 (5)
O6—Zn2—N1E—C3E	105.0 (3)	C4H—C1H—N2H—C3H	178.4 (5)
O1ⁱ—Zn2—N1E—C3E	−20.1 (4)	N1H—C1H—N2H—Zn1^iv	−172.7 (3)
N1H—Zn2—N1E—C3E	−141.7 (3)	C4H—C1H—N2H—Zn1^iv	5.7 (7)
N1E—C1E—N2E—C2E	0.2 (5)	C2H—C3H—N2H—C1H	−0.4 (5)
C4E—C1E—N2E—C2E	−179.9 (5)	C2H—C3H—N2H—Zn1^iv	173.0 (3)
C3E—C2E—N2E—C1E	−0.2 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2E—H2EN···O3^v	0.86	2.06	2.912 (5)	169
N2F—H2FN···O2^vi	0.86	1.84	2.693 (5)	172
N2G—H2GN···O5^vii	0.86	1.94	2.798 (5)	175

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

Experimental details

Crystal data
Chemical formula	[Zn₂(C₉H₃O₆)(C₄H₅N₂)(C₄H₆N₂)₃]
M_r	665.28
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	18.9722 (6), 18.2247 (4), 16.5585 (4)
V (Å³)	5725.3 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.73
Crystal size (mm)	0.16 × 0.09 × 0.07

Data collection
Diffractometer	Stoe IPDS1 diffractometer
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe & Cie, 2008)
T_min, T_max	0.684, 0.814
No. of measured, independent and observed [I > 2σ(I)] reflections	38494, 7732, 6222
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.143, 1.13
No. of reflections	7732
No. of parameters	370
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.54

Computer programs: X-AREA (Stoe & Cie, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010), XCIF in SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Zn1—O4	1.942 (3)	Zn2—N1E	2.027 (3)
Zn2—O6	1.968 (3)	O1—C7	1.265 (4)
Zn2—O1ⁱ	1.976 (2)	O2—C7	1.228 (5)
Zn1—N2Hⁱⁱ	1.971 (3)	O3—C8	1.236 (5)
Zn1—N1F	1.998 (3)	O4—C8	1.274 (5)
Zn1—N1G	2.015 (4)	O5—C9	1.236 (5)
Zn2—N1H	1.992 (3)	O6—C9	1.269 (4)

O4—Zn1—N2Hⁱⁱ	111.87 (13)	O6—Zn2—O1ⁱ	122.12 (11)
O4—Zn1—N1F	112.28 (13)	O6—Zn2—N1H	106.66 (12)
N2Hⁱⁱ—Zn1—N1F	110.38 (14)	O1ⁱ—Zn2—N1H	116.64 (13)
O4—Zn1—N1G	100.42 (14)	O6—Zn2—N1E	102.68 (13)
N2Hⁱⁱ—Zn1—N1G	116.61 (16)	O1ⁱ—Zn2—N1E	96.73 (13)
N1F—Zn1—N1G	104.81 (15)	N1H—Zn2—N1E	110.08 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2E—H2EN···O3ⁱⁱⁱ	0.86	2.06	2.912 (5)	169
N2F—H2FN···O2^iv	0.86	1.84	2.693 (5)	172
N2G—H2GN···O5^v	0.86	1.94	2.798 (5)	175

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

Acknowledgements

The authors thank Dr Christian Näther and Inke Jess (University of Kiel) for the acquisition of the single-crystal data. This work was supported by the State of Schleswig–Holstein, Germany and the German Research Foundation (DFG; SPP-1362).

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