Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807016893/gg3085sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807016893/gg3085Isup2.hkl |
CCDC reference: 660044
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.048
- wR factor = 0.099
- Data-to-parameter ratio = 12.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C29 PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.12 Ratio
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For related literature, see: Cheng et al. (2006); Chui et al. (1999); Dietzel et al. (2006); Fujita et al. (1994); He et al. (2006); Hong (2005); Li et al. (1999); Sun et al. (2006); Wang et al. (2006); Xiao et al. (2006); Zheng et al. (2006).
A mixture of Zn(CH3CO2)2.2H2O (0.120 g, 0.55 mmol), 4,4'-oxyphthalic anhydride (0.081 g, 0.26 mmol), 4,4'-bpy (0.088 g, 0.56 mmol) in a molar ratio of about 2.1:1:2.1 and water (15 ml) were placed in a 25 ml Teflon-lined stainless steel reactor and heated to 453 K for 76 h. When the reactor was cooled to room temperature over a period of 3 d, yellow prismatic single crystals suitable for X-ray diffraction were obtained.
All H atoms, except for the aqua H atoms, were positioned geometrically and refined using a riding model [C—H = 0.93 Å] and Uiso(H) = 1.2Ueq(C). The water H atoms were located from difference maps and refined isotropically, with O—H distances fixed at 0.82/0.85 Å and with Uiso(H) = 1.5Ueq(O).
The rational design and synthesis of extended metal-organic frameworks (MOFs) is important and amongst the new classes of solid functional materials has applications in magnetism, as optical materials, in catalysis and gas absorption/separation, but also by their novel diverse molecular architectures and topologies (Zheng et al., 2006; Sun et al., 2006; Fujita et al., 1994; Dietzel et al., 2006). In this family, metal carboxylates have attracted much attention: among the numerous ligands employed in this field, by far the most common are the rigid aromatic polycarboxylate ligands including 1,2-benzenedicarboxylate, 1,3,5-benzenetricarboxylate and 1,2,4,5-benzenetetracarboxylate, which have been extensively utilized in the fabrication of extended MOFs with interesting structures and desired properties (Cheng et al., 2006; Chui et al., 1999; Li et al., 1999). However, reports on MOFs based on flexible polycarboxylate ligands have been relatively scarce. Against this background, we have selected a flexible divergent carboxylic acid 3,3',4,4'-diphenyl ether-tetracarboxylic acid (H4DETA), to construct new complexes with the cooperativity of an auxiliary bpy ligand as a rigid organic spacer. The title compound, (I), was obtained under hydrothermal conditions as a pale yellow solid in good yield.
There are two crystallographically independent Zn centers in the asymmetric unit (Fig. 1). The Zn1 center has a distorted tetrahedral coordination geometry being defined by three carboxylate atoms from three different DETA ligands with Zn—O distances from 1.942 (3) to 1.975 (3) Å, and a N atom (Zn1—N = 2.045 (3) Å) from a bpy ligand occupying the 4t h site, whereas the Zn2 center is coordinated by four carboxylate atoms from two distinct DETA ligands Zn—O 2.008 (3) to 2.099 (3) Å, a longer Zn—O 2.373 (4) Å, Zn—Oaqua 2.180 (3) Å and one bipy N atom Zn—N at 2.086 (4) Å, providing a highly distorted octahedral coordination polyhedron (with two O sites at symmetry related positions). The Zn—O and Zn—N distances at Zn2 are slightly longer than those at Zn1 but all values are comparable with those reported for Zn related complexes (Tao et al., 2000; Wang et al., 2006; He et al., 2006; Hong 2005). There is also a unique DETA ligand in the fundamental unit of (I), which is bent about the central ether bond with a dihedral angle between the two phenyl rings of 72.28 (2)°. The V-shaped DETA favors the formation of helices as authenticated by BTDC (where BTDC is 3,3',4,4'-benzophenone tetracarboxylate). (Hong 2005; Xiao et al., 2006). It serves as a tetra-connector with its four carboxylate arms in three coordination modes, monodentate, bidentate and syn—anti bridging bidentate, linking Zn atoms into 2-D (two-dimensional) helical double layer subunit, (Fig. 2). There are no Zn···Zn interactions.
A feature of (I) is the two-dimensional helical double layers which are further pillared up by bpy ligands resulting in a 3-D host–guest structure: the neutral 3-D host architecture of Zn—DETA—bpy, which consists of one-dimensional rhombus channels along the [100] direction (Fig. 3), encapsulates the guest bpy ligands via hydrogen bonding interactions between the guest bpy ligands and the nearest coordinated water molecules (O1W—H1W···N3, 2.859 (6) Å).
For related literature, see: Cheng et al. (2006); Chui et al. (1999); Dietzel et al. (2006); Fujita et al. (1994); He et al. (2006); Hong (2005); Li et al. (1999); Sun et al. (2006); Wang et al. (2006); Xiao et al. (2006); Zheng et al. (2006).
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1996); data reduction: XPREP (Siemens, 1996); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Zn2(C16H6O9)(C10H8N2)(H2O)]·0.5C10H8N2 | F(000) = 1468 |
Mr = 725.28 | Dx = 1.759 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4772 reflections |
a = 10.9516 (4) Å | θ = 1.8–25.7° |
b = 15.1202 (5) Å | µ = 1.82 mm−1 |
c = 16.5498 (4) Å | T = 293 K |
β = 92.063 (1)° | Prism, yellow |
V = 2738.71 (15) Å3 | 0.28 × 0.25 × 0.20 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 5211 independent reflections |
Radiation source: fine-focus sealed tube | 3672 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
φ and ω scans | θmax = 25.7°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −13→13 |
Tmin = 0.606, Tmax = 0.695 | k = −18→18 |
13598 measured reflections | l = −20→11 |
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)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0268P)2 + 5.3897P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
5211 reflections | Δρmax = 0.50 e Å−3 |
415 parameters | Δρmin = −0.63 e Å−3 |
2 restraints |
[Zn2(C16H6O9)(C10H8N2)(H2O)]·0.5C10H8N2 | V = 2738.71 (15) Å3 |
Mr = 725.28 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.9516 (4) Å | µ = 1.82 mm−1 |
b = 15.1202 (5) Å | T = 293 K |
c = 16.5498 (4) Å | 0.28 × 0.25 × 0.20 mm |
β = 92.063 (1)° |
Siemens SMART CCD area-detector diffractometer | 5211 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3672 reflections with I > 2σ(I) |
Tmin = 0.606, Tmax = 0.695 | Rint = 0.054 |
13598 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 415 parameters |
wR(F2) = 0.099 | 2 restraints |
S = 1.08 | Δρmax = 0.50 e Å−3 |
5211 reflections | Δρmin = −0.63 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Zn1 | 0.28659 (5) | 0.39722 (3) | 0.03206 (3) | 0.02325 (14) | |
Zn2 | −0.10394 (5) | 0.35096 (3) | −0.13285 (3) | 0.02633 (15) | |
O1W | −0.2490 (3) | 0.3177 (2) | −0.22115 (19) | 0.0378 (8) | |
H1WA | −0.2298 | 0.2733 | −0.2462 | 0.057* | |
H1WB | −0.2648 | 0.3551 | −0.2583 | 0.057* | |
O1 | 0.0277 (3) | 0.3752 (2) | −0.04076 (17) | 0.0335 (8) | |
O2 | 0.1330 (3) | 0.3517 (2) | 0.07326 (18) | 0.0320 (7) | |
O3 | −0.2645 (3) | 0.49931 (19) | 0.03977 (18) | 0.0319 (8) | |
O4 | −0.2214 (3) | 0.4210 (2) | −0.06792 (18) | 0.0374 (8) | |
O5 | 0.0825 (3) | −0.0796 (2) | 0.38851 (18) | 0.0323 (8) | |
O6 | 0.1656 (3) | −0.1681 (2) | 0.29850 (19) | 0.0379 (8) | |
O7 | −0.0057 (3) | −0.2528 (2) | 0.1830 (2) | 0.0473 (10) | |
O8 | 0.1323 (4) | −0.1990 (3) | 0.1029 (2) | 0.0599 (11) | |
O9 | −0.1372 (3) | 0.1490 (2) | 0.22898 (18) | 0.0388 (8) | |
N1 | −0.0411 (3) | 0.4590 (2) | −0.1978 (2) | 0.0270 (9) | |
N2 | 0.1499 (3) | 0.8058 (2) | −0.4527 (2) | 0.0266 (9) | |
N3 | −0.2168 (5) | 0.3922 (4) | −0.3780 (3) | 0.0637 (14) | |
C1 | −0.1547 (4) | 0.2161 (3) | 0.1711 (3) | 0.0311 (11) | |
C2 | −0.0578 (4) | 0.2483 (3) | 0.1292 (3) | 0.0291 (11) | |
H2B | 0.0197 | 0.2242 | 0.1377 | 0.035* | |
C3 | −0.0761 (4) | 0.3176 (3) | 0.0734 (2) | 0.0216 (9) | |
C4 | −0.1928 (4) | 0.3543 (3) | 0.0637 (2) | 0.0223 (9) | |
C5 | −0.2867 (4) | 0.3236 (3) | 0.1104 (3) | 0.0299 (11) | |
H5 | −0.3627 | 0.3510 | 0.1062 | 0.036* | |
C6 | −0.2696 (4) | 0.2530 (3) | 0.1631 (3) | 0.0326 (11) | |
H6 | −0.3340 | 0.2311 | 0.1923 | 0.039* | |
C7 | 0.0348 (4) | 0.3511 (3) | 0.0313 (3) | 0.0235 (10) | |
C8 | −0.2258 (4) | 0.4302 (3) | 0.0075 (3) | 0.0225 (10) | |
C9 | −0.0858 (4) | 0.0700 (3) | 0.2056 (3) | 0.0280 (11) | |
C10 | −0.0280 (4) | 0.0212 (3) | 0.2669 (3) | 0.0296 (11) | |
H10 | −0.0210 | 0.0444 | 0.3189 | 0.036* | |
C11 | 0.0193 (4) | −0.0620 (3) | 0.2513 (3) | 0.0236 (10) | |
C12 | 0.0088 (4) | −0.0963 (3) | 0.1728 (3) | 0.0273 (10) | |
C13 | −0.0484 (5) | −0.0449 (3) | 0.1119 (3) | 0.0357 (12) | |
H13 | −0.0554 | −0.0673 | 0.0596 | 0.043* | |
C14 | −0.0945 (4) | 0.0380 (3) | 0.1275 (3) | 0.0345 (12) | |
H14 | −0.1309 | 0.0716 | 0.0862 | 0.041* | |
C15 | 0.0944 (4) | −0.1088 (3) | 0.3168 (3) | 0.0263 (10) | |
C16 | 0.0501 (5) | −0.1880 (3) | 0.1511 (3) | 0.0389 (13) | |
C17 | 0.0756 (4) | 0.4700 (3) | −0.2140 (3) | 0.0367 (12) | |
H17 | 0.1326 | 0.4294 | −0.1935 | 0.044* | |
C18 | 0.1155 (5) | 0.5394 (3) | −0.2603 (3) | 0.0410 (13) | |
H18 | 0.1983 | 0.5451 | −0.2698 | 0.049* | |
C19 | 0.0339 (4) | 0.6006 (3) | −0.2929 (2) | 0.0241 (10) | |
C20 | −0.0867 (4) | 0.5901 (3) | −0.2732 (3) | 0.0361 (12) | |
H20 | −0.1453 | 0.6306 | −0.2915 | 0.043* | |
C21 | −0.1202 (5) | 0.5192 (3) | −0.2263 (3) | 0.0354 (12) | |
H21 | −0.2019 | 0.5133 | −0.2139 | 0.042* | |
C22 | 0.2286 (5) | 0.7506 (3) | −0.4162 (3) | 0.0451 (14) | |
H22 | 0.3112 | 0.7563 | −0.4265 | 0.054* | |
C23 | 0.1937 (5) | 0.6853 (3) | −0.3639 (3) | 0.0460 (14) | |
H23 | 0.2527 | 0.6488 | −0.3397 | 0.055* | |
C24 | 0.0727 (4) | 0.6734 (3) | −0.3469 (3) | 0.0268 (10) | |
C25 | −0.0089 (4) | 0.7326 (3) | −0.3832 (3) | 0.0374 (12) | |
H25 | −0.0918 | 0.7287 | −0.3731 | 0.045* | |
C26 | 0.0329 (4) | 0.7973 (3) | −0.4344 (3) | 0.0358 (12) | |
H26 | −0.0235 | 0.8369 | −0.4573 | 0.043* | |
C27 | −0.2418 (6) | 0.4675 (5) | −0.4165 (4) | 0.073 (2) | |
H27 | −0.3186 | 0.4923 | −0.4107 | 0.088* | |
C28 | −0.1606 (6) | 0.5114 (4) | −0.4650 (4) | 0.0627 (18) | |
H28 | −0.1836 | 0.5640 | −0.4904 | 0.075* | |
C29 | −0.0460 (5) | 0.4770 (4) | −0.4753 (3) | 0.0437 (14) | |
C30 | −0.0191 (6) | 0.3989 (4) | −0.4357 (4) | 0.0646 (18) | |
H30 | 0.0573 | 0.3728 | −0.4403 | 0.077* | |
C31 | −0.1056 (7) | 0.3594 (4) | −0.3892 (4) | 0.074 (2) | |
H31 | −0.0852 | 0.3062 | −0.3640 | 0.089* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0235 (3) | 0.0229 (3) | 0.0233 (3) | 0.0029 (2) | 0.0008 (2) | −0.0003 (2) |
Zn2 | 0.0308 (3) | 0.0257 (3) | 0.0228 (3) | 0.0013 (2) | 0.0042 (2) | 0.0018 (2) |
O1W | 0.035 (2) | 0.0387 (19) | 0.040 (2) | 0.0004 (15) | 0.0028 (16) | −0.0032 (16) |
O1 | 0.0298 (19) | 0.051 (2) | 0.0194 (17) | −0.0076 (15) | −0.0007 (14) | 0.0065 (14) |
O2 | 0.0225 (18) | 0.0423 (19) | 0.0310 (17) | −0.0011 (15) | −0.0006 (14) | 0.0051 (15) |
O3 | 0.044 (2) | 0.0240 (17) | 0.0278 (17) | 0.0096 (15) | 0.0028 (15) | 0.0020 (14) |
O4 | 0.046 (2) | 0.046 (2) | 0.0207 (17) | 0.0228 (17) | 0.0052 (15) | 0.0053 (15) |
O5 | 0.0323 (19) | 0.0406 (19) | 0.0237 (17) | 0.0031 (15) | −0.0011 (14) | −0.0015 (14) |
O6 | 0.037 (2) | 0.0361 (19) | 0.040 (2) | 0.0130 (16) | −0.0106 (16) | −0.0065 (15) |
O7 | 0.045 (2) | 0.0231 (18) | 0.073 (3) | 0.0018 (16) | −0.020 (2) | −0.0029 (18) |
O8 | 0.075 (3) | 0.060 (3) | 0.046 (2) | 0.022 (2) | 0.012 (2) | −0.007 (2) |
O9 | 0.057 (2) | 0.0313 (18) | 0.0287 (18) | 0.0116 (17) | 0.0087 (16) | 0.0111 (15) |
N1 | 0.033 (2) | 0.025 (2) | 0.023 (2) | −0.0009 (17) | 0.0020 (17) | 0.0011 (16) |
N2 | 0.026 (2) | 0.026 (2) | 0.029 (2) | −0.0028 (17) | 0.0012 (17) | 0.0047 (17) |
N3 | 0.070 (4) | 0.071 (4) | 0.051 (3) | −0.008 (3) | 0.010 (3) | 0.000 (3) |
C1 | 0.038 (3) | 0.025 (2) | 0.030 (3) | 0.001 (2) | 0.007 (2) | 0.007 (2) |
C2 | 0.025 (3) | 0.025 (2) | 0.037 (3) | 0.007 (2) | 0.002 (2) | 0.004 (2) |
C3 | 0.025 (3) | 0.023 (2) | 0.018 (2) | 0.0019 (19) | 0.0005 (18) | 0.0011 (18) |
C4 | 0.023 (2) | 0.019 (2) | 0.025 (2) | 0.0032 (19) | 0.0013 (18) | 0.0013 (19) |
C5 | 0.021 (3) | 0.031 (3) | 0.038 (3) | 0.009 (2) | 0.007 (2) | 0.006 (2) |
C6 | 0.025 (3) | 0.032 (3) | 0.041 (3) | 0.000 (2) | 0.009 (2) | 0.007 (2) |
C7 | 0.022 (2) | 0.021 (2) | 0.027 (3) | 0.0039 (19) | 0.002 (2) | −0.001 (2) |
C8 | 0.012 (2) | 0.026 (2) | 0.029 (3) | 0.0018 (18) | 0.0020 (19) | 0.0027 (19) |
C9 | 0.026 (3) | 0.017 (2) | 0.041 (3) | 0.0009 (19) | 0.005 (2) | 0.005 (2) |
C10 | 0.034 (3) | 0.024 (2) | 0.031 (3) | −0.002 (2) | −0.003 (2) | 0.001 (2) |
C11 | 0.023 (2) | 0.020 (2) | 0.027 (2) | −0.0007 (19) | −0.0024 (19) | 0.0027 (19) |
C12 | 0.025 (3) | 0.020 (2) | 0.037 (3) | −0.0017 (19) | −0.002 (2) | 0.002 (2) |
C13 | 0.044 (3) | 0.032 (3) | 0.030 (3) | −0.001 (2) | −0.006 (2) | 0.000 (2) |
C14 | 0.040 (3) | 0.026 (3) | 0.037 (3) | −0.001 (2) | −0.004 (2) | 0.007 (2) |
C15 | 0.021 (2) | 0.025 (2) | 0.033 (3) | −0.007 (2) | −0.001 (2) | −0.002 (2) |
C16 | 0.046 (3) | 0.037 (3) | 0.033 (3) | 0.009 (3) | −0.020 (3) | −0.007 (2) |
C17 | 0.026 (3) | 0.038 (3) | 0.046 (3) | 0.006 (2) | −0.001 (2) | 0.019 (2) |
C18 | 0.026 (3) | 0.044 (3) | 0.053 (3) | −0.002 (2) | −0.001 (2) | 0.020 (3) |
C19 | 0.025 (3) | 0.024 (2) | 0.023 (2) | −0.001 (2) | 0.0007 (19) | 0.0003 (19) |
C20 | 0.032 (3) | 0.027 (3) | 0.050 (3) | 0.006 (2) | 0.014 (2) | 0.013 (2) |
C21 | 0.030 (3) | 0.033 (3) | 0.044 (3) | 0.008 (2) | 0.012 (2) | 0.008 (2) |
C22 | 0.022 (3) | 0.049 (3) | 0.065 (4) | −0.002 (2) | 0.006 (3) | 0.028 (3) |
C23 | 0.033 (3) | 0.046 (3) | 0.058 (4) | 0.007 (3) | 0.004 (3) | 0.029 (3) |
C24 | 0.032 (3) | 0.022 (2) | 0.026 (2) | −0.001 (2) | 0.002 (2) | −0.0018 (19) |
C25 | 0.026 (3) | 0.042 (3) | 0.045 (3) | −0.001 (2) | 0.009 (2) | 0.015 (2) |
C26 | 0.030 (3) | 0.034 (3) | 0.043 (3) | 0.008 (2) | 0.005 (2) | 0.012 (2) |
C27 | 0.048 (4) | 0.101 (6) | 0.071 (5) | −0.001 (4) | −0.002 (4) | 0.015 (4) |
C28 | 0.053 (4) | 0.079 (5) | 0.055 (4) | 0.003 (4) | −0.013 (3) | 0.022 (3) |
C29 | 0.055 (4) | 0.050 (3) | 0.025 (3) | −0.002 (3) | −0.004 (2) | −0.007 (2) |
C30 | 0.082 (5) | 0.050 (4) | 0.064 (4) | 0.012 (3) | 0.024 (4) | 0.008 (3) |
C31 | 0.111 (6) | 0.049 (4) | 0.065 (4) | 0.005 (4) | 0.035 (4) | 0.002 (3) |
Zn1—O2 | 1.962 (3) | C5—C6 | 1.388 (6) |
Zn1—O3i | 1.975 (3) | C5—H5 | 0.9300 |
Zn1—O5ii | 1.942 (3) | C6—H6 | 0.9300 |
Zn1—N2iii | 2.045 (3) | C9—C14 | 1.380 (6) |
Zn2—N1 | 2.086 (3) | C9—C10 | 1.388 (6) |
Zn2—O1 | 2.092 (3) | C10—C11 | 1.389 (6) |
Zn2—O4 | 2.008 (3) | C10—H10 | 0.9300 |
Zn2—O7iv | 2.099 (3) | C11—C12 | 1.399 (6) |
Zn2—O8iv | 2.373 (4) | C11—C15 | 1.513 (6) |
Zn2—O1W | 2.179 (3) | C12—C13 | 1.402 (6) |
Zn2—C16iv | 2.554 (5) | C12—C16 | 1.506 (6) |
O1W—H1WA | 0.8200 | C13—C14 | 1.379 (6) |
O1W—H1WB | 0.8486 | C13—H13 | 0.9300 |
O1—C7 | 1.246 (5) | C14—H14 | 0.9300 |
O2—C7 | 1.260 (5) | C16—Zn2iv | 2.554 (5) |
O3—C8 | 1.254 (5) | C17—C18 | 1.380 (6) |
O3—Zn1i | 1.975 (3) | C17—H17 | 0.9300 |
O4—C8 | 1.258 (5) | C18—C19 | 1.383 (6) |
O5—C15 | 1.278 (5) | C18—H18 | 0.9300 |
O5—Zn1v | 1.942 (3) | C19—C20 | 1.381 (6) |
O6—C15 | 1.233 (5) | C19—C24 | 1.489 (6) |
O7—C16 | 1.278 (6) | C20—C21 | 1.381 (6) |
O7—Zn2iv | 2.099 (3) | C20—H20 | 0.9300 |
O8—C16 | 1.235 (6) | C21—H21 | 0.9300 |
O8—Zn2iv | 2.373 (4) | C22—C23 | 1.376 (6) |
O9—C9 | 1.381 (5) | C22—H22 | 0.9300 |
O9—C1 | 1.404 (5) | C23—C24 | 1.377 (6) |
N1—C17 | 1.326 (6) | C23—H23 | 0.9300 |
N1—C21 | 1.331 (6) | C24—C25 | 1.387 (6) |
N2—C22 | 1.330 (6) | C25—C26 | 1.384 (6) |
N2—C26 | 1.334 (6) | C25—H25 | 0.9300 |
N2—Zn1vi | 2.045 (3) | C26—H26 | 0.9300 |
N3—C27 | 1.328 (8) | C27—C28 | 1.388 (8) |
N3—C31 | 1.334 (8) | C27—H27 | 0.9300 |
C1—C6 | 1.378 (6) | C28—C29 | 1.375 (8) |
C1—C2 | 1.378 (6) | C28—H28 | 0.9300 |
C2—C3 | 1.405 (6) | C29—C30 | 1.379 (7) |
C2—H2B | 0.9300 | C29—C29vii | 1.491 (11) |
C3—C4 | 1.398 (6) | C30—C31 | 1.377 (8) |
C3—C7 | 1.509 (6) | C30—H30 | 0.9300 |
C4—C5 | 1.388 (6) | C31—H31 | 0.9300 |
C4—C8 | 1.513 (6) | ||
O5ii—Zn1—O2 | 116.70 (13) | O9—C9—C10 | 115.8 (4) |
O5ii—Zn1—O3i | 109.63 (13) | C9—C10—C11 | 120.6 (4) |
O2—Zn1—O3i | 113.51 (13) | C9—C10—H10 | 119.7 |
O5ii—Zn1—N2iii | 107.27 (14) | C11—C10—H10 | 119.7 |
O2—Zn1—N2iii | 107.57 (14) | C10—C11—C12 | 119.3 (4) |
O3i—Zn1—N2iii | 100.73 (13) | C10—C11—C15 | 119.2 (4) |
O4—Zn2—N1 | 95.29 (14) | C12—C11—C15 | 121.1 (4) |
O4—Zn2—O1 | 87.45 (13) | C11—C12—C13 | 118.8 (4) |
N1—Zn2—O1 | 90.38 (13) | C11—C12—C16 | 123.1 (4) |
O4—Zn2—O7iv | 166.27 (14) | C13—C12—C16 | 118.0 (4) |
N1—Zn2—O7iv | 98.40 (14) | C14—C13—C12 | 121.7 (4) |
O1—Zn2—O7iv | 91.34 (13) | C14—C13—H13 | 119.1 |
O4—Zn2—O1W | 90.86 (13) | C12—C13—H13 | 119.1 |
N1—Zn2—O1W | 94.67 (13) | C13—C14—C9 | 118.7 (4) |
O1—Zn2—O1W | 174.81 (12) | C13—C14—H14 | 120.6 |
O7iv—Zn2—O1W | 89.13 (12) | C9—C14—H14 | 120.6 |
O4—Zn2—O8iv | 107.94 (14) | O6—C15—O5 | 124.5 (4) |
N1—Zn2—O8iv | 156.04 (14) | O6—C15—C11 | 119.7 (4) |
O1—Zn2—O8iv | 96.31 (13) | O5—C15—C11 | 115.6 (4) |
O7iv—Zn2—O8iv | 58.59 (14) | O8—C16—O7 | 122.3 (5) |
O1W—Zn2—O8iv | 79.54 (13) | O8—C16—C12 | 120.6 (5) |
O4—Zn2—C16iv | 136.67 (17) | O7—C16—C12 | 117.1 (5) |
N1—Zn2—C16iv | 127.79 (17) | O8—C16—Zn2iv | 67.5 (3) |
O1—Zn2—C16iv | 95.69 (14) | O7—C16—Zn2iv | 54.9 (2) |
O7iv—Zn2—C16iv | 29.90 (16) | C12—C16—Zn2iv | 171.5 (4) |
O1W—Zn2—C16iv | 82.18 (13) | N1—C17—C18 | 122.3 (4) |
O8iv—Zn2—C16iv | 28.74 (15) | N1—C17—H17 | 118.9 |
Zn2—O1W—H1WA | 109.5 | C18—C17—H17 | 118.9 |
Zn2—O1W—H1WB | 117.2 | C17—C18—C19 | 120.9 (5) |
H1WA—O1W—H1WB | 103.2 | C17—C18—H18 | 119.6 |
C7—O1—Zn2 | 131.5 (3) | C19—C18—H18 | 119.6 |
C7—O2—Zn1 | 122.5 (3) | C20—C19—C18 | 116.1 (4) |
C8—O3—Zn1i | 116.1 (3) | C20—C19—C24 | 121.6 (4) |
C8—O4—Zn2 | 129.6 (3) | C18—C19—C24 | 122.3 (4) |
C15—O5—Zn1v | 117.9 (3) | C21—C20—C19 | 119.9 (4) |
C16—O7—Zn2iv | 95.2 (3) | C21—C20—H20 | 120.1 |
C16—O8—Zn2iv | 83.8 (3) | C19—C20—H20 | 120.1 |
C9—O9—C1 | 118.8 (3) | N1—C21—C20 | 123.2 (4) |
C17—N1—C21 | 117.5 (4) | N1—C21—H21 | 118.4 |
C17—N1—Zn2 | 122.7 (3) | C20—C21—H21 | 118.4 |
C21—N1—Zn2 | 119.7 (3) | N2—C22—C23 | 123.1 (5) |
C22—N2—C26 | 116.7 (4) | N2—C22—H22 | 118.4 |
C22—N2—Zn1vi | 119.1 (3) | C23—C22—H22 | 118.4 |
C26—N2—Zn1vi | 124.3 (3) | C22—C23—C24 | 120.9 (5) |
C27—N3—C31 | 115.1 (6) | C22—C23—H23 | 119.5 |
C6—C1—C2 | 121.7 (4) | C24—C23—H23 | 119.5 |
C6—C1—O9 | 117.4 (4) | C23—C24—C25 | 116.0 (4) |
C2—C1—O9 | 120.7 (4) | C23—C24—C19 | 121.2 (4) |
C1—C2—C3 | 120.0 (4) | C25—C24—C19 | 122.9 (4) |
C1—C2—H2B | 120.0 | C26—C25—C24 | 120.0 (4) |
C3—C2—H2B | 120.0 | C26—C25—H25 | 120.0 |
C4—C3—C2 | 118.6 (4) | C24—C25—H25 | 120.0 |
C4—C3—C7 | 124.1 (4) | N2—C26—C25 | 123.3 (4) |
C2—C3—C7 | 117.1 (4) | N2—C26—H26 | 118.3 |
C5—C4—C3 | 119.8 (4) | C25—C26—H26 | 118.3 |
C5—C4—C8 | 115.4 (4) | N3—C27—C28 | 124.2 (7) |
C3—C4—C8 | 124.7 (4) | N3—C27—H27 | 117.9 |
C6—C5—C4 | 121.4 (4) | C28—C27—H27 | 117.9 |
C6—C5—H5 | 119.3 | C29—C28—C27 | 119.8 (6) |
C4—C5—H5 | 119.3 | C29—C28—H28 | 120.1 |
C1—C6—C5 | 118.3 (4) | C27—C28—H28 | 120.1 |
C1—C6—H6 | 120.8 | C28—C29—C30 | 116.4 (5) |
C5—C6—H6 | 120.8 | C28—C29—C29vii | 122.0 (7) |
O1—C7—O2 | 123.2 (4) | C30—C29—C29vii | 121.6 (7) |
O1—C7—C3 | 121.1 (4) | C31—C30—C29 | 119.8 (6) |
O2—C7—C3 | 115.6 (4) | C31—C30—H30 | 120.1 |
O3—C8—O4 | 122.7 (4) | C29—C30—H30 | 120.1 |
O3—C8—C4 | 116.6 (4) | N3—C31—C30 | 124.5 (6) |
O4—C8—C4 | 120.6 (4) | N3—C31—H31 | 117.7 |
C14—C9—O9 | 123.4 (4) | C30—C31—H31 | 117.7 |
C14—C9—C10 | 120.8 (4) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z−1/2; (iv) −x, −y, −z; (v) −x+1/2, y−1/2, −z+1/2; (vi) −x+1/2, y+1/2, −z−1/2; (vii) −x, −y+1, −z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O6iv | 0.82 | 1.95 | 2.770 (4) | 173 |
O1W—H1WB···N3 | 0.85 | 2.14 | 2.863 (6) | 143 |
Symmetry code: (iv) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C16H6O9)(C10H8N2)(H2O)]·0.5C10H8N2 |
Mr | 725.28 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.9516 (4), 15.1202 (5), 16.5498 (4) |
β (°) | 92.063 (1) |
V (Å3) | 2738.71 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.82 |
Crystal size (mm) | 0.28 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.606, 0.695 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13598, 5211, 3672 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.099, 1.08 |
No. of reflections | 5211 |
No. of parameters | 415 |
No. of restraints | 2 |
Δρmax, Δρmin (e Å−3) | 0.50, −0.63 |
Computer programs: SMART (Siemens, 1996), SMART and SAINT (Siemens, 1996), XPREP (Siemens, 1996), SHELXTL (Bruker, 1997), SHELXTL.
Zn1—O2 | 1.962 (3) | Zn2—O1 | 2.092 (3) |
Zn1—O3i | 1.975 (3) | Zn2—O4 | 2.008 (3) |
Zn1—O5ii | 1.942 (3) | Zn2—O7iv | 2.099 (3) |
Zn1—N2iii | 2.045 (3) | Zn2—O8iv | 2.373 (4) |
Zn2—N1 | 2.086 (3) | Zn2—O1W | 2.179 (3) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z−1/2; (iv) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O6iv | 0.82 | 1.95 | 2.770 (4) | 173 |
O1W—H1WB···N3 | 0.85 | 2.14 | 2.863 (6) | 143 |
Symmetry code: (iv) −x, −y, −z. |
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The rational design and synthesis of extended metal-organic frameworks (MOFs) is important and amongst the new classes of solid functional materials has applications in magnetism, as optical materials, in catalysis and gas absorption/separation, but also by their novel diverse molecular architectures and topologies (Zheng et al., 2006; Sun et al., 2006; Fujita et al., 1994; Dietzel et al., 2006). In this family, metal carboxylates have attracted much attention: among the numerous ligands employed in this field, by far the most common are the rigid aromatic polycarboxylate ligands including 1,2-benzenedicarboxylate, 1,3,5-benzenetricarboxylate and 1,2,4,5-benzenetetracarboxylate, which have been extensively utilized in the fabrication of extended MOFs with interesting structures and desired properties (Cheng et al., 2006; Chui et al., 1999; Li et al., 1999). However, reports on MOFs based on flexible polycarboxylate ligands have been relatively scarce. Against this background, we have selected a flexible divergent carboxylic acid 3,3',4,4'-diphenyl ether-tetracarboxylic acid (H4DETA), to construct new complexes with the cooperativity of an auxiliary bpy ligand as a rigid organic spacer. The title compound, (I), was obtained under hydrothermal conditions as a pale yellow solid in good yield.
There are two crystallographically independent Zn centers in the asymmetric unit (Fig. 1). The Zn1 center has a distorted tetrahedral coordination geometry being defined by three carboxylate atoms from three different DETA ligands with Zn—O distances from 1.942 (3) to 1.975 (3) Å, and a N atom (Zn1—N = 2.045 (3) Å) from a bpy ligand occupying the 4t h site, whereas the Zn2 center is coordinated by four carboxylate atoms from two distinct DETA ligands Zn—O 2.008 (3) to 2.099 (3) Å, a longer Zn—O 2.373 (4) Å, Zn—Oaqua 2.180 (3) Å and one bipy N atom Zn—N at 2.086 (4) Å, providing a highly distorted octahedral coordination polyhedron (with two O sites at symmetry related positions). The Zn—O and Zn—N distances at Zn2 are slightly longer than those at Zn1 but all values are comparable with those reported for Zn related complexes (Tao et al., 2000; Wang et al., 2006; He et al., 2006; Hong 2005). There is also a unique DETA ligand in the fundamental unit of (I), which is bent about the central ether bond with a dihedral angle between the two phenyl rings of 72.28 (2)°. The V-shaped DETA favors the formation of helices as authenticated by BTDC (where BTDC is 3,3',4,4'-benzophenone tetracarboxylate). (Hong 2005; Xiao et al., 2006). It serves as a tetra-connector with its four carboxylate arms in three coordination modes, monodentate, bidentate and syn—anti bridging bidentate, linking Zn atoms into 2-D (two-dimensional) helical double layer subunit, (Fig. 2). There are no Zn···Zn interactions.
A feature of (I) is the two-dimensional helical double layers which are further pillared up by bpy ligands resulting in a 3-D host–guest structure: the neutral 3-D host architecture of Zn—DETA—bpy, which consists of one-dimensional rhombus channels along the [100] direction (Fig. 3), encapsulates the guest bpy ligands via hydrogen bonding interactions between the guest bpy ligands and the nearest coordinated water molecules (O1W—H1W···N3, 2.859 (6) Å).