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The solvothermal reaction of zinc(II) acetate with 1,3,5-benzenetricarboxylic acid and 4,4'-bipyridine in 1-butanol and acetic acid solution gives the title complex, [Zn3(C9H3O6)2(C10H8N2)(H2O)2]n. There are two different coordination environments for the Zn atom, namely ZnNO2(H2O) and ZnO4; in the latter case, the Zn atom lies on a twofold symmetry axis. Carboxylate-bridged Zn3(O2C)6 clusters are connected through 1,3,5-benzenetricarboxylate and 4,4'-bipyridine ligands (which lie about inversion centers), yielding a three-dimensional framework.
Supporting information
CCDC reference: 219558
In a typical synthetic procedure, Zn(CH3COO)2.2H2O (0.220 g), H3btc (0.105 g), 4,4'-bipy.2H2O (0.096 g), 1-butanol (2 ml) and acetic acid (3 ml) were mixed, sealed in a Teflon-lined steel autoclave and allowed to crystallize at 433 K for 120 h. Colourless product crystals were washed with deionized water, filtered and dried in air at room temperature.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXP97 (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Crystal data top
[Zn3(C9H4O6)2(C10H8N2)(H2O)2] | F(000) = 1608 |
Mr = 802.55 | Dx = 1.860 Mg m−3 |
Monoclinic, C2/c | Melting point: not measured K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3816 (3) Å | Cell parameters from 4171 reflections |
b = 18.6749 (6) Å | θ = 2.2–30.0° |
c = 14.8264 (4) Å | µ = 2.57 mm−1 |
β = 94.517 (2)° | T = 293 K |
V = 2865.55 (15) Å3 | Block, colourless |
Z = 4 | 0.29 × 0.22 × 0.14 mm |
Data collection top
CCD area detector diffractometer | 4171 independent reflections |
Radiation source: fine-focus sealed tube | 2817 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: Bruker SMART CCD area-detector pixels mm-1 | θmax = 30.0°, θmin = 2.2° |
ϕ and ω scans | h = −14→9 |
Absorption correction: empirical (using intensity measurements) SADABS; Sheldrick, (1996) | k = −22→26 |
Tmin = 0.478, Tmax = 0.695 | l = −20→19 |
11594 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | w = 1/[σ2(Fo2) + (0.0357P)2] where P = (Fo2 + 2Fc2)/3 |
4171 reflections | (Δ/σ)max = 0.001 |
221 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
[Zn3(C9H4O6)2(C10H8N2)(H2O)2] | V = 2865.55 (15) Å3 |
Mr = 802.55 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.3816 (3) Å | µ = 2.57 mm−1 |
b = 18.6749 (6) Å | T = 293 K |
c = 14.8264 (4) Å | 0.29 × 0.22 × 0.14 mm |
β = 94.517 (2)° | |
Data collection top
CCD area detector diffractometer | 4171 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS; Sheldrick, (1996) | 2817 reflections with I > 2σ(I) |
Tmin = 0.478, Tmax = 0.695 | Rint = 0.027 |
11594 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.91 | Δρmax = 0.44 e Å−3 |
4171 reflections | Δρmin = −0.36 e Å−3 |
221 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 | Uiso*/Ueq | |
Zn1 | 0.19754 (3) | 0.191761 (14) | 0.669521 (16) | 0.03369 (8) | |
Zn2 | 0.0000 | 0.020299 (18) | 0.7500 | 0.02657 (9) | |
O1 | 0.23244 (15) | 0.15940 (9) | 0.79357 (9) | 0.0413 (4) | |
O2 | 0.0912 (2) | 0.08090 (10) | 0.84212 (11) | 0.0608 (5) | |
O3 | 0.54131 (15) | 0.25649 (10) | 1.15223 (10) | 0.0462 (4) | |
O4 | 0.57208 (15) | 0.26405 (9) | 1.00704 (10) | 0.0440 (4) | |
O5 | 0.10314 (16) | 0.02738 (9) | 1.16640 (10) | 0.0434 (4) | |
O6 | 0.19437 (19) | 0.10394 (10) | 1.26608 (10) | 0.0569 (5) | |
O1W | 0.3411 (2) | 0.26376 (12) | 0.66461 (15) | 0.0518 (5) | |
N1 | 0.28291 (18) | 0.11320 (10) | 0.60416 (12) | 0.0355 (4) | |
C1 | 0.2373 (2) | 0.13687 (11) | 0.94896 (13) | 0.0285 (4) | |
C2 | 0.3446 (2) | 0.18083 (11) | 0.96519 (13) | 0.0283 (4) | |
H2 | 0.3823 | 0.2019 | 0.9169 | 0.080* | |
C3 | 0.39582 (19) | 0.19355 (11) | 1.05264 (13) | 0.0282 (4) | |
C4 | 0.3377 (2) | 0.16266 (11) | 1.12551 (13) | 0.0303 (4) | |
H4 | 0.3701 | 0.1725 | 1.1845 | 0.080* | |
C5 | 0.2322 (2) | 0.11755 (11) | 1.11003 (13) | 0.0304 (5) | |
C6 | 0.1818 (2) | 0.10442 (11) | 1.02150 (13) | 0.0307 (5) | |
H6 | 0.1112 | 0.0741 | 1.0108 | 0.080* | |
C7 | 0.1814 (2) | 0.12423 (12) | 0.85379 (13) | 0.0314 (5) | |
C8 | 0.5114 (2) | 0.24111 (11) | 1.06957 (14) | 0.0323 (5) | |
C9 | 0.1723 (2) | 0.08149 (12) | 1.18810 (14) | 0.0355 (5) | |
C10 | 0.3778 (3) | 0.07875 (17) | 0.65139 (16) | 0.0590 (8) | |
H10 | 0.3869 | 0.0855 | 0.7137 | 0.080* | |
C11 | 0.4628 (3) | 0.03400 (16) | 0.61357 (16) | 0.0563 (8) | |
H11 | 0.5269 | 0.0109 | 0.6500 | 0.080* | |
C12 | 0.4533 (2) | 0.02323 (11) | 0.52179 (14) | 0.0325 (5) | |
C13 | 0.3519 (3) | 0.05645 (14) | 0.47256 (16) | 0.0511 (7) | |
H13 | 0.3388 | 0.0491 | 0.4105 | 0.080* | |
C14 | 0.2700 (3) | 0.10084 (15) | 0.51636 (16) | 0.0514 (7) | |
H14 | 0.2025 | 0.1230 | 0.4821 | 0.080* | |
H1A | 0.324 (3) | 0.3003 (19) | 0.688 (2) | 0.091 (14)* | |
H1B | 0.371 (3) | 0.2651 (17) | 0.620 (2) | 0.070 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Zn1 | 0.03618 (15) | 0.04109 (16) | 0.02371 (13) | 0.00914 (11) | 0.00186 (10) | 0.00237 (10) |
Zn2 | 0.03236 (19) | 0.03134 (19) | 0.01593 (15) | 0.000 | 0.00131 (12) | 0.000 |
O1 | 0.0389 (9) | 0.0628 (11) | 0.0220 (8) | −0.0009 (8) | 0.0011 (6) | 0.0092 (7) |
O2 | 0.0818 (14) | 0.0676 (13) | 0.0310 (9) | −0.0373 (11) | −0.0074 (9) | −0.0077 (8) |
O3 | 0.0419 (10) | 0.0667 (12) | 0.0304 (8) | −0.0233 (8) | 0.0054 (7) | −0.0104 (8) |
O4 | 0.0422 (10) | 0.0562 (11) | 0.0349 (9) | −0.0158 (8) | 0.0111 (7) | −0.0001 (7) |
O5 | 0.0562 (11) | 0.0428 (10) | 0.0329 (9) | −0.0197 (8) | 0.0150 (7) | −0.0046 (7) |
O6 | 0.0868 (14) | 0.0622 (12) | 0.0227 (8) | −0.0260 (10) | 0.0100 (8) | −0.0032 (8) |
O1W | 0.0611 (13) | 0.0552 (13) | 0.0407 (11) | −0.0102 (10) | 0.0149 (9) | −0.0020 (9) |
N1 | 0.0399 (11) | 0.0379 (11) | 0.0286 (10) | 0.0087 (8) | 0.0017 (8) | 0.0013 (8) |
C1 | 0.0335 (12) | 0.0317 (11) | 0.0203 (10) | 0.0024 (9) | 0.0021 (8) | −0.0009 (8) |
C2 | 0.0321 (11) | 0.0297 (11) | 0.0235 (10) | 0.0011 (9) | 0.0052 (8) | 0.0001 (8) |
C3 | 0.0273 (11) | 0.0323 (11) | 0.0252 (10) | −0.0008 (9) | 0.0037 (8) | −0.0013 (8) |
C4 | 0.0337 (12) | 0.0348 (11) | 0.0224 (10) | −0.0019 (9) | 0.0014 (8) | −0.0021 (8) |
C5 | 0.0343 (12) | 0.0340 (12) | 0.0234 (10) | −0.0028 (9) | 0.0046 (8) | 0.0005 (8) |
C6 | 0.0329 (12) | 0.0324 (11) | 0.0270 (10) | −0.0042 (9) | 0.0030 (8) | −0.0016 (8) |
C7 | 0.0346 (12) | 0.0351 (12) | 0.0243 (10) | 0.0032 (10) | 0.0006 (8) | −0.0044 (8) |
C8 | 0.0289 (11) | 0.0355 (12) | 0.0328 (12) | 0.0003 (9) | 0.0039 (9) | −0.0047 (9) |
C9 | 0.0379 (13) | 0.0396 (13) | 0.0296 (11) | −0.0043 (10) | 0.0070 (9) | 0.0015 (9) |
C10 | 0.0623 (18) | 0.087 (2) | 0.0265 (13) | 0.0320 (16) | −0.0023 (11) | −0.0032 (13) |
C11 | 0.0559 (17) | 0.084 (2) | 0.0282 (12) | 0.0365 (15) | −0.0043 (11) | −0.0030 (12) |
C12 | 0.0355 (12) | 0.0302 (11) | 0.0317 (11) | 0.0004 (9) | 0.0010 (9) | −0.0013 (9) |
C13 | 0.0663 (18) | 0.0563 (17) | 0.0290 (12) | 0.0260 (14) | −0.0068 (11) | −0.0070 (11) |
C14 | 0.0586 (17) | 0.0605 (17) | 0.0332 (13) | 0.0278 (13) | −0.0086 (11) | −0.0048 (11) |
Geometric parameters (Å, º) top
Zn1—O3i | 1.8880 (15) | C1—C6 | 1.398 (3) |
Zn1—O1 | 1.9428 (14) | C1—C7 | 1.502 (3) |
Zn1—N1 | 2.0031 (17) | C2—C3 | 1.383 (3) |
Zn1—O1W | 2.013 (2) | C2—H2 | 0.9300 |
Zn2—O5ii | 1.9195 (14) | C3—C4 | 1.402 (3) |
Zn2—O5iii | 1.9195 (14) | C3—C8 | 1.498 (3) |
Zn2—O2 | 1.9592 (16) | C4—C5 | 1.387 (3) |
Zn2—O2iv | 1.9592 (16) | C4—H4 | 0.9300 |
O1—C7 | 1.258 (2) | C5—C6 | 1.396 (3) |
O2—C7 | 1.240 (3) | C5—C9 | 1.514 (3) |
O3—C8 | 1.273 (2) | C6—H6 | 0.9300 |
O3—Zn1v | 1.8880 (15) | C10—C11 | 1.367 (3) |
O4—C8 | 1.238 (2) | C10—H10 | 0.9300 |
O5—C9 | 1.266 (3) | C11—C12 | 1.371 (3) |
O5—Zn2iii | 1.9195 (14) | C11—H11 | 0.9300 |
O6—C9 | 1.234 (3) | C12—C13 | 1.380 (3) |
O1W—H1A | 0.79 (3) | C12—C12vi | 1.486 (4) |
O1W—H1B | 0.75 (3) | C13—C14 | 1.386 (3) |
N1—C14 | 1.319 (3) | C13—H13 | 0.9300 |
N1—C10 | 1.329 (3) | C14—H14 | 0.9300 |
C1—C2 | 1.390 (3) | | |
| | | |
O3i—Zn1—O1 | 112.45 (7) | C5—C4—H4 | 119.8 |
O3i—Zn1—N1 | 135.84 (8) | C3—C4—H4 | 119.8 |
O1—Zn1—N1 | 99.99 (7) | C4—C5—C6 | 119.67 (18) |
O3i—Zn1—O1W | 106.49 (9) | C4—C5—C9 | 120.67 (18) |
O1—Zn1—O1W | 99.12 (8) | C6—C5—C9 | 119.66 (19) |
N1—Zn1—O1W | 96.58 (9) | C5—C6—C1 | 120.04 (19) |
O5ii—Zn2—O5iii | 124.73 (10) | C5—C6—H6 | 120.0 |
O5ii—Zn2—O2 | 117.04 (8) | C1—C6—H6 | 120.0 |
O5iii—Zn2—O2 | 94.66 (7) | O2—C7—O1 | 126.7 (2) |
O5ii—Zn2—O2iv | 94.66 (7) | O2—C7—C1 | 117.75 (19) |
O5iii—Zn2—O2iv | 117.04 (8) | O1—C7—C1 | 115.56 (19) |
O2—Zn2—O2iv | 109.43 (12) | O4—C8—O3 | 122.9 (2) |
C7—O1—Zn1 | 140.94 (15) | O4—C8—C3 | 121.87 (19) |
C7—O2—Zn2 | 142.43 (16) | O3—C8—C3 | 115.26 (17) |
C8—O3—Zn1v | 112.84 (13) | O6—C9—O5 | 124.7 (2) |
C9—O5—Zn2iii | 122.69 (14) | O6—C9—C5 | 120.5 (2) |
Zn1—O1W—H1A | 112 (3) | O5—C9—C5 | 114.79 (19) |
Zn1—O1W—H1B | 114 (2) | N1—C10—C11 | 123.7 (2) |
H1A—O1W—H1B | 118 (3) | N1—C10—H10 | 118.1 |
C14—N1—C10 | 116.7 (2) | C11—C10—H10 | 118.1 |
C14—N1—Zn1 | 126.25 (16) | C10—C11—C12 | 119.9 (2) |
C10—N1—Zn1 | 115.95 (16) | C10—C11—H11 | 120.0 |
C2—C1—C6 | 119.77 (18) | C12—C11—H11 | 120.0 |
C2—C1—C7 | 120.06 (17) | C11—C12—C13 | 116.8 (2) |
C6—C1—C7 | 120.17 (19) | C11—C12—C12vi | 121.3 (2) |
C3—C2—C1 | 120.50 (18) | C13—C12—C12vi | 121.9 (2) |
C3—C2—H2 | 119.8 | C12—C13—C14 | 119.5 (2) |
C1—C2—H2 | 119.8 | C12—C13—H13 | 120.3 |
C2—C3—C4 | 119.67 (19) | C14—C13—H13 | 120.3 |
C2—C3—C8 | 120.17 (18) | N1—C14—C13 | 123.3 (2) |
C4—C3—C8 | 120.15 (18) | N1—C14—H14 | 118.4 |
C5—C4—C3 | 120.30 (18) | C13—C14—H14 | 118.4 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x, −y, z−1/2; (iii) −x, −y, −z+2; (iv) −x, y, −z+3/2; (v) x+1/2, −y+1/2, z+1/2; (vi) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1A···O6vii | 0.79 (3) | 1.93 (4) | 2.712 (3) | 170 (4) |
O1W—H1B···O4viii | 0.75 (3) | 2.02 (3) | 2.766 (3) | 172 (3) |
Symmetry codes: (vii) −x+1/2, −y+1/2, −z+2; (viii) −x+1, y, −z+3/2. |
Experimental details
Crystal data |
Chemical formula | [Zn3(C9H4O6)2(C10H8N2)(H2O)2] |
Mr | 802.55 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 10.3816 (3), 18.6749 (6), 14.8264 (4) |
β (°) | 94.517 (2) |
V (Å3) | 2865.55 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.57 |
Crystal size (mm) | 0.29 × 0.22 × 0.14 |
|
Data collection |
Diffractometer | CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) SADABS; Sheldrick, (1996) |
Tmin, Tmax | 0.478, 0.695 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11594, 4171, 2817 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.704 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.068, 0.91 |
No. of reflections | 4171 |
No. of parameters | 221 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.44, −0.36 |
Selected geometric parameters (Å, º) topZn1—O3i | 1.8880 (15) | Zn2—O5ii | 1.9195 (14) |
Zn1—O1 | 1.9428 (14) | Zn2—O5iii | 1.9195 (14) |
Zn1—N1 | 2.0031 (17) | Zn2—O2 | 1.9592 (16) |
Zn1—O1W | 2.013 (2) | Zn2—O2iv | 1.9592 (16) |
| | | |
O3i—Zn1—O1 | 112.45 (7) | O5iii—Zn2—O2 | 94.66 (7) |
O3i—Zn1—N1 | 135.84 (8) | O5ii—Zn2—O2iv | 94.66 (7) |
O1—Zn1—N1 | 99.99 (7) | O5iii—Zn2—O2iv | 117.04 (8) |
O3i—Zn1—O1W | 106.49 (9) | O2—Zn2—O2iv | 109.43 (12) |
O1—Zn1—O1W | 99.12 (8) | C7—O1—Zn1 | 140.94 (15) |
N1—Zn1—O1W | 96.58 (9) | C7—O2—Zn2 | 142.43 (16) |
O5ii—Zn2—O5iii | 124.73 (10) | C8—O3—Zn1v | 112.84 (13) |
O5ii—Zn2—O2 | 117.04 (8) | C9—O5—Zn2iii | 122.69 (14) |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x, −y, z−1/2; (iii) −x, −y, −z+2; (iv) −x, y, −z+3/2; (v) x+1/2, −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···O6vi | 0.79 (3) | 1.93 (4) | 2.712 (3) | 170 (4) |
O1W—H1B···O4vii | 0.75 (3) | 2.02 (3) | 2.766 (3) | 172 (3) |
Symmetry codes: (vi) −x+1/2, −y+1/2, −z+2; (vii) −x+1, y, −z+3/2. |
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In recent years, studies of the synthesis of metal–organic frameworks from transition metals and organic ligands have been extensively developed for their crystallographic diversity and potential applications in catalysis, non-linear optics, magnetism and molecular recognition (Eddaoudi et al., 2001; Evans & Lin, 2002; Zaworotko, 2001). Ligands with pyridyl or carboxylate groups are the most often employed to design and synthesize novel metal–organic frameworks. For instance, 1,3,5-benzenetricarboxylic acid (H3btc) and 4,4'-bipyridine (4,4'-bipy) have been widely applied to the construction of frameworks (Livage et al., 2001; Chui et al., 1999; Yaghi et al., 1997). Recent efforts in this field have largely focused on the combination of pyridyl and carboxylate ligands (Karanovic et al., 2002; Suresh et al., 2001). Lee et al. reported a one-dimensional metal–organic framework with a formula of Cu(H2btc)2(4,4'-bipy) synthesized by a hydrothermal reaction, which is the only example of mixed ligands of H3btc and 4,4'-bipy (Huh et al., 2002). We report here the solvothermal synthesis and crystal structure of a three-dimentional zinc(II)-based metal–organic framework solid, [Zn3(H2O)2(btc)2(4,4'-bipy)]n, (I).
The asymmetric unit and the labeling scheme are shown in Fig. 1. There are two different coordination environments for the Zn atoms, namely Zn1 and Zn2, both having tetrahedral geometry. Atom Zn1 is coordinated to two carboxylate O atoms of two btc ligands, one N atom of a 4,4'-bipy ligand and one coordinated water O atom. In the environment of atom Zn2 (which lies on a twofold axis), four O atoms from four different carboxylate groups occupy the coordinated positions. Three btc carboxylate groups have two different coordination modes, viz. as a monodentate ligand with atoms Zn1 or Zn2, and as a bidentate ligand with atoms Zn1 and Zn2. In the structure of (I), two Zn1 and one Zn2 centers linked by six carboxylate groups from six separate btc ligands produce a trinuclear Zn3(O2C–)6 secondary building unit, which forms an `S' helical configuration. The 4,4'-bipy ligand lies about an inversion centre and these ligands link the `S' units into one-dimensional zigzag chains, which lie on the (204) Miller planes, as shown in Fig. 2. Each btc ligand links three zigzag chains through its three carboxyl groups, thus yielding a three-dimensional framework (Fig. 3).