In the title compound, [Mn
2(C
8H
4O
7S)
2(C
10H
8N
2)
2(H
2O)
2], pairs of hexacoordinated manganese(II) centres are bridged by 2-sulfonatoterephthalate(2−) anions to form cyclic centrosymmetric dimers, which are linked into sheets by O—H
O hydrogen bonds.
Supporting information
CCDC reference: 665485
A mixture of STP (0.025 g, 0.1 mmol), MnCl2(0.013 g, 0.1 mmol), 2,2'-bipyridine (0.016 g, 0.1 mmol) and water (7 ml) was stirred for about 30 min. The pH of the resulting solution was adjusted to 7.0 using aqueous sodium hydroxide solution (0.1 mol dm−3), and then sealed in a Teflon-lined stainless steel autoclave and heated to 393 K for 3 d. The autoclave was then allowed to cool to ambient temperature. Compound (I) was obtained as yellow block crystals, recovered by vacuum filtration and dried in air (yield ca 82%).
The C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding, with Uiso(H) values of 1.2Ueq(C). The O-bound H atoms were located in difference maps and refined as riding in their as-found relative positions with Uiso(H) set at 1.2Ueq(Oaqua) or 1.5Ueq(OOH), giving O—H distances of 0.82–0.83 Å.
Data collection: CrysAlis CCD (Oxford Diffraction, 2000); cell refinement: CrysAlis RED (Oxford Diffraction, 2000); data reduction: CrysAlis RED (Oxford Diffraction, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Bis(µ-4-carboxy-2-sulfonatobenzoato)bis[aqua(2,2'-bipyridyl)manganese(II)]
top
Crystal data top
[Mn2(C8H4O7S)2(C10H8N2)2(H2O)2] | Z = 1 |
Mr = 946.62 | F(000) = 482 |
Triclinic, P1 | Dx = 1.754 Mg m−3 |
Hall symbol: -P1 | Cu Kα radiation, λ = 1.54178 Å |
a = 7.317 (7) Å | Cell parameters from 7219 reflections |
b = 9.604 (3) Å | θ = 12–18° |
c = 12.799 (5) Å | µ = 7.58 mm−1 |
α = 88.47 (3)° | T = 293 K |
β = 86.06 (5)° | Block, yellow |
γ = 87.74 (5)° | 0.30 × 0.25 × 0.20 mm |
V = 896.4 (10) Å3 | |
Data collection top
Manufacturer? Model? 4-circle diffractometer | 3189 independent reflections |
Radiation source: Enhance (Cu) X-ray Source | 2685 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
scintillation counter scans | θmax = 67.5°, θmin = 3.5° |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2000) | h = −7→8 |
Tmin = 0.163, Tmax = 0.220 | k = −11→11 |
7219 measured reflections | l = −13→15 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0662P)2 + 0.0716P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
3189 reflections | Δρmax = 0.40 e Å−3 |
273 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0096 (8) |
Crystal data top
[Mn2(C8H4O7S)2(C10H8N2)2(H2O)2] | γ = 87.74 (5)° |
Mr = 946.62 | V = 896.4 (10) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.317 (7) Å | Cu Kα radiation |
b = 9.604 (3) Å | µ = 7.58 mm−1 |
c = 12.799 (5) Å | T = 293 K |
α = 88.47 (3)° | 0.30 × 0.25 × 0.20 mm |
β = 86.06 (5)° | |
Data collection top
Manufacturer? Model? 4-circle diffractometer | 3189 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2000) | 2685 reflections with I > 2σ(I) |
Tmin = 0.163, Tmax = 0.220 | Rint = 0.040 |
7219 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.40 e Å−3 |
3189 reflections | Δρmin = −0.36 e Å−3 |
273 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 | |
Mn1 | 0.35301 (6) | 0.37188 (4) | 0.73148 (3) | 0.02815 (17) | |
S1 | 0.73354 (9) | 0.18304 (6) | 0.75083 (4) | 0.02792 (19) | |
O1 | 0.5524 (3) | 0.43997 (19) | 0.61665 (14) | 0.0357 (4) | |
O2 | 0.7981 (3) | 0.47575 (19) | 0.51285 (15) | 0.0349 (4) | |
O3 | 0.7646 (4) | −0.2693 (2) | 0.54026 (16) | 0.0465 (6) | |
H3A | 0.7647 | −0.3499 | 0.5206 | 0.070* | |
O4 | 0.7466 (3) | −0.2198 (2) | 0.37026 (15) | 0.0402 (5) | |
O5 | 0.5427 (3) | 0.2084 (2) | 0.78411 (15) | 0.0382 (5) | |
O6 | 0.8338 (3) | 0.3073 (2) | 0.75568 (15) | 0.0416 (5) | |
O7 | 0.8095 (3) | 0.0634 (2) | 0.80357 (15) | 0.0423 (5) | |
O8 | 0.0978 (3) | 0.4927 (2) | 0.69620 (15) | 0.0377 (5) | |
H81 | 0.0150 | 0.4407 | 0.7164 | 0.045* | |
H82 | 0.1059 | 0.5185 | 0.6339 | 0.045* | |
N1 | 0.4045 (3) | 0.5604 (2) | 0.82531 (17) | 0.0325 (5) | |
N2 | 0.2270 (3) | 0.3340 (3) | 0.89299 (17) | 0.0330 (5) | |
C1 | 0.4819 (4) | 0.6756 (3) | 0.7863 (2) | 0.0397 (7) | |
H1 | 0.5402 | 0.6737 | 0.7194 | 0.048* | |
C2 | 0.4790 (5) | 0.7972 (3) | 0.8409 (3) | 0.0478 (8) | |
H2 | 0.5317 | 0.8765 | 0.8107 | 0.057* | |
C3 | 0.3981 (5) | 0.7996 (4) | 0.9397 (3) | 0.0503 (8) | |
H3 | 0.3948 | 0.8808 | 0.9779 | 0.060* | |
C4 | 0.3210 (5) | 0.6810 (3) | 0.9827 (2) | 0.0432 (7) | |
H4 | 0.2678 | 0.6800 | 1.0508 | 0.052* | |
C5 | 0.3244 (4) | 0.5631 (3) | 0.9226 (2) | 0.0321 (6) | |
C6 | 0.2394 (4) | 0.4340 (3) | 0.9632 (2) | 0.0319 (6) | |
C7 | 0.1778 (4) | 0.4143 (4) | 1.0670 (2) | 0.0416 (7) | |
H7 | 0.1825 | 0.4859 | 1.1142 | 0.050* | |
C8 | 0.1101 (5) | 0.2889 (4) | 1.0995 (2) | 0.0496 (8) | |
H8 | 0.0700 | 0.2736 | 1.1693 | 0.059* | |
C9 | 0.1017 (5) | 0.1861 (4) | 1.0285 (3) | 0.0486 (8) | |
H9 | 0.0581 | 0.0994 | 1.0494 | 0.058* | |
C10 | 0.1590 (4) | 0.2131 (3) | 0.9256 (2) | 0.0412 (7) | |
H10 | 0.1497 | 0.1439 | 0.8769 | 0.049* | |
C11 | 0.7180 (4) | 0.2445 (3) | 0.53918 (19) | 0.0274 (5) | |
C12 | 0.7361 (4) | 0.1419 (3) | 0.61668 (19) | 0.0268 (5) | |
C13 | 0.7541 (4) | 0.0030 (3) | 0.5913 (2) | 0.0287 (5) | |
H13 | 0.7683 | −0.0648 | 0.6437 | 0.034* | |
C14 | 0.7511 (4) | −0.0356 (3) | 0.4876 (2) | 0.0285 (6) | |
C15 | 0.7398 (4) | 0.0655 (3) | 0.4099 (2) | 0.0348 (6) | |
H15 | 0.7408 | 0.0402 | 0.3402 | 0.042* | |
C16 | 0.7269 (4) | 0.2043 (3) | 0.4354 (2) | 0.0352 (6) | |
H16 | 0.7241 | 0.2721 | 0.3823 | 0.042* | |
C17 | 0.6853 (4) | 0.3976 (3) | 0.55979 (18) | 0.0278 (6) | |
C18 | 0.7551 (4) | −0.1853 (3) | 0.4612 (2) | 0.0315 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn1 | 0.0375 (3) | 0.0253 (3) | 0.0218 (2) | −0.00349 (18) | 0.00001 (17) | −0.00709 (16) |
S1 | 0.0393 (4) | 0.0244 (3) | 0.0205 (3) | −0.0019 (3) | −0.0035 (2) | −0.0032 (2) |
O1 | 0.0459 (12) | 0.0264 (10) | 0.0332 (10) | −0.0006 (8) | 0.0090 (9) | −0.0020 (8) |
O2 | 0.0464 (11) | 0.0213 (9) | 0.0361 (10) | −0.0045 (8) | 0.0067 (8) | −0.0038 (7) |
O3 | 0.0838 (17) | 0.0183 (10) | 0.0377 (10) | −0.0018 (10) | −0.0047 (11) | −0.0049 (8) |
O4 | 0.0588 (13) | 0.0289 (10) | 0.0341 (10) | −0.0053 (9) | −0.0057 (9) | −0.0128 (8) |
O5 | 0.0443 (12) | 0.0408 (12) | 0.0285 (9) | −0.0005 (9) | 0.0027 (8) | −0.0002 (8) |
O6 | 0.0567 (13) | 0.0380 (12) | 0.0316 (10) | −0.0143 (10) | −0.0025 (9) | −0.0123 (8) |
O7 | 0.0606 (13) | 0.0380 (12) | 0.0289 (10) | 0.0046 (10) | −0.0113 (9) | 0.0013 (8) |
O8 | 0.0436 (11) | 0.0368 (11) | 0.0327 (9) | −0.0035 (9) | −0.0007 (8) | −0.0031 (8) |
N1 | 0.0381 (12) | 0.0326 (12) | 0.0275 (11) | −0.0030 (10) | −0.0050 (9) | −0.0064 (9) |
N2 | 0.0371 (12) | 0.0353 (13) | 0.0269 (10) | −0.0013 (10) | −0.0016 (9) | −0.0057 (9) |
C1 | 0.0446 (17) | 0.0385 (16) | 0.0369 (14) | −0.0056 (13) | −0.0067 (13) | −0.0048 (12) |
C2 | 0.057 (2) | 0.0337 (17) | 0.0546 (19) | −0.0087 (15) | −0.0125 (16) | −0.0049 (14) |
C3 | 0.060 (2) | 0.0381 (18) | 0.0547 (19) | 0.0009 (15) | −0.0132 (16) | −0.0208 (15) |
C4 | 0.0492 (18) | 0.0450 (18) | 0.0364 (15) | 0.0020 (14) | −0.0053 (13) | −0.0162 (13) |
C5 | 0.0338 (14) | 0.0358 (15) | 0.0275 (13) | 0.0044 (12) | −0.0076 (11) | −0.0108 (11) |
C6 | 0.0313 (13) | 0.0375 (15) | 0.0270 (12) | 0.0057 (11) | −0.0055 (10) | −0.0063 (11) |
C7 | 0.0444 (17) | 0.0526 (19) | 0.0276 (13) | 0.0026 (14) | −0.0028 (12) | −0.0063 (12) |
C8 | 0.0492 (18) | 0.068 (2) | 0.0312 (14) | −0.0022 (16) | −0.0010 (13) | 0.0045 (15) |
C9 | 0.0478 (18) | 0.053 (2) | 0.0451 (17) | −0.0092 (15) | −0.0024 (14) | 0.0127 (15) |
C10 | 0.0463 (17) | 0.0391 (17) | 0.0386 (15) | −0.0062 (14) | −0.0041 (13) | −0.0022 (12) |
C11 | 0.0355 (14) | 0.0205 (13) | 0.0263 (12) | −0.0029 (10) | −0.0002 (10) | −0.0035 (9) |
C12 | 0.0333 (13) | 0.0230 (12) | 0.0244 (12) | −0.0037 (10) | −0.0008 (10) | −0.0042 (9) |
C13 | 0.0387 (14) | 0.0218 (12) | 0.0259 (12) | −0.0020 (11) | −0.0027 (10) | −0.0018 (9) |
C14 | 0.0367 (14) | 0.0219 (13) | 0.0275 (12) | −0.0030 (11) | −0.0035 (10) | −0.0066 (10) |
C15 | 0.0517 (17) | 0.0300 (14) | 0.0235 (12) | −0.0024 (12) | −0.0045 (11) | −0.0071 (10) |
C16 | 0.0561 (18) | 0.0238 (13) | 0.0258 (12) | −0.0017 (12) | −0.0042 (12) | −0.0003 (10) |
C17 | 0.0418 (15) | 0.0216 (13) | 0.0202 (11) | −0.0026 (11) | −0.0026 (10) | −0.0010 (9) |
C18 | 0.0379 (15) | 0.0240 (13) | 0.0331 (14) | −0.0035 (11) | −0.0016 (11) | −0.0084 (11) |
Geometric parameters (Å, º) top
Mn1—O1 | 2.108 (2) | C2—H2 | 0.9300 |
Mn1—O4i | 2.163 (2) | C3—C4 | 1.376 (5) |
Mn1—O5 | 2.179 (3) | C3—H3 | 0.9300 |
Mn1—O8 | 2.226 (3) | C4—C5 | 1.384 (4) |
Mn1—N2 | 2.232 (3) | C4—H4 | 0.9300 |
Mn1—N1 | 2.257 (2) | C5—C6 | 1.475 (4) |
S1—O7 | 1.430 (2) | C6—C7 | 1.385 (4) |
S1—O6 | 1.430 (2) | C7—C8 | 1.364 (5) |
S1—O5 | 1.445 (3) | C7—H7 | 0.9300 |
S1—C12 | 1.771 (3) | C8—C9 | 1.365 (5) |
O1—C17 | 1.237 (4) | C8—H8 | 0.9300 |
O2—C17 | 1.250 (3) | C9—C10 | 1.376 (5) |
O3—C18 | 1.281 (3) | C9—H9 | 0.9300 |
O3—H3A | 0.8200 | C10—H10 | 0.9300 |
O4—C18 | 1.225 (3) | C11—C12 | 1.389 (4) |
O4—Mn1i | 2.163 (2) | C11—C16 | 1.390 (4) |
O8—H81 | 0.8239 | C11—C17 | 1.507 (4) |
O8—H82 | 0.8280 | C12—C13 | 1.380 (4) |
N1—C1 | 1.332 (4) | C13—C14 | 1.390 (4) |
N1—C5 | 1.340 (4) | C13—H13 | 0.9300 |
N2—C10 | 1.327 (4) | C14—C15 | 1.376 (4) |
N2—C6 | 1.342 (4) | C14—C18 | 1.484 (4) |
C1—C2 | 1.376 (5) | C15—C16 | 1.379 (4) |
C1—H1 | 0.9300 | C15—H15 | 0.9300 |
C2—C3 | 1.359 (5) | C16—H16 | 0.9300 |
| | | |
O1—Mn1—O4i | 92.90 (9) | C3—C4—H4 | 120.7 |
O1—Mn1—O5 | 90.57 (9) | C5—C4—H4 | 120.7 |
O4i—Mn1—O5 | 87.09 (9) | N1—C5—C4 | 121.9 (3) |
O1—Mn1—O8 | 104.73 (9) | N1—C5—C6 | 116.8 (2) |
O4i—Mn1—O8 | 84.08 (9) | C4—C5—C6 | 121.3 (3) |
O5—Mn1—O8 | 162.66 (8) | N2—C6—C7 | 121.2 (3) |
O1—Mn1—N2 | 156.51 (8) | N2—C6—C5 | 115.8 (2) |
O4i—Mn1—N2 | 108.28 (9) | C7—C6—C5 | 123.0 (3) |
O5—Mn1—N2 | 80.75 (10) | C8—C7—C6 | 119.4 (3) |
O8—Mn1—N2 | 87.89 (10) | C8—C7—H7 | 120.3 |
O1—Mn1—N1 | 88.62 (9) | C6—C7—H7 | 120.3 |
O4i—Mn1—N1 | 167.23 (9) | C7—C8—C9 | 119.3 (3) |
O5—Mn1—N1 | 105.59 (9) | C7—C8—H8 | 120.4 |
O8—Mn1—N1 | 83.27 (9) | C9—C8—H8 | 120.4 |
N2—Mn1—N1 | 73.02 (9) | C8—C9—C10 | 118.9 (3) |
O7—S1—O6 | 115.26 (14) | C8—C9—H9 | 120.6 |
O7—S1—O5 | 111.48 (14) | C10—C9—H9 | 120.6 |
O6—S1—O5 | 110.89 (14) | N2—C10—C9 | 122.5 (3) |
O7—S1—C12 | 106.60 (13) | N2—C10—H10 | 118.7 |
O6—S1—C12 | 106.44 (12) | C9—C10—H10 | 118.7 |
O5—S1—C12 | 105.46 (13) | C12—C11—C16 | 118.3 (2) |
C17—O1—Mn1 | 142.07 (18) | C12—C11—C17 | 124.4 (2) |
C18—O3—H3A | 109.5 | C16—C11—C17 | 117.2 (2) |
C18—O4—Mn1i | 145.31 (19) | C13—C12—C11 | 120.7 (2) |
S1—O5—Mn1 | 128.78 (12) | C13—C12—S1 | 117.59 (19) |
Mn1—O8—H81 | 104.0 | C11—C12—S1 | 121.7 (2) |
Mn1—O8—H82 | 108.8 | C12—C13—C14 | 120.1 (2) |
H81—O8—H82 | 118.6 | C12—C13—H13 | 120.0 |
C1—N1—C5 | 118.3 (3) | C14—C13—H13 | 120.0 |
C1—N1—Mn1 | 124.84 (19) | C15—C14—C13 | 119.7 (2) |
C5—N1—Mn1 | 115.97 (19) | C15—C14—C18 | 120.2 (2) |
C10—N2—C6 | 118.7 (3) | C13—C14—C18 | 120.1 (2) |
C10—N2—Mn1 | 123.3 (2) | C14—C15—C16 | 119.9 (2) |
C6—N2—Mn1 | 117.60 (19) | C14—C15—H15 | 120.0 |
N1—C1—C2 | 122.7 (3) | C16—C15—H15 | 120.0 |
N1—C1—H1 | 118.7 | C15—C16—C11 | 121.1 (2) |
C2—C1—H1 | 118.7 | C15—C16—H16 | 119.4 |
C3—C2—C1 | 118.9 (3) | C11—C16—H16 | 119.4 |
C3—C2—H2 | 120.5 | O1—C17—O2 | 123.8 (3) |
C1—C2—H2 | 120.5 | O1—C17—C11 | 121.2 (2) |
C2—C3—C4 | 119.5 (3) | O2—C17—C11 | 115.0 (2) |
C2—C3—H3 | 120.3 | O4—C18—O3 | 125.4 (3) |
C4—C3—H3 | 120.3 | O4—C18—C14 | 120.3 (2) |
C3—C4—C5 | 118.7 (3) | O3—C18—C14 | 114.4 (2) |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O2ii | 0.82 | 1.69 | 2.483 (4) | 163 |
O8—H81···O6iii | 0.82 | 1.91 | 2.735 (4) | 175 |
O8—H82···O2iv | 0.83 | 1.96 | 2.743 (4) | 158 |
Symmetry codes: (ii) x, y−1, z; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | [Mn2(C8H4O7S)2(C10H8N2)2(H2O)2] |
Mr | 946.62 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.317 (7), 9.604 (3), 12.799 (5) |
α, β, γ (°) | 88.47 (3), 86.06 (5), 87.74 (5) |
V (Å3) | 896.4 (10) |
Z | 1 |
Radiation type | Cu Kα |
µ (mm−1) | 7.58 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Manufacturer? Model? 4-circle diffractometer |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2000) |
Tmin, Tmax | 0.163, 0.220 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7219, 3189, 2685 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.599 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.105, 1.09 |
No. of reflections | 3189 |
No. of parameters | 273 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.36 |
Selected geometric parameters (Å, º) topMn1—O1 | 2.108 (2) | Mn1—N1 | 2.257 (2) |
Mn1—O4i | 2.163 (2) | O1—C17 | 1.237 (4) |
Mn1—O5 | 2.179 (3) | O2—C17 | 1.250 (3) |
Mn1—O8 | 2.226 (3) | O3—C18 | 1.281 (3) |
Mn1—N2 | 2.232 (3) | O4—C18 | 1.225 (3) |
| | | |
O1—Mn1—O4i | 92.90 (9) | O5—Mn1—N2 | 80.75 (10) |
O1—Mn1—O5 | 90.57 (9) | O8—Mn1—N2 | 87.89 (10) |
O4i—Mn1—O5 | 87.09 (9) | O1—Mn1—N1 | 88.62 (9) |
O1—Mn1—O8 | 104.73 (9) | O4i—Mn1—N1 | 167.23 (9) |
O4i—Mn1—O8 | 84.08 (9) | O5—Mn1—N1 | 105.59 (9) |
O5—Mn1—O8 | 162.66 (8) | O8—Mn1—N1 | 83.27 (9) |
O1—Mn1—N2 | 156.51 (8) | N2—Mn1—N1 | 73.02 (9) |
O4i—Mn1—N2 | 108.28 (9) | | |
Symmetry code: (i) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3A···O2ii | 0.82 | 1.69 | 2.483 (4) | 163 |
O8—H81···O6iii | 0.82 | 1.91 | 2.735 (4) | 175 |
O8—H82···O2iv | 0.83 | 1.96 | 2.743 (4) | 158 |
Symmetry codes: (ii) x, y−1, z; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+1. |
The rational design and synthesis of metal-organic frameworks have recently received extensive attention owing to their potential applications in catalysis, chemical separation and gas storage (Chae et al., 2004; Eddaoudi et al., 2002; Rosi et al.,2003; Rowsell et al., 2004; Seo et al., 2000; Jesse & Yaghi, 2005). Multidentate O/N-donor ligands containing rigid frameworks, such as polycarboxylates, polybipyridines or their derivatives, and mixed polycarboxylate and polybipyridine ligands, have been employed to construct metal coordination frameworks (Rosi et al., 2005; Zhang et al., 2003; Wen et al., 2007; Sun et al., 2001, 2003). Among such ligands, rod-like multidentate bridging ligands, such as terephthalate (tp), are known to form one-, two- and three-dimensional coordination networks.
The coordination chemistry of the deprotonated forms of H2tp with up to four potential O-atom donors, which can adopt different coordination modes in different chemical environments, has been widely investigated. Terephthalate anions can act as bridging ligands, forming short bridges by use of just one carboxylate unit or long bridges by use of both carboxylate groups. 2-Sulfoterephthalic acid (STP) has been little explored (Horike, Matsuda, Tanaka, Matsubara et al., 2006; Horike, Matsuda, Tanaka, Mizuno et al., 2006). However, the sulfonate group shows interesting functional properties owing to flexible coordination modes caused by weak interactions between metal centres and the sulfonate group (Cote & Shimizu, 2003). By introduction of a soft sulfonate group into rigid multicarboxylate ligands, coordination complexes with diverse structural frameworks can be expected. We report here the synthesis and crystal structure of the title compound, (I), which exemplifies this type of coordination.
The asymmetric unit of (I) consists of one MnII ion, one 2,2'-bipyridine molecule, one HSTP2− anion and one water molecule (Fig. 1). The six-coordinate metal centre is located on a general position, and the [N2O4] chromophore about the Mn centre involves the two pyridine N atoms from a 2,2'-bipyridine molecule and two cis carboxylate O atoms from two symmetry-related STP ligands at the equatorial sites; the axial positions are occupied by a water molecule and a sulfonate O atom. The Mn—N distances (Table 1) are in agreement with values observed previously (Ma et al., 2004). The Mn—O distances are similar to those documented elsewhere (Chen et al., 2003). The C—O distances are consistent with the location of the H atoms deduced from difference maps, which indicate that the STP ligand carries a charge of −2, so satisfying the charge-balance requirement. The angles subtended at Mn by cis pairs of ligating atoms cover the range 80.75 (10)–108.28 (9)°, and angles of subtended by the trans pairs are in the range 156.51 (8) to 167.23 (9)°, indicating that the Mn(N2O4) unit is distorted from regular octahedral geometry.
The two symmetry-related STP ligands in (I) act as bridging ligands, forming long bridges that link metal centres to generate a dimeric unit containing a 16-membered ring. Although some examples of H-shaped dimeric units or pseudo-honeycomb coordination nets constructed by the tp or 5-sulfoisophthalate ligands have been reported (Cano et al., 1997; Chen et al., 2003; Kulynych & Shimizu, 2002), the pattern found here for (I) has not been reported previously. The sulfonate groups of 2-sulfoterephthalate adopt a µ1 mode coordinated to metal centers, similar to that of the Cu derivative (Kulynych & Shimizu, 2002) but different from that of the Cd derivative (Horike, Matsuda, Tanaka, Matsubara et al., 2006; Horike, Matsuda, Tanaka, Mizuno et al., 2006). The sulfonate O atom and cis carboxylate O atom coordinated to the metal center form a seven-membered chelate ring. The carboxylate group acts as a bismonodentate ligand toward two metal centres. The whole STP ligand adopts a µ2 mode bridging two metal centers. The dihedral angle between the mean plane of the benzene ring and the plane of the carboxylate group is 57.0°, while the protonated carboxylate group and the aromatic ring are coplanar. The rings of the 2,2'-bipyridine ligand are also twisted by 10.55°. Three types of hydrogen bonds are observed (Table 2), and these link the dimers into sheets parallel to (001) (Fig. 2).