Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104007565/fa1056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104007565/fa1056Isup2.hkl |
CCDC reference: 226382
A mixture of Mn(NO3)2·6H2O (1 mmol, 0.28 g), dipotassium terephthalate (1 mmol, 0.24 g) and 2,2'-bipyridine (1 mmol, 0.16 g) in mixed methanol–water solvent (1:2, v/v, 15 ml) was heated at 413 K for 4 d under autogenous pressure in a 25 ml sealed Teflon-lined stainless steel vessel, and then cooled to room temperature over a period of 5 h, yielding yellow crystals of (I). Analysis calculated for C18H14MnN2O5: C 54.98, H 3.59, N 7.12%; found: C 54.92, H 3.61, N 7.08%. FT–IR (KBr, N, cm−1): 3205 (br, s), 1605 (s), 1577 (versus), 1531 (m), 1505 (m), 1475 (m), 1439 (s), 1379 (versus), 1313 (m), 1247 (w), 1151 (m), 1089 (w), 1050 (m), 1019 (m), 882 (w), 864 (w), 806 (m), 760 (s), 750 (s), 670 (m), 650 (m), 628 (m), 569 (w), 525 (m), 413 (m).
The water H atoms were located from difference maps and included in the refinement with a DFIX restraint of 0.85 (2) Å applied to the two O—H distances. Aromatic H atoms were placed in calculated positions and treated as riding atoms (C–H = 0.93 Å).
Data collection: SMART (Siemens,1996); cell refinement: SAINT (Siemens,1994); data reduction: SHELXTL (Siemens,1994) and SAINT; program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Mn(C8H4O4)(C10H8N2)(H2O)] | F(000) = 804 |
Mr = 393.25 | Dx = 1.543 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2431 reflections |
a = 9.8637 (2) Å | θ = 2.3–25.0° |
b = 16.3316 (5) Å | µ = 0.81 mm−1 |
c = 11.3110 (1) Å | T = 293 K |
β = 111.726 (2)° | Block, pale yellow |
V = 1692.66 (6) Å3 | 0.54 × 0.53 × 0.30 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 2973 independent reflections |
Radiation source: fine-focus sealed tube | 2230 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | h = −9→11 |
Tmin = 0.626, Tmax = 0.784 | k = −12→19 |
5399 measured reflections | l = −13→9 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
2973 reflections | (Δ/σ)max < 0.001 |
243 parameters | Δρmax = 0.40 e Å−3 |
2 restraints | Δρmin = −0.30 e Å−3 |
[Mn(C8H4O4)(C10H8N2)(H2O)] | V = 1692.66 (6) Å3 |
Mr = 393.25 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8637 (2) Å | µ = 0.81 mm−1 |
b = 16.3316 (5) Å | T = 293 K |
c = 11.3110 (1) Å | 0.54 × 0.53 × 0.30 mm |
β = 111.726 (2)° |
Siemens SMART CCD area-detector diffractometer | 2973 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 1996) | 2230 reflections with I > 2σ(I) |
Tmin = 0.626, Tmax = 0.784 | Rint = 0.026 |
5399 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 2 restraints |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.40 e Å−3 |
2973 reflections | Δρmin = −0.30 e Å−3 |
243 parameters |
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 | ||
Mn | 0.29665 (5) | 0.04021 (3) | 0.12849 (5) | 0.0325 (2) | |
O1 | 0.0809 (2) | 0.09837 (15) | 0.1140 (2) | 0.0420 (6) | |
O2 | 0.2808 (2) | 0.13618 (15) | 0.2681 (2) | 0.0390 (6) | |
O3 | −0.1197 (3) | 0.38453 (16) | 0.5214 (2) | 0.0452 (6) | |
O4 | −0.3006 (3) | 0.38864 (19) | 0.3321 (3) | 0.0605 (8) | |
O5 | 0.1858 (3) | −0.02654 (17) | −0.0456 (3) | 0.0434 (6) | |
H5B | 0.105 (3) | −0.054 (3) | −0.067 (5) | 0.085 (18)* | |
H5C | 0.172 (5) | 0.011 (2) | −0.101 (4) | 0.088 (19)* | |
N1 | 0.2832 (3) | −0.06673 (18) | 0.2505 (3) | 0.0395 (7) | |
N2 | 0.5235 (3) | 0.01268 (19) | 0.2626 (3) | 0.0391 (7) | |
C1 | 0.0596 (3) | 0.1985 (2) | 0.2614 (3) | 0.0304 (7) | |
C2 | 0.1288 (4) | 0.2408 (2) | 0.3730 (3) | 0.0453 (10) | |
H2A | 0.2284 | 0.2338 | 0.4172 | 0.054* | |
C3 | 0.0514 (4) | 0.2933 (2) | 0.4196 (3) | 0.0471 (10) | |
H3A | 0.0993 | 0.3209 | 0.4956 | 0.057* | |
C4 | −0.0965 (3) | 0.3057 (2) | 0.3552 (3) | 0.0330 (8) | |
C5 | −0.1640 (4) | 0.2656 (2) | 0.2410 (3) | 0.0395 (9) | |
H5A | −0.2623 | 0.2752 | 0.1943 | 0.047* | |
C6 | −0.0877 (4) | 0.2115 (2) | 0.1951 (3) | 0.0386 (8) | |
H6A | −0.1356 | 0.1836 | 0.1194 | 0.046* | |
C7 | 0.1469 (4) | 0.1414 (2) | 0.2124 (3) | 0.0324 (8) | |
C8 | −0.1799 (4) | 0.3642 (2) | 0.4064 (3) | 0.0359 (8) | |
C9 | 0.1606 (4) | −0.1075 (3) | 0.2371 (4) | 0.0530 (10) | |
H9A | 0.0757 | −0.0945 | 0.1688 | 0.064* | |
C10 | 0.1548 (5) | −0.1676 (3) | 0.3197 (5) | 0.0604 (12) | |
H10A | 0.0679 | −0.1951 | 0.3069 | 0.072* | |
C11 | 0.2787 (5) | −0.1866 (3) | 0.4209 (4) | 0.0628 (12) | |
H11A | 0.2769 | −0.2269 | 0.4783 | 0.075* | |
C12 | 0.4063 (5) | −0.1456 (2) | 0.4373 (4) | 0.0507 (10) | |
H12A | 0.4914 | −0.1576 | 0.5060 | 0.061* | |
C13 | 0.4058 (4) | −0.0861 (2) | 0.3494 (3) | 0.0378 (8) | |
C14 | 0.5393 (4) | −0.0403 (2) | 0.3574 (3) | 0.0377 (8) | |
C15 | 0.6717 (4) | −0.0510 (2) | 0.4556 (4) | 0.0473 (10) | |
H15A | 0.6807 | −0.0880 | 0.5206 | 0.057* | |
C16 | 0.7904 (5) | −0.0066 (3) | 0.4568 (4) | 0.0601 (12) | |
H16A | 0.8802 | −0.0129 | 0.5230 | 0.072* | |
C17 | 0.7753 (5) | 0.0475 (3) | 0.3589 (4) | 0.0597 (12) | |
H17A | 0.8544 | 0.0779 | 0.3572 | 0.072* | |
C18 | 0.6407 (4) | 0.0552 (3) | 0.2645 (4) | 0.0507 (11) | |
H18A | 0.6298 | 0.0917 | 0.1985 | 0.061* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn | 0.0343 (3) | 0.0301 (3) | 0.0347 (3) | 0.0015 (2) | 0.0148 (2) | 0.0019 (2) |
O1 | 0.0390 (13) | 0.0423 (15) | 0.0456 (15) | −0.0017 (11) | 0.0168 (12) | −0.0144 (12) |
O2 | 0.0342 (14) | 0.0414 (15) | 0.0397 (14) | 0.0070 (11) | 0.0117 (11) | −0.0030 (11) |
O3 | 0.0473 (15) | 0.0525 (16) | 0.0358 (14) | 0.0105 (13) | 0.0154 (12) | −0.0077 (12) |
O4 | 0.0434 (16) | 0.074 (2) | 0.0537 (17) | 0.0192 (14) | 0.0052 (13) | −0.0207 (15) |
O5 | 0.0475 (17) | 0.0363 (15) | 0.0471 (16) | −0.0104 (13) | 0.0182 (13) | −0.0071 (12) |
N1 | 0.0415 (18) | 0.0333 (16) | 0.0464 (18) | 0.0014 (14) | 0.0194 (15) | 0.0035 (13) |
N2 | 0.0383 (17) | 0.0412 (18) | 0.0414 (17) | 0.0052 (14) | 0.0189 (14) | 0.0070 (14) |
C1 | 0.0339 (18) | 0.0280 (18) | 0.0312 (18) | 0.0021 (14) | 0.0144 (14) | 0.0022 (14) |
C2 | 0.034 (2) | 0.054 (2) | 0.042 (2) | 0.0106 (18) | 0.0059 (17) | −0.0085 (18) |
C3 | 0.041 (2) | 0.054 (2) | 0.036 (2) | 0.0084 (19) | 0.0035 (17) | −0.0135 (18) |
C4 | 0.0343 (19) | 0.0334 (19) | 0.0341 (19) | 0.0002 (15) | 0.0157 (15) | −0.0022 (15) |
C5 | 0.0290 (18) | 0.040 (2) | 0.045 (2) | 0.0018 (15) | 0.0086 (16) | −0.0076 (16) |
C6 | 0.0353 (19) | 0.041 (2) | 0.038 (2) | −0.0033 (16) | 0.0123 (16) | −0.0139 (16) |
C7 | 0.039 (2) | 0.0279 (18) | 0.0331 (18) | 0.0010 (15) | 0.0162 (16) | 0.0035 (14) |
C8 | 0.0316 (19) | 0.0344 (19) | 0.043 (2) | 0.0017 (15) | 0.0150 (16) | −0.0057 (16) |
C9 | 0.046 (2) | 0.046 (2) | 0.067 (3) | −0.0056 (19) | 0.021 (2) | 0.004 (2) |
C10 | 0.060 (3) | 0.046 (3) | 0.084 (3) | −0.011 (2) | 0.037 (3) | 0.008 (2) |
C11 | 0.085 (3) | 0.039 (2) | 0.078 (3) | −0.002 (2) | 0.046 (3) | 0.013 (2) |
C12 | 0.060 (2) | 0.040 (2) | 0.058 (3) | 0.007 (2) | 0.028 (2) | 0.0095 (19) |
C13 | 0.045 (2) | 0.032 (2) | 0.040 (2) | 0.0065 (16) | 0.0212 (18) | 0.0006 (16) |
C14 | 0.049 (2) | 0.0309 (19) | 0.0371 (19) | 0.0106 (16) | 0.0207 (17) | 0.0033 (15) |
C15 | 0.047 (2) | 0.051 (2) | 0.041 (2) | 0.0074 (19) | 0.0129 (19) | 0.0110 (17) |
C16 | 0.038 (2) | 0.081 (3) | 0.055 (3) | 0.009 (2) | 0.0095 (19) | 0.009 (2) |
C17 | 0.037 (2) | 0.078 (3) | 0.062 (3) | −0.004 (2) | 0.015 (2) | 0.007 (2) |
C18 | 0.040 (2) | 0.062 (3) | 0.053 (2) | 0.0032 (19) | 0.021 (2) | 0.018 (2) |
Mn—O3i | 2.098 (2) | C3—H3A | 0.9300 |
Mn—O5 | 2.160 (3) | C4—C5 | 1.379 (5) |
Mn—N2 | 2.235 (3) | C4—C8 | 1.509 (4) |
Mn—N1 | 2.260 (3) | C5—C6 | 1.380 (5) |
Mn—O2 | 2.271 (2) | C5—H5A | 0.9300 |
Mn—O1 | 2.281 (2) | C6—H6A | 0.9300 |
Mn—C7 | 2.617 (3) | C9—C10 | 1.371 (6) |
O1—C7 | 1.272 (4) | C9—H9A | 0.9300 |
O2—C7 | 1.238 (4) | C10—C11 | 1.365 (6) |
O3—C8 | 1.259 (4) | C10—H10A | 0.9300 |
O3—Mnii | 2.098 (2) | C11—C12 | 1.375 (6) |
O4—C8 | 1.241 (4) | C11—H11A | 0.9300 |
O5—H5B | 0.861 (19) | C12—C13 | 1.389 (5) |
O5—H5C | 0.847 (19) | C12—H12A | 0.9300 |
N1—C9 | 1.340 (5) | C13—C14 | 1.487 (5) |
N1—C13 | 1.346 (5) | C14—C15 | 1.377 (5) |
N2—C18 | 1.341 (5) | C15—C16 | 1.373 (6) |
N2—C14 | 1.341 (4) | C15—H15A | 0.9300 |
C1—C2 | 1.378 (5) | C16—C17 | 1.381 (6) |
C1—C6 | 1.382 (4) | C16—H16A | 0.9300 |
C1—C7 | 1.508 (4) | C17—C18 | 1.367 (6) |
C2—C3 | 1.376 (5) | C17—H17A | 0.9300 |
C2—H2A | 0.9300 | C18—H18A | 0.9300 |
C3—C4 | 1.383 (5) | ||
O3i—Mn—O5 | 86.79 (10) | C4—C5—C6 | 121.0 (3) |
O3i—Mn—N2 | 90.04 (10) | C4—C5—H5A | 119.5 |
O5—Mn—N2 | 123.97 (11) | C6—C5—H5A | 119.5 |
O3i—Mn—N1 | 158.43 (11) | C5—C6—C1 | 120.3 (3) |
O5—Mn—N1 | 92.42 (11) | C5—C6—H6A | 119.9 |
N2—Mn—N1 | 72.56 (11) | C1—C6—H6A | 119.9 |
O3i—Mn—O2 | 98.05 (10) | O2—C7—O1 | 120.8 (3) |
O5—Mn—O2 | 147.16 (10) | O2—C7—C1 | 120.2 (3) |
N2—Mn—O2 | 88.63 (10) | O1—C7—C1 | 119.1 (3) |
N1—Mn—O2 | 94.26 (10) | O2—C7—Mn | 60.14 (17) |
O3i—Mn—O1 | 105.72 (9) | O1—C7—Mn | 60.62 (17) |
O5—Mn—O1 | 90.04 (10) | C1—C7—Mn | 179.0 (2) |
N2—Mn—O1 | 143.66 (10) | O4—C8—O3 | 125.6 (3) |
N1—Mn—O1 | 95.83 (10) | O4—C8—C4 | 117.8 (3) |
O2—Mn—O1 | 57.31 (8) | O3—C8—C4 | 116.6 (3) |
O3i—Mn—C7 | 103.58 (10) | N1—C9—C10 | 122.9 (4) |
O5—Mn—C7 | 119.07 (11) | N1—C9—H9A | 118.6 |
N2—Mn—C7 | 116.00 (11) | C10—C9—H9A | 118.6 |
N1—Mn—C7 | 95.64 (10) | C11—C10—C9 | 118.9 (4) |
O2—Mn—C7 | 28.22 (9) | C11—C10—H10A | 120.5 |
O1—Mn—C7 | 29.09 (9) | C9—C10—H10A | 120.5 |
C7—O1—Mn | 90.30 (19) | C10—C11—C12 | 119.5 (4) |
C7—O2—Mn | 91.6 (2) | C10—C11—H11A | 120.2 |
C8—O3—Mnii | 128.0 (2) | C12—C11—H11A | 120.2 |
Mn—O5—H5B | 128 (3) | C11—C12—C13 | 118.9 (4) |
Mn—O5—H5C | 102 (4) | C11—C12—H12A | 120.5 |
H5B—O5—H5C | 106 (5) | C13—C12—H12A | 120.5 |
C9—N1—C13 | 118.2 (3) | N1—C13—C12 | 121.5 (3) |
C9—N1—Mn | 124.7 (3) | N1—C13—C14 | 115.8 (3) |
C13—N1—Mn | 116.8 (2) | C12—C13—C14 | 122.7 (3) |
C18—N2—C14 | 118.5 (3) | N2—C14—C15 | 121.4 (4) |
C18—N2—Mn | 123.1 (2) | N2—C14—C13 | 115.9 (3) |
C14—N2—Mn | 117.6 (2) | C15—C14—C13 | 122.6 (3) |
C2—C1—C6 | 119.0 (3) | C16—C15—C14 | 119.4 (4) |
C2—C1—C7 | 119.4 (3) | C16—C15—H15A | 120.3 |
C6—C1—C7 | 121.6 (3) | C14—C15—H15A | 120.3 |
C3—C2—C1 | 120.4 (3) | C15—C16—C17 | 119.5 (4) |
C3—C2—H2A | 119.8 | C15—C16—H16A | 120.3 |
C1—C2—H2A | 119.8 | C17—C16—H16A | 120.3 |
C2—C3—C4 | 121.0 (3) | C18—C17—C16 | 118.0 (4) |
C2—C3—H3A | 119.5 | C18—C17—H17A | 121.0 |
C4—C3—H3A | 119.5 | C16—C17—H17A | 121.0 |
C5—C4—C3 | 118.3 (3) | N2—C18—C17 | 123.2 (4) |
C5—C4—C8 | 121.1 (3) | N2—C18—H18A | 118.4 |
C3—C4—C8 | 120.6 (3) | C17—C18—H18A | 118.4 |
O3i—Mn—O1—C7 | −89.8 (2) | Mn—O1—C7—C1 | −179.0 (3) |
O5—Mn—O1—C7 | −176.4 (2) | C2—C1—C7—O2 | −4.1 (5) |
N2—Mn—O1—C7 | 22.8 (3) | C6—C1—C7—O2 | 173.9 (3) |
N1—Mn—O1—C7 | 91.1 (2) | C2—C1—C7—O1 | 175.3 (3) |
O2—Mn—O1—C7 | −0.21 (18) | C6—C1—C7—O1 | −6.7 (5) |
O3i—Mn—O2—C7 | 103.8 (2) | O3i—Mn—C7—O2 | −81.6 (2) |
O5—Mn—O2—C7 | 7.2 (3) | O5—Mn—C7—O2 | −175.55 (18) |
N2—Mn—O2—C7 | −166.4 (2) | N2—Mn—C7—O2 | 15.2 (2) |
N1—Mn—O2—C7 | −94.0 (2) | N1—Mn—C7—O2 | 88.5 (2) |
O1—Mn—O2—C7 | 0.21 (18) | O1—Mn—C7—O2 | −179.6 (3) |
O3i—Mn—N1—C9 | −139.0 (3) | O3i—Mn—C7—O1 | 97.99 (19) |
O5—Mn—N1—C9 | −51.7 (3) | O5—Mn—C7—O1 | 4.1 (2) |
N2—Mn—N1—C9 | −176.6 (3) | N2—Mn—C7—O1 | −165.20 (19) |
O2—Mn—N1—C9 | 96.2 (3) | N1—Mn—C7—O1 | −91.9 (2) |
O1—Mn—N1—C9 | 38.6 (3) | O2—Mn—C7—O1 | 179.6 (3) |
C7—Mn—N1—C9 | 67.9 (3) | Mnii—O3—C8—O4 | 3.5 (5) |
O3i—Mn—N1—C13 | 46.3 (4) | Mnii—O3—C8—C4 | −177.2 (2) |
O5—Mn—N1—C13 | 133.7 (3) | C5—C4—C8—O4 | −15.1 (5) |
N2—Mn—N1—C13 | 8.8 (2) | C3—C4—C8—O4 | 162.5 (4) |
O2—Mn—N1—C13 | −78.5 (2) | C5—C4—C8—O3 | 165.5 (3) |
O1—Mn—N1—C13 | −136.0 (2) | C3—C4—C8—O3 | −16.9 (5) |
C7—Mn—N1—C13 | −106.8 (2) | C13—N1—C9—C10 | 0.2 (6) |
O3i—Mn—N2—C18 | 13.2 (3) | Mn—N1—C9—C10 | −174.4 (3) |
O5—Mn—N2—C18 | 99.4 (3) | N1—C9—C10—C11 | 0.6 (7) |
N1—Mn—N2—C18 | −179.7 (3) | C9—C10—C11—C12 | −0.5 (7) |
O2—Mn—N2—C18 | −84.8 (3) | C10—C11—C12—C13 | −0.4 (6) |
O1—Mn—N2—C18 | −104.1 (3) | C9—N1—C13—C12 | −1.1 (5) |
C7—Mn—N2—C18 | −92.0 (3) | Mn—N1—C13—C12 | 173.9 (3) |
O3i—Mn—N2—C14 | −177.3 (3) | C9—N1—C13—C14 | 178.4 (3) |
O5—Mn—N2—C14 | −91.1 (3) | Mn—N1—C13—C14 | −6.6 (4) |
N1—Mn—N2—C14 | −10.2 (3) | C11—C12—C13—N1 | 1.2 (6) |
O2—Mn—N2—C14 | 84.7 (3) | C11—C12—C13—C14 | −178.3 (3) |
O1—Mn—N2—C14 | 65.5 (3) | C18—N2—C14—C15 | 0.5 (5) |
C7—Mn—N2—C14 | 77.6 (3) | Mn—N2—C14—C15 | −169.5 (3) |
C6—C1—C2—C3 | 1.8 (6) | C18—N2—C14—C13 | −179.6 (3) |
C7—C1—C2—C3 | 179.9 (3) | Mn—N2—C14—C13 | 10.4 (4) |
C1—C2—C3—C4 | −0.8 (6) | N1—C13—C14—N2 | −2.4 (5) |
C2—C3—C4—C5 | −1.7 (6) | C12—C13—C14—N2 | 177.1 (3) |
C2—C3—C4—C8 | −179.3 (3) | N1—C13—C14—C15 | 177.5 (3) |
C3—C4—C5—C6 | 3.1 (6) | C12—C13—C14—C15 | −3.0 (6) |
C8—C4—C5—C6 | −179.3 (3) | N2—C14—C15—C16 | 0.0 (6) |
C4—C5—C6—C1 | −2.1 (6) | C13—C14—C15—C16 | −180.0 (4) |
C2—C1—C6—C5 | −0.4 (5) | C14—C15—C16—C17 | −0.6 (7) |
C7—C1—C6—C5 | −178.5 (3) | C15—C16—C17—C18 | 0.7 (7) |
Mn—O2—C7—O1 | −0.4 (3) | C14—N2—C18—C17 | −0.4 (6) |
Mn—O2—C7—C1 | 179.0 (3) | Mn—N2—C18—C17 | 169.0 (3) |
Mn—O1—C7—O2 | 0.4 (3) | C16—C17—C18—N2 | −0.2 (7) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1/2, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···O1iii | 0.86 (2) | 1.86 (2) | 2.718 (4) | 172 (5) |
O5—H5C···O4i | 0.85 (2) | 1.87 (3) | 2.672 (4) | 157 (5) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (iii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C8H4O4)(C10H8N2)(H2O)] |
Mr | 393.25 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.8637 (2), 16.3316 (5), 11.3110 (1) |
β (°) | 111.726 (2) |
V (Å3) | 1692.66 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.81 |
Crystal size (mm) | 0.54 × 0.53 × 0.30 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.626, 0.784 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5399, 2973, 2230 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.150, 1.03 |
No. of reflections | 2973 |
No. of parameters | 243 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.30 |
Computer programs: SMART (Siemens,1996), SAINT (Siemens,1994), SHELXTL (Siemens,1994) and SAINT, SHELXTL.
Mn—O3i | 2.098 (2) | Mn—N1 | 2.260 (3) |
Mn—O5 | 2.160 (3) | Mn—O2 | 2.271 (2) |
Mn—N2 | 2.235 (3) | Mn—O1 | 2.281 (2) |
O3i—Mn—O5 | 86.79 (10) | N2—Mn—O2 | 88.63 (10) |
O3i—Mn—N2 | 90.04 (10) | N1—Mn—O2 | 94.26 (10) |
O5—Mn—N2 | 123.97 (11) | O3i—Mn—O1 | 105.72 (9) |
O3i—Mn—N1 | 158.43 (11) | O5—Mn—O1 | 90.04 (10) |
O5—Mn—N1 | 92.42 (11) | N2—Mn—O1 | 143.66 (10) |
N2—Mn—N1 | 72.56 (11) | N1—Mn—O1 | 95.83 (10) |
O3i—Mn—O2 | 98.05 (10) | O2—Mn—O1 | 57.31 (8) |
O5—Mn—O2 | 147.16 (10) |
Symmetry code: (i) x+1/2, −y+1/2, z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5B···O1ii | 0.86 (2) | 1.86 (2) | 2.718 (4) | 172 (5) |
O5—H5C···O4i | 0.85 (2) | 1.87 (3) | 2.672 (4) | 157 (5) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x, −y, −z. |
Owing to the great variety of intriguing structural topologies (Zaworotko, 1994) and potential applications in such fields as catalysis (Fujita et al., 1994) and molecular magnetism (Miller & Epstein, 1994), the crystal engineering of supramolecular architectures organized by coordinate covalent bonds and/or supramolecular contacts, such as hydrogen bonds and π–π interactions, has been investigated actively. A commonly used strategy for obtaining such systems is to select appropriate bridging ligands with versatile bonding modes, in order to bind more than one metal ion, and with the ability to form hydrogen bonds. Aromatic chelating ligands, such as 2,2'-bipyridine and 1,10-phenanthroline, are often introduced as ancillary ligands, with the hope of providing potential supramolecular recognition sites for π–π stacking interactions.
Terephthalate has been proved to be an appropriate bridging ligand for mediating magnetic exchange interactions between paramagnetic metal centers over a limited distance (about 11 Å; Bürger et al., 1995). Its versatile binding ability has been manifested by the formation of one mononuclear (Xiang et al., 1998), one dinuclear (Cano et al., 1997), three one-dimensional (Hong & Do, 1997; Li et al., 2002; Yang et al., 2003) and four three-dimensional (Hong & Do, 1997; Sun et al., 2001; Kaduk, 2002; Cano et al., 1994; Ma et al., 2003a) manganese(II) terephthalate complexes, and various bonding modes, including unidentate, bidentate and tetradentate for the tp ligands, were observed in these complexes. In this paper, we report the single-crystal structure of a new polymeric MnII terephthalate complex, (I), in which the tp dianion acts as a tridentate bridging ligand, a rare coordination mode that has not been reported previously in manganese terephthalate complexes.
Compound (I) consists of infinite one-dimensional chains, in which successive MnII atoms are bridged by one tp ligand, as shown in Fig. 1. Each MnII atom has a severely distorted six-coordinate geometry (Table 1), with three trans angles [147.16 (10), 158.43 (11) and 143.66 (10)°] deviating significantly from the ideal value of 180°. The Mn atom is coordinated by three carboxy O atoms [Mn—O = 2.098 (2)–2.281 (2) Å] from two tp ligands, one water O atom [Mn—O5 = 2.160 (3) Å] and two pyridyl N atoms [Mn—N = 2.235 (3) and 2.260 (3) Å] from the chelating bipy ligand. The Mn—N and Mn—O(carboxyl) bond lengths are similar to those found for another ternary Mn—tp—bipy polymeric complex, [Mn2(tp)(bipy)2]n(ClO4)2n (Cano et al., 1994). The Mn—O5(water) distance is comparable to those in other MnII–water complexes (Okabe & Koizumi, 1997; Hao et al., 2000; Ma et al., 2002; Schlueter & Geiser, 2003; Ma, et al., 2003b). The main distortion from ideal octahedral geometry is caused by the double chelation by the rigid bipy ligand and the chelating carboxylate group of the tp ligand. The N1—Mn—N2 bipy chelate angle of 72.56 (11)° is in agreement with other bipy-containing MnII complexes (Shen, 2003; Zhang et al., 2002; Baumeister & Hartung, 1997). The O1—Mn—O2 carboxy chelate angle of 57.31 (8)° is very close to that in [Mn(tp)(4,4'-bipy)]n [57.07 (11)°; Ma et al., 2003a], but significantly larger than that in [Mn2(tp)(dca)2(terpy)2(MeOH)2]n [52.94 (10)°; Escuer et al., 2002].
Each tp dianion acts as a tridentate bridging ligand, joining two Mn atoms in a head-to-tail fashion; one of the carboxylate groups chelates one Mn atom, while the other binds the second Mn atom in a monodentate fashion. The present work is the first time that this tridentate µ2 bridging mode has been observed for the tp ligand in Mn complexes, and to date it has been encountered in just one five-coordinate copper(II) complex (Yang et al., 2003). The two tp ligands coordinated to a given Mn center are cis to one another, resulting in a one-dimensional zigzag chain. The Mn···Mn···Mn angle formed by three successive Mn ions is 104.01 (2)° and successive bipy moieties are oriented at an angle of 89.5 (8)° to one another. The intrachain Mn···Mn separation is 11.132 (2) Å; the closest interchain contact is 5.642 (2) Å. Neighboring chains are arranged in an antiparallel fashion (Fig. 2a).
The neighboring zigzag chains are cross-linked by O5—H5B···O1(-x, −y, −z) hydrogen bonds, formed by the coordinated water molecule with one of the chelating carboxy O atoms of a symmetry-related chain (Table 2), thus resulting in the formation of a two-dimensional hydrogen-bonded pleated sheet, as shown in Fig. 2 b. The second water H atom is donated to form an intrachain O5—H5C···O4(x + 1/2, −y + 1/2, z − 1/2) hydrogen bond with the uncoordinated carboxy O atom. These two-dimensional hydrogen-bonded sheets are further packed into a three-dimensional herringbone-like supramolecular network via two kinds of π–π stacking interactions, namely between the bipy ligands and between the phenyl ring of the tp ligand and the bipy ligand, with perpendicular ring separations of 3.459 (8) and 3.542 (9) Å, respectively. A view along the a axis is shown in Fig. 3.