Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011758/ci6041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011758/ci6041Isup2.hkl |
CCDC reference: 170877
5-Hydroxyisophthalic acid ((51.4 mg, 0.285 mmol), manganese acetate tetrahydrate (69.2 mg, 0.282 mmol), phenanthroline (51.1 mg, 0.284 mmol) and water (10 ml) were placed in a 23 ml Parr bomb. After sealing, the bomb was heated at 100 K h-1 to 513 K. This temperature was maintained for 2 h, after which the bomb was cooled at 5 K h-1 to 453 K, left for 6 h, then cooled at 4 K h-1 to 293 K. The bomb was opened, and the product was collected by filtration, washed with water and dried in air. This method produced a mixture of yellow crystals and brown non-crystalline material.
In general, H atoms were placed in geometrical positions and refined using a riding model. Those for the water molecule and the hydroxyl were located from the difference map and refined freely.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX in OSCAIL (McArdle, 1994), ATOMS (Dowty, 1999) and ORTEP-3 for Windows (Farrugia, 1997).
C20H12MnN2O5·H2O | F(000) = 884 |
Mr = 433.27 | Dx = 1.609 Mg m−3 |
Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6089 (5) Å | Cell parameters from 3745 reflections |
b = 12.2249 (7) Å | θ = 2.4–29.2° |
c = 17.3057 (11) Å | µ = 0.78 mm−1 |
β = 100.860 (2)° | T = 298 K |
V = 1788.68 (18) Å3 | Block, yellow |
Z = 4 | 0.30 × 0.10 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 5186 independent reflections |
Radiation source: fine-focus sealed tube | 2944 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
ϕ–ω scans | θmax = 30.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −12→12 |
Tmin = 0.798, Tmax = 0.928 | k = −16→17 |
15609 measured reflections | l = −24→14 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0291P)2] where P = (Fo2 + 2Fc2)/3 |
5186 reflections | (Δ/σ)max = 0.001 |
274 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
C20H12MnN2O5·H2O | V = 1788.68 (18) Å3 |
Mr = 433.27 | Z = 4 |
Monoclinic, P2/n | Mo Kα radiation |
a = 8.6089 (5) Å | µ = 0.78 mm−1 |
b = 12.2249 (7) Å | T = 298 K |
c = 17.3057 (11) Å | 0.30 × 0.10 × 0.10 mm |
β = 100.860 (2)° |
Bruker SMART CCD area-detector diffractometer | 5186 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 2944 reflections with I > 2σ(I) |
Tmin = 0.798, Tmax = 0.928 | Rint = 0.059 |
15609 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.079 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | Δρmax = 0.33 e Å−3 |
5186 reflections | Δρmin = −0.43 e Å−3 |
274 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. In general, H-atoms were placed geometrically and refined using a riding model, with the exception of those of the water molecule and the hydroxy-group, which were located from the difference Fourier map and refined freely. |
x | y | z | Uiso*/Ueq | ||
Mn | −0.05181 (4) | 0.29828 (2) | 0.834278 (19) | 0.02495 (9) | |
N1 | −0.0089 (2) | 0.15142 (13) | 0.76292 (10) | 0.0286 (4) | |
C1 | 0.0556 (3) | 0.15319 (19) | 0.69917 (14) | 0.0409 (6) | |
H1 | 0.0774 | 0.2205 | 0.6785 | 0.049* | |
C2 | 0.0920 (3) | 0.0580 (2) | 0.66198 (16) | 0.0549 (8) | |
H2 | 0.1374 | 0.0622 | 0.6174 | 0.066* | |
C3 | 0.0608 (3) | −0.0414 (2) | 0.69138 (16) | 0.0527 (7) | |
H3 | 0.0846 | −0.1052 | 0.6668 | 0.063* | |
C4 | −0.0074 (3) | −0.04704 (18) | 0.75869 (15) | 0.0389 (6) | |
C5 | −0.0391 (2) | 0.05284 (16) | 0.79275 (13) | 0.0275 (5) | |
C6 | −0.1064 (2) | 0.05264 (16) | 0.86280 (13) | 0.0275 (5) | |
C7 | −0.1417 (3) | −0.04739 (18) | 0.89636 (15) | 0.0368 (6) | |
C8 | −0.2048 (3) | −0.0412 (2) | 0.96504 (16) | 0.0514 (7) | |
H8 | −0.2292 | −0.1050 | 0.9895 | 0.062* | |
C9 | −0.2307 (3) | 0.0582 (2) | 0.99622 (16) | 0.0526 (7) | |
H9 | −0.2736 | 0.0627 | 1.0416 | 0.063* | |
C10 | −0.1921 (3) | 0.15286 (19) | 0.95922 (14) | 0.0402 (6) | |
H10 | −0.2100 | 0.2203 | 0.9809 | 0.048* | |
N2 | −0.1313 (2) | 0.15085 (14) | 0.89481 (10) | 0.0296 (4) | |
C11 | −0.0449 (3) | −0.14692 (18) | 0.79488 (17) | 0.0486 (7) | |
H11 | −0.0244 | −0.2133 | 0.7725 | 0.058* | |
C12 | −0.1081 (3) | −0.14759 (19) | 0.85967 (17) | 0.0482 (7) | |
H12 | −0.1308 | −0.2140 | 0.8813 | 0.058* | |
O1 | 0.05605 (18) | 0.39574 (12) | 0.93858 (9) | 0.0423 (4) | |
O2 | 0.20632 (18) | 0.26756 (13) | 0.90374 (9) | 0.0429 (4) | |
C13 | 0.1855 (3) | 0.34409 (17) | 0.94849 (13) | 0.0288 (5) | |
C14 | 0.3144 (2) | 0.37423 (16) | 1.01624 (12) | 0.0264 (5) | |
C15 | 0.4530 (2) | 0.31323 (16) | 1.03078 (13) | 0.0304 (5) | |
H15 | 0.4659 | 0.2551 | 0.9979 | 0.036* | |
C16 | 0.5724 (2) | 0.33829 (16) | 1.09399 (13) | 0.0291 (5) | |
O3 | 0.7052 (2) | 0.27397 (13) | 1.10686 (11) | 0.0420 (4) | |
H3O | 0.783 (3) | 0.314 (2) | 1.1164 (16) | 0.059 (9)* | |
C17 | 0.5532 (2) | 0.42466 (16) | 1.14291 (13) | 0.0316 (5) | |
H17 | 0.6329 | 0.4415 | 1.1854 | 0.038* | |
C18 | 0.4149 (2) | 0.48653 (16) | 1.12879 (12) | 0.0268 (5) | |
C19 | 0.2965 (2) | 0.46190 (16) | 1.06460 (12) | 0.0262 (5) | |
H19 | 0.2052 | 0.5043 | 1.0541 | 0.031* | |
C20 | 0.3924 (3) | 0.57772 (16) | 1.18346 (13) | 0.0284 (5) | |
O4 | 0.48673 (18) | 0.58274 (11) | 1.24954 (9) | 0.0376 (4) | |
O5 | 0.28260 (17) | 0.64449 (11) | 1.16270 (9) | 0.0363 (4) | |
O6 | 0.0413 (2) | 0.59854 (16) | 0.85348 (19) | 0.0574 (6) | |
H6WA | 0.043 (4) | 0.575 (3) | 0.896 (2) | 0.098 (16)* | |
H6WB | 0.027 (4) | 0.550 (3) | 0.814 (2) | 0.101 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn | 0.03209 (18) | 0.01810 (14) | 0.02339 (16) | 0.00149 (15) | 0.00195 (12) | 0.00036 (15) |
N1 | 0.0357 (11) | 0.0257 (9) | 0.0243 (10) | 0.0026 (8) | 0.0056 (8) | −0.0006 (8) |
C1 | 0.0563 (16) | 0.0375 (13) | 0.0318 (13) | 0.0040 (12) | 0.0157 (12) | 0.0007 (11) |
C2 | 0.078 (2) | 0.0527 (16) | 0.0393 (16) | 0.0140 (15) | 0.0255 (15) | −0.0069 (14) |
C3 | 0.0697 (19) | 0.0405 (14) | 0.0478 (17) | 0.0145 (14) | 0.0110 (15) | −0.0178 (13) |
C4 | 0.0439 (15) | 0.0284 (12) | 0.0407 (15) | 0.0077 (11) | −0.0011 (12) | −0.0076 (11) |
C5 | 0.0285 (12) | 0.0218 (10) | 0.0301 (12) | 0.0033 (9) | 0.0003 (10) | −0.0018 (10) |
C6 | 0.0279 (12) | 0.0227 (10) | 0.0302 (12) | 0.0021 (9) | 0.0012 (10) | 0.0033 (10) |
C7 | 0.0360 (13) | 0.0276 (11) | 0.0447 (15) | −0.0017 (10) | 0.0019 (11) | 0.0097 (11) |
C8 | 0.0597 (18) | 0.0405 (14) | 0.0565 (18) | −0.0059 (13) | 0.0171 (15) | 0.0201 (14) |
C9 | 0.0635 (19) | 0.0536 (17) | 0.0477 (17) | 0.0008 (14) | 0.0284 (15) | 0.0147 (15) |
C10 | 0.0527 (16) | 0.0354 (13) | 0.0367 (14) | 0.0046 (11) | 0.0190 (12) | 0.0029 (12) |
N2 | 0.0334 (10) | 0.0254 (9) | 0.0314 (11) | 0.0047 (8) | 0.0093 (9) | 0.0038 (8) |
C11 | 0.0616 (18) | 0.0207 (12) | 0.0589 (18) | 0.0059 (11) | −0.0003 (15) | −0.0092 (13) |
C12 | 0.0573 (17) | 0.0218 (12) | 0.0627 (19) | −0.0028 (12) | 0.0045 (15) | 0.0072 (13) |
O1 | 0.0368 (10) | 0.0410 (9) | 0.0423 (10) | 0.0100 (8) | −0.0097 (8) | −0.0108 (8) |
O2 | 0.0417 (10) | 0.0482 (10) | 0.0362 (9) | 0.0032 (8) | 0.0009 (8) | −0.0190 (8) |
C13 | 0.0351 (13) | 0.0268 (11) | 0.0238 (12) | −0.0024 (10) | 0.0034 (10) | −0.0002 (10) |
C14 | 0.0292 (11) | 0.0252 (10) | 0.0247 (11) | 0.0008 (9) | 0.0046 (9) | −0.0013 (9) |
C15 | 0.0347 (12) | 0.0268 (11) | 0.0304 (12) | 0.0022 (10) | 0.0080 (10) | −0.0079 (10) |
C16 | 0.0255 (11) | 0.0265 (10) | 0.0342 (13) | 0.0047 (9) | 0.0029 (10) | −0.0040 (10) |
O3 | 0.0288 (9) | 0.0347 (10) | 0.0594 (12) | 0.0085 (8) | 0.0006 (8) | −0.0142 (8) |
C17 | 0.0305 (12) | 0.0301 (11) | 0.0306 (13) | 0.0030 (9) | −0.0036 (10) | −0.0066 (10) |
C18 | 0.0304 (12) | 0.0228 (10) | 0.0266 (12) | 0.0009 (9) | 0.0037 (10) | −0.0049 (9) |
C19 | 0.0265 (11) | 0.0247 (10) | 0.0259 (11) | 0.0027 (9) | 0.0012 (9) | −0.0012 (9) |
C20 | 0.0297 (12) | 0.0232 (10) | 0.0317 (13) | −0.0006 (9) | 0.0038 (10) | −0.0052 (9) |
O4 | 0.0436 (10) | 0.0325 (8) | 0.0314 (9) | 0.0097 (7) | −0.0067 (8) | −0.0096 (7) |
O5 | 0.0373 (9) | 0.0288 (8) | 0.0408 (10) | 0.0129 (7) | 0.0026 (8) | −0.0046 (7) |
O6 | 0.0578 (13) | 0.0325 (10) | 0.0788 (18) | −0.0061 (9) | 0.0046 (13) | 0.0045 (12) |
Mn—O5i | 2.1163 (14) | C10—H10 | 0.9300 |
Mn—O4ii | 2.1354 (15) | C11—C12 | 1.336 (4) |
Mn—O1 | 2.2156 (15) | C11—H11 | 0.9300 |
Mn—N1 | 2.2486 (17) | C12—H12 | 0.9300 |
Mn—N2 | 2.2546 (17) | O1—C13 | 1.264 (2) |
Mn—O2 | 2.3490 (16) | O2—C13 | 1.249 (2) |
N1—C1 | 1.326 (3) | C13—C14 | 1.500 (3) |
N1—C5 | 1.355 (3) | C14—C19 | 1.386 (3) |
C1—C2 | 1.394 (3) | C14—C15 | 1.390 (3) |
C1—H1 | 0.9300 | C15—C16 | 1.387 (3) |
C2—C3 | 1.363 (4) | C15—H15 | 0.9300 |
C2—H2 | 0.9300 | C16—O3 | 1.371 (2) |
C3—C4 | 1.401 (3) | C16—C17 | 1.383 (3) |
C3—H3 | 0.9300 | O3—H3O | 0.82 (3) |
C4—C5 | 1.405 (3) | C17—C18 | 1.392 (3) |
C4—C11 | 1.436 (3) | C17—H17 | 0.9300 |
C5—C6 | 1.439 (3) | C18—C19 | 1.392 (3) |
C6—N2 | 1.356 (3) | C18—C20 | 1.498 (3) |
C6—C7 | 1.411 (3) | C19—H19 | 0.9300 |
C7—C8 | 1.399 (3) | C20—O5 | 1.249 (2) |
C7—C12 | 1.434 (3) | C20—O4 | 1.273 (2) |
C8—C9 | 1.365 (3) | O4—Mniii | 2.1354 (15) |
C8—H8 | 0.9300 | O5—Mni | 2.1163 (14) |
C9—C10 | 1.392 (3) | O6—H6WA | 0.79 (4) |
C9—H9 | 0.9300 | O6—H6WB | 0.90 (3) |
C10—N2 | 1.318 (3) | ||
O5i—Mn—O4ii | 93.43 (6) | C8—C9—H9 | 120.4 |
O5i—Mn—O1 | 93.06 (6) | C10—C9—H9 | 120.4 |
O4ii—Mn—O1 | 95.61 (6) | N2—C10—C9 | 122.7 (2) |
O5i—Mn—N1 | 121.98 (6) | N2—C10—H10 | 118.6 |
O4ii—Mn—N1 | 95.96 (6) | C9—C10—H10 | 118.6 |
O1—Mn—N1 | 142.17 (6) | C10—N2—C6 | 118.72 (19) |
O5i—Mn—N2 | 83.36 (6) | C10—N2—Mn | 125.57 (15) |
O4ii—Mn—N2 | 164.49 (6) | C6—N2—Mn | 115.64 (13) |
O1—Mn—N2 | 99.71 (6) | C12—C11—C4 | 122.1 (2) |
N1—Mn—N2 | 73.29 (6) | C12—C11—H11 | 118.9 |
O5i—Mn—O2 | 147.38 (6) | C4—C11—H11 | 118.9 |
O4ii—Mn—O2 | 101.88 (6) | C11—C12—C7 | 121.0 (2) |
O1—Mn—O2 | 57.19 (5) | C11—C12—H12 | 119.5 |
N1—Mn—O2 | 85.18 (6) | C7—C12—H12 | 119.5 |
N2—Mn—O2 | 88.57 (6) | O2—C13—O1 | 121.1 (2) |
C1—N1—C5 | 118.16 (19) | O2—C13—C14 | 119.82 (19) |
C1—N1—Mn | 125.59 (15) | O1—C13—C14 | 119.11 (19) |
C5—N1—Mn | 115.96 (14) | C19—C14—C15 | 119.67 (19) |
N1—C1—C2 | 122.4 (2) | C19—C14—C13 | 120.77 (18) |
N1—C1—H1 | 118.8 | C15—C14—C13 | 119.55 (18) |
C2—C1—H1 | 118.8 | C16—C15—C14 | 120.53 (19) |
C3—C2—C1 | 119.6 (2) | C16—C15—H15 | 119.7 |
C3—C2—H2 | 120.2 | C14—C15—H15 | 119.7 |
C1—C2—H2 | 120.2 | O3—C16—C17 | 122.08 (19) |
C2—C3—C4 | 119.8 (2) | O3—C16—C15 | 118.23 (18) |
C2—C3—H3 | 120.1 | C17—C16—C15 | 119.68 (19) |
C4—C3—H3 | 120.1 | C16—O3—H3O | 108.0 (18) |
C3—C4—C5 | 116.8 (2) | C16—C17—C18 | 120.29 (19) |
C3—C4—C11 | 124.6 (2) | C16—C17—H17 | 119.9 |
C5—C4—C11 | 118.6 (2) | C18—C17—H17 | 119.9 |
N1—C5—C4 | 123.1 (2) | C19—C18—C17 | 119.74 (19) |
N1—C5—C6 | 117.32 (18) | C19—C18—C20 | 120.16 (18) |
C4—C5—C6 | 119.5 (2) | C17—C18—C20 | 120.09 (19) |
N2—C6—C7 | 122.4 (2) | C14—C19—C18 | 120.06 (19) |
N2—C6—C5 | 117.54 (18) | C14—C19—H19 | 120.0 |
C7—C6—C5 | 120.0 (2) | C18—C19—H19 | 120.0 |
C8—C7—C6 | 116.8 (2) | O5—C20—O4 | 123.15 (19) |
C8—C7—C12 | 124.4 (2) | O5—C20—C18 | 119.05 (19) |
C6—C7—C12 | 118.8 (2) | O4—C20—C18 | 117.81 (18) |
C9—C8—C7 | 120.1 (2) | C20—O4—Mniii | 119.62 (13) |
C9—C8—H8 | 119.9 | C20—O5—Mni | 150.68 (15) |
C7—C8—H8 | 119.9 | H6WA—O6—H6WB | 117 (3) |
C8—C9—C10 | 119.2 (2) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x−1/2, −y+1, z−1/2; (iii) x+1/2, −y+1, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O6iv | 0.82 (3) | 1.85 (3) | 2.664 (3) | 175 (3) |
O6—H6WA···O1 | 0.79 (4) | 2.31 (3) | 2.874 (3) | 130 (3) |
O6—H6WB···O4ii | 0.90 (3) | 1.96 (4) | 2.837 (3) | 164 (3) |
Symmetry codes: (ii) x−1/2, −y+1, z−1/2; (iv) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C20H12MnN2O5·H2O |
Mr | 433.27 |
Crystal system, space group | Monoclinic, P2/n |
Temperature (K) | 298 |
a, b, c (Å) | 8.6089 (5), 12.2249 (7), 17.3057 (11) |
β (°) | 100.860 (2) |
V (Å3) | 1788.68 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.78 |
Crystal size (mm) | 0.30 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.798, 0.928 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15609, 5186, 2944 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.079, 0.85 |
No. of reflections | 5186 |
No. of parameters | 274 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.43 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX in OSCAIL (McArdle, 1994), ATOMS (Dowty, 1999) and ORTEP-3 for Windows (Farrugia, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O6i | 0.82 (3) | 1.85 (3) | 2.664 (3) | 175 (3) |
O6—H6WA···O1 | 0.79 (4) | 2.31 (3) | 2.874 (3) | 130 (3) |
O6—H6WB···O4ii | 0.90 (3) | 1.96 (4) | 2.837 (3) | 164 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x−1/2, −y+1, z−1/2. |
The title compound, (I), was synthesized as part of a study into polymeric compounds containing metals and 5-hydroxyisophthalic acid (HIA), which may possess interesting magnetic properties.
The asymmetric unit is shown in Fig. 1. Mn is coordinated to two N and three O atoms; a fourth O, from a coordinated carboxyl group, is located at a slightly longer distance of 2.3490 (16) Å.
The structure was confirmed to be polymeric; each metal ion is bonded to three O atoms of two carboxylate groups from two distinct HIA molecules. This effectively gives a dimer of two metal and three HIA molecules, which links to form a (Mn2+)2n(C8H4O5 2-)2n chain (Fig. 2). This chain forms a zigzag parallel to (101), as shown in Fig. 3.
The chelating phenanthroline ligand is coordinated to the metal via the two N atoms, and is oriented approximately perpendicular (83.7°) to the Mn–HIA network. This gives layers of Mn–HIA and phenanthroline, the layers stacking at an angle of approximately 34° to (100) (Fig. 3). The phenanthroline molecules are, on average, separated by 3.51 (5) Å, typical for π-π stacking.
There is one free water molecule per formula unit, which is hydrogen bonded to two O atoms of the carboxylate groups of HIA, whilst the hydroxyl is hydrogen bonded to the water.
The Zn analogue was also synthesized and shown to be isostructural, but due to the poor quality of crystals and hence data, the full structure is not reported.