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The title compound, {[Mn(C8H4O5)(C12H8N2)]·H2O}n, forms a polymeric chain via Mn2+–C8H4O52− (Mn–HIA) dimers which zigzag parallel to [101]. The 1,10-phenanthroline mol­ecules are coordinated to the metal via the N atoms and are arranged approximately perpendicular to the Mn–HIA layers. The phenanthroline ligands are stacked parallel to one another at intervals of 3.54 Å, which is characteristic of π–π interaction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011758/ci6041sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011758/ci6041Isup2.hkl
Contains datablock I

CCDC reference: 170877

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.040
  • wR factor = 0.079
  • Data-to-parameter ratio = 18.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound (symmetry codes: (i) x - 1/2, -y + 1, z - 1/2; (ii) -x, -y + 1, -z + 2). Ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. Projection of structure down (010), showing the formation of the Mn–HIA chain along (101).
[Figure 3] Fig. 3. Projection of structure showing the zigzag of the Mn–HIA dimeric chain and relative orientation of the phenanthroline molecules. The projection is offset from (100) by approx. 34° so that the phenanthroline molecules are superposed.
Catena-(µ2-(1-Hydroxybenzene-3,5-dicarboxylato-O,O',O'',O''')(1,10-phenanthr oline)manganese(II) hydrate) top
Crystal data top
C20H12MnN2O5·H2OF(000) = 884
Mr = 433.27Dx = 1.609 Mg m3
Monoclinic, P2/nMo Kα radiation, λ = 0.71073 Å
a = 8.6089 (5) ÅCell parameters from 3745 reflections
b = 12.2249 (7) Åθ = 2.4–29.2°
c = 17.3057 (11) ŵ = 0.78 mm1
β = 100.860 (2)°T = 298 K
V = 1788.68 (18) Å3Block, yellow
Z = 40.30 × 0.10 × 0.10 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
5186 independent reflections
Radiation source: fine-focus sealed tube2944 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.059
ϕω scansθmax = 30.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 1212
Tmin = 0.798, Tmax = 0.928k = 1617
15609 measured reflectionsl = 2414
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079H 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 parametersΔρmax = 0.33 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C20H12MnN2O5·H2OV = 1788.68 (18) Å3
Mr = 433.27Z = 4
Monoclinic, P2/nMo Kα radiation
a = 8.6089 (5) ŵ = 0.78 mm1
b = 12.2249 (7) ÅT = 298 K
c = 17.3057 (11) Å0.30 × 0.10 × 0.10 mm
β = 100.860 (2)°
Data collection top
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 = 0.928Rint = 0.059
15609 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.079H atoms treated by a mixture of independent and constrained refinement
S = 0.85Δρmax = 0.33 e Å3
5186 reflectionsΔρmin = 0.43 e Å3
274 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.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn0.05181 (4)0.29828 (2)0.834278 (19)0.02495 (9)
N10.0089 (2)0.15142 (13)0.76292 (10)0.0286 (4)
C10.0556 (3)0.15319 (19)0.69917 (14)0.0409 (6)
H10.07740.22050.67850.049*
C20.0920 (3)0.0580 (2)0.66198 (16)0.0549 (8)
H20.13740.06220.61740.066*
C30.0608 (3)0.0414 (2)0.69138 (16)0.0527 (7)
H30.08460.10520.66680.063*
C40.0074 (3)0.04704 (18)0.75869 (15)0.0389 (6)
C50.0391 (2)0.05284 (16)0.79275 (13)0.0275 (5)
C60.1064 (2)0.05264 (16)0.86280 (13)0.0275 (5)
C70.1417 (3)0.04739 (18)0.89636 (15)0.0368 (6)
C80.2048 (3)0.0412 (2)0.96504 (16)0.0514 (7)
H80.22920.10500.98950.062*
C90.2307 (3)0.0582 (2)0.99622 (16)0.0526 (7)
H90.27360.06271.04160.063*
C100.1921 (3)0.15286 (19)0.95922 (14)0.0402 (6)
H100.21000.22030.98090.048*
N20.1313 (2)0.15085 (14)0.89481 (10)0.0296 (4)
C110.0449 (3)0.14692 (18)0.79488 (17)0.0486 (7)
H110.02440.21330.77250.058*
C120.1081 (3)0.14759 (19)0.85967 (17)0.0482 (7)
H120.13080.21400.88130.058*
O10.05605 (18)0.39574 (12)0.93858 (9)0.0423 (4)
O20.20632 (18)0.26756 (13)0.90374 (9)0.0429 (4)
C130.1855 (3)0.34409 (17)0.94849 (13)0.0288 (5)
C140.3144 (2)0.37423 (16)1.01624 (12)0.0264 (5)
C150.4530 (2)0.31323 (16)1.03078 (13)0.0304 (5)
H150.46590.25510.99790.036*
C160.5724 (2)0.33829 (16)1.09399 (13)0.0291 (5)
O30.7052 (2)0.27397 (13)1.10686 (11)0.0420 (4)
H3O0.783 (3)0.314 (2)1.1164 (16)0.059 (9)*
C170.5532 (2)0.42466 (16)1.14291 (13)0.0316 (5)
H170.63290.44151.18540.038*
C180.4149 (2)0.48653 (16)1.12879 (12)0.0268 (5)
C190.2965 (2)0.46190 (16)1.06460 (12)0.0262 (5)
H190.20520.50431.05410.031*
C200.3924 (3)0.57772 (16)1.18346 (13)0.0284 (5)
O40.48673 (18)0.58274 (11)1.24954 (9)0.0376 (4)
O50.28260 (17)0.64449 (11)1.16270 (9)0.0363 (4)
O60.0413 (2)0.59854 (16)0.85348 (19)0.0574 (6)
H6WA0.043 (4)0.575 (3)0.896 (2)0.098 (16)*
H6WB0.027 (4)0.550 (3)0.814 (2)0.101 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn0.03209 (18)0.01810 (14)0.02339 (16)0.00149 (15)0.00195 (12)0.00036 (15)
N10.0357 (11)0.0257 (9)0.0243 (10)0.0026 (8)0.0056 (8)0.0006 (8)
C10.0563 (16)0.0375 (13)0.0318 (13)0.0040 (12)0.0157 (12)0.0007 (11)
C20.078 (2)0.0527 (16)0.0393 (16)0.0140 (15)0.0255 (15)0.0069 (14)
C30.0697 (19)0.0405 (14)0.0478 (17)0.0145 (14)0.0110 (15)0.0178 (13)
C40.0439 (15)0.0284 (12)0.0407 (15)0.0077 (11)0.0011 (12)0.0076 (11)
C50.0285 (12)0.0218 (10)0.0301 (12)0.0033 (9)0.0003 (10)0.0018 (10)
C60.0279 (12)0.0227 (10)0.0302 (12)0.0021 (9)0.0012 (10)0.0033 (10)
C70.0360 (13)0.0276 (11)0.0447 (15)0.0017 (10)0.0019 (11)0.0097 (11)
C80.0597 (18)0.0405 (14)0.0565 (18)0.0059 (13)0.0171 (15)0.0201 (14)
C90.0635 (19)0.0536 (17)0.0477 (17)0.0008 (14)0.0284 (15)0.0147 (15)
C100.0527 (16)0.0354 (13)0.0367 (14)0.0046 (11)0.0190 (12)0.0029 (12)
N20.0334 (10)0.0254 (9)0.0314 (11)0.0047 (8)0.0093 (9)0.0038 (8)
C110.0616 (18)0.0207 (12)0.0589 (18)0.0059 (11)0.0003 (15)0.0092 (13)
C120.0573 (17)0.0218 (12)0.0627 (19)0.0028 (12)0.0045 (15)0.0072 (13)
O10.0368 (10)0.0410 (9)0.0423 (10)0.0100 (8)0.0097 (8)0.0108 (8)
O20.0417 (10)0.0482 (10)0.0362 (9)0.0032 (8)0.0009 (8)0.0190 (8)
C130.0351 (13)0.0268 (11)0.0238 (12)0.0024 (10)0.0034 (10)0.0002 (10)
C140.0292 (11)0.0252 (10)0.0247 (11)0.0008 (9)0.0046 (9)0.0013 (9)
C150.0347 (12)0.0268 (11)0.0304 (12)0.0022 (10)0.0080 (10)0.0079 (10)
C160.0255 (11)0.0265 (10)0.0342 (13)0.0047 (9)0.0029 (10)0.0040 (10)
O30.0288 (9)0.0347 (10)0.0594 (12)0.0085 (8)0.0006 (8)0.0142 (8)
C170.0305 (12)0.0301 (11)0.0306 (13)0.0030 (9)0.0036 (10)0.0066 (10)
C180.0304 (12)0.0228 (10)0.0266 (12)0.0009 (9)0.0037 (10)0.0049 (9)
C190.0265 (11)0.0247 (10)0.0259 (11)0.0027 (9)0.0012 (9)0.0012 (9)
C200.0297 (12)0.0232 (10)0.0317 (13)0.0006 (9)0.0038 (10)0.0052 (9)
O40.0436 (10)0.0325 (8)0.0314 (9)0.0097 (7)0.0067 (8)0.0096 (7)
O50.0373 (9)0.0288 (8)0.0408 (10)0.0129 (7)0.0026 (8)0.0046 (7)
O60.0578 (13)0.0325 (10)0.0788 (18)0.0061 (9)0.0046 (13)0.0045 (12)
Geometric parameters (Å, º) top
Mn—O5i2.1163 (14)C10—H100.9300
Mn—O4ii2.1354 (15)C11—C121.336 (4)
Mn—O12.2156 (15)C11—H110.9300
Mn—N12.2486 (17)C12—H120.9300
Mn—N22.2546 (17)O1—C131.264 (2)
Mn—O22.3490 (16)O2—C131.249 (2)
N1—C11.326 (3)C13—C141.500 (3)
N1—C51.355 (3)C14—C191.386 (3)
C1—C21.394 (3)C14—C151.390 (3)
C1—H10.9300C15—C161.387 (3)
C2—C31.363 (4)C15—H150.9300
C2—H20.9300C16—O31.371 (2)
C3—C41.401 (3)C16—C171.383 (3)
C3—H30.9300O3—H3O0.82 (3)
C4—C51.405 (3)C17—C181.392 (3)
C4—C111.436 (3)C17—H170.9300
C5—C61.439 (3)C18—C191.392 (3)
C6—N21.356 (3)C18—C201.498 (3)
C6—C71.411 (3)C19—H190.9300
C7—C81.399 (3)C20—O51.249 (2)
C7—C121.434 (3)C20—O41.273 (2)
C8—C91.365 (3)O4—Mniii2.1354 (15)
C8—H80.9300O5—Mni2.1163 (14)
C9—C101.392 (3)O6—H6WA0.79 (4)
C9—H90.9300O6—H6WB0.90 (3)
C10—N21.318 (3)
O5i—Mn—O4ii93.43 (6)C8—C9—H9120.4
O5i—Mn—O193.06 (6)C10—C9—H9120.4
O4ii—Mn—O195.61 (6)N2—C10—C9122.7 (2)
O5i—Mn—N1121.98 (6)N2—C10—H10118.6
O4ii—Mn—N195.96 (6)C9—C10—H10118.6
O1—Mn—N1142.17 (6)C10—N2—C6118.72 (19)
O5i—Mn—N283.36 (6)C10—N2—Mn125.57 (15)
O4ii—Mn—N2164.49 (6)C6—N2—Mn115.64 (13)
O1—Mn—N299.71 (6)C12—C11—C4122.1 (2)
N1—Mn—N273.29 (6)C12—C11—H11118.9
O5i—Mn—O2147.38 (6)C4—C11—H11118.9
O4ii—Mn—O2101.88 (6)C11—C12—C7121.0 (2)
O1—Mn—O257.19 (5)C11—C12—H12119.5
N1—Mn—O285.18 (6)C7—C12—H12119.5
N2—Mn—O288.57 (6)O2—C13—O1121.1 (2)
C1—N1—C5118.16 (19)O2—C13—C14119.82 (19)
C1—N1—Mn125.59 (15)O1—C13—C14119.11 (19)
C5—N1—Mn115.96 (14)C19—C14—C15119.67 (19)
N1—C1—C2122.4 (2)C19—C14—C13120.77 (18)
N1—C1—H1118.8C15—C14—C13119.55 (18)
C2—C1—H1118.8C16—C15—C14120.53 (19)
C3—C2—C1119.6 (2)C16—C15—H15119.7
C3—C2—H2120.2C14—C15—H15119.7
C1—C2—H2120.2O3—C16—C17122.08 (19)
C2—C3—C4119.8 (2)O3—C16—C15118.23 (18)
C2—C3—H3120.1C17—C16—C15119.68 (19)
C4—C3—H3120.1C16—O3—H3O108.0 (18)
C3—C4—C5116.8 (2)C16—C17—C18120.29 (19)
C3—C4—C11124.6 (2)C16—C17—H17119.9
C5—C4—C11118.6 (2)C18—C17—H17119.9
N1—C5—C4123.1 (2)C19—C18—C17119.74 (19)
N1—C5—C6117.32 (18)C19—C18—C20120.16 (18)
C4—C5—C6119.5 (2)C17—C18—C20120.09 (19)
N2—C6—C7122.4 (2)C14—C19—C18120.06 (19)
N2—C6—C5117.54 (18)C14—C19—H19120.0
C7—C6—C5120.0 (2)C18—C19—H19120.0
C8—C7—C6116.8 (2)O5—C20—O4123.15 (19)
C8—C7—C12124.4 (2)O5—C20—C18119.05 (19)
C6—C7—C12118.8 (2)O4—C20—C18117.81 (18)
C9—C8—C7120.1 (2)C20—O4—Mniii119.62 (13)
C9—C8—H8119.9C20—O5—Mni150.68 (15)
C7—C8—H8119.9H6WA—O6—H6WB117 (3)
C8—C9—C10119.2 (2)
Symmetry codes: (i) x, y+1, z+2; (ii) x1/2, y+1, z1/2; (iii) x+1/2, y+1, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O6iv0.82 (3)1.85 (3)2.664 (3)175 (3)
O6—H6WA···O10.79 (4)2.31 (3)2.874 (3)130 (3)
O6—H6WB···O4ii0.90 (3)1.96 (4)2.837 (3)164 (3)
Symmetry codes: (ii) x1/2, y+1, z1/2; (iv) x+1, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC20H12MnN2O5·H2O
Mr433.27
Crystal system, space groupMonoclinic, P2/n
Temperature (K)298
a, b, c (Å)8.6089 (5), 12.2249 (7), 17.3057 (11)
β (°) 100.860 (2)
V3)1788.68 (18)
Z4
Radiation typeMo Kα
µ (mm1)0.78
Crystal size (mm)0.30 × 0.10 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.798, 0.928
No. of measured, independent and
observed [I > 2σ(I)] reflections
15609, 5186, 2944
Rint0.059
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.079, 0.85
No. of reflections5186
No. of parameters274
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O6i0.82 (3)1.85 (3)2.664 (3)175 (3)
O6—H6WA···O10.79 (4)2.31 (3)2.874 (3)130 (3)
O6—H6WB···O4ii0.90 (3)1.96 (4)2.837 (3)164 (3)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x1/2, y+1, z1/2.
 

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