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Acta Cryst. (2011). E67, m1072    [ doi:10.1107/S1600536811025335 ]

Tetraaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato-[kappa]N1]manganese(II) decahydrate

Y.-A. Piao and Z.-Y. Xuan

Abstract top

In the title compound, [Mn(C9H6N3O2)2(H2O)4]·10H2O, the MnII ion is coordinated by two N atoms from two 4-(4H-1,2,4-triazol-4-yl)benzoate ligands and four water molecules in a distorted octahedral geometry. The MnII ion and two coordinated water molecules lie on a twofold rotation axis. The water molecules are involved in O-H...N and O-H...O hydrogen bonds with the triazole N atoms and carboxylate O atoms, yielding a three-dimensional supramolecular network. [pi]-[pi] interactions between the benzene rings [centroid-centroid distance = 3.836 (9) Å] are observed.

Comment top

The construction of novel coordination polymers is the current interest in the field of supramolecular chemistry and crystal engineering, not only for their interesting topologies and crystal packing motifs but also for their potential applications as functional materials (Wang et al., 2009; Zang et al., 2006). As an important family of multidentate O-donor ligands, organic aromatic carboxylate ligands have been extensively employed in the preparation of metal-organic complexes (Guo et al., 2009). In this paper, we selected 4-(1,2,4-triazol-4-yl)benzoic acid as an organic carboxylate ligand, generating the title compound, which is reported here.

In the title compound, the MnII ions lies on a twofold rotation axis and is approximately octahedrally coordinated by two N atoms from two 4-(1,2,4-triazol-4-yl)benzoate ligands and four water molecules, two of which lie on the twofold rotation axis (Fig. 1). The Mn—N and Mn—O bond lengths and the O—Mn—O and N—Mn—O bond angles are comparable to those found in the other crystallographically characterized Mn(II) complexes (Wang, 2011). The water molecules are involved in O—H···N and O—H···O hydrogen bonds with the triazole N atoms and carboxylate O atoms (Table 1), yielding a three-dimensional supramolecular network (Fig. 2). π–π interactions between the benzene rings [centroid–centroid distance = 3.836 (9) Å] are observed.

Related literature top

For general background to the applications of coordination polymers, see: Guo et al. (2009); Wang et al. (2009); Zang et al. (2006). For a related structure, see: Wang (2011).

Experimental top

The synthesis was performed under hydrothermal conditions. A mixture of Mn(CH3COO)2.4H2O (0.2 mmol, 0.049 g), 4-(1,2,4-triazol-4-yl)benzoic acid (0.4 mmol, 0.075 g), NaOH (0.4 mmol, 0.016 g) and H2O (15 ml) in a 25 ml stainless steel reactor with a Teflon liner was heated from 293 to 443 K in 2 h and a constant temperature was maintained at 443 K for 72 h. After the mixture was cooled to 298 K, purple crystals of the title compound were obtained from the reaction.

Refinement top

H atoms on C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). H atoms of water molecules were located in a difference Fourier map and refined with an O—H distance restraint of 0.85 (2) Å and with Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x, y, 3/2-z.]
[Figure 2] Fig. 2. View of the three-dimensional network of the title compound, built by hydrogen bonds (dashed lines).
Tetraaquabis[4-(4H-1,2,4-triazol-4-yl)benzoato- κN1]manganese(II) decahydrate top
Crystal data top
[Mn(C9H6N3O2)2(H2O)4]·10H2OF(000) = 1436
Mr = 683.50Dx = 1.410 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3198 reflections
a = 25.9966 (13) Åθ = 1.0–26.1°
b = 7.9393 (4) ŵ = 0.49 mm−1
c = 16.8495 (9) ÅT = 76 K
β = 112.214 (1)°Block, purple
V = 3219.5 (3) Å30.28 × 0.23 × 0.20 mm
Z = 4
Data collection top
Bruker APEX CCD
diffractometer		3189 independent reflections
Radiation source: fine-focus sealed tube2760 reflections with I > 2σ(I)
graphiteRint = 0.023
φ and ω scansθmax = 26.1°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −19→32
Tmin = 0.85, Tmax = 0.91k = −8→9
8592 measured reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.036P)2 + 1.9266P]
where P = (Fo2 + 2Fc2)/3
3189 reflections(Δ/σ)max = 0.008
238 parametersΔρmax = 0.27 e Å−3
14 restraintsΔρmin = −0.22 e Å−3
Crystal data top
[Mn(C9H6N3O2)2(H2O)4]·10H2OV = 3219.5 (3) Å3
Mr = 683.50Z = 4
Monoclinic, C2/cMo Kα radiation
a = 25.9966 (13) ŵ = 0.49 mm−1
b = 7.9393 (4) ÅT = 76 K
c = 16.8495 (9) Å0.28 × 0.23 × 0.20 mm
β = 112.214 (1)°
Data collection top
Bruker APEX CCD
diffractometer		3189 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		2760 reflections with I > 2σ(I)
Tmin = 0.85, Tmax = 0.91Rint = 0.023
8592 measured reflectionsθmax = 26.1°
Refinement top
R[F2 > 2σ(F2)] = 0.029H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073Δρmax = 0.27 e Å−3
S = 0.99Δρmin = −0.22 e Å−3
3189 reflectionsAbsolute structure: ?
238 parametersFlack parameter: ?
14 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.12836 (6)0.4382 (2)0.87216 (9)0.0226 (3)
H10.13680.46740.82370.027*
C20.13557 (6)0.3880 (2)1.00119 (10)0.0263 (4)
H20.15040.37521.06170.032*
C30.22362 (6)0.48018 (19)0.98458 (9)0.0195 (3)
C40.24336 (6)0.5736 (2)0.93267 (9)0.0229 (3)
H40.21900.60710.87700.027*
C50.29901 (6)0.6175 (2)0.96291 (10)0.0232 (3)
H50.31290.68010.92720.028*
C60.33496 (6)0.57157 (18)1.04481 (9)0.0200 (3)
C70.31413 (6)0.47742 (19)1.09554 (9)0.0229 (3)
H70.33830.44511.15150.027*
C80.25869 (6)0.42984 (19)1.06575 (10)0.0231 (3)
H80.24500.36381.10050.028*
C90.39483 (6)0.62809 (19)1.07889 (10)0.0210 (3)
N10.07926 (5)0.39357 (16)0.86873 (8)0.0218 (3)
N20.08381 (5)0.36106 (18)0.95205 (8)0.0266 (3)
N30.16569 (5)0.43720 (16)0.95412 (8)0.0203 (3)
O10.42246 (4)0.60776 (13)1.15861 (7)0.0245 (2)
O20.41384 (4)0.69525 (16)1.02887 (7)0.0324 (3)
Mn10.00000.39602 (4)0.75000.01689 (10)
O1W0.05118 (5)0.41965 (15)0.67562 (7)0.0284 (3)
H1A0.0417 (8)0.493 (2)0.6382 (11)0.043*
H1B0.0664 (8)0.341 (2)0.6578 (12)0.043*
O2W0.00000.6681 (2)0.75000.0256 (3)
H2A0.0229 (7)0.732 (2)0.7865 (11)0.038*
O3W0.00000.1260 (2)0.75000.0381 (4)
H3A0.0248 (8)0.065 (3)0.7856 (12)0.057*
O4W0.02208 (5)0.69006 (15)0.56446 (7)0.0278 (3)
H4A−0.0110 (6)0.724 (2)0.5514 (12)0.042*
H4B0.0298 (8)0.688 (3)0.5212 (11)0.042*
O5W0.10937 (5)0.17426 (16)0.63970 (8)0.0301 (3)
H5A0.1048 (8)0.174 (3)0.5870 (10)0.045*
H5B0.1054 (9)0.075 (2)0.6528 (13)0.045*
O6W0.29468 (5)0.16683 (18)1.25059 (9)0.0427 (3)
H6A0.2976 (10)0.062 (2)1.2643 (15)0.064*
H6B0.3218 (8)0.217 (3)1.2862 (13)0.064*
O7W0.19555 (5)0.32849 (17)1.21048 (8)0.0363 (3)
H7A0.2252 (7)0.272 (3)1.2263 (14)0.054*
H7B0.1697 (8)0.268 (3)1.2113 (14)0.054*
O8W0.39715 (5)0.64318 (16)1.30252 (8)0.0318 (3)
H8A0.4037 (8)0.640 (3)1.2571 (11)0.048*
H8B0.4240 (7)0.696 (3)1.3407 (12)0.048*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0166 (7)0.0320 (8)0.0177 (7)−0.0016 (6)0.0046 (6)0.0000 (6)
C20.0190 (8)0.0397 (9)0.0194 (8)−0.0045 (7)0.0061 (6)0.0039 (7)
C30.0131 (7)0.0232 (8)0.0205 (7)−0.0022 (6)0.0043 (6)−0.0030 (6)
C40.0179 (7)0.0326 (9)0.0153 (7)−0.0009 (6)0.0030 (6)0.0011 (6)
C50.0192 (8)0.0307 (9)0.0202 (8)−0.0038 (6)0.0081 (6)0.0007 (6)
C60.0163 (7)0.0214 (8)0.0213 (7)−0.0010 (6)0.0059 (6)−0.0036 (6)
C70.0181 (7)0.0271 (8)0.0187 (7)−0.0005 (6)0.0015 (6)0.0020 (6)
C80.0197 (8)0.0272 (8)0.0208 (8)−0.0035 (6)0.0059 (6)0.0049 (6)
C90.0171 (7)0.0219 (8)0.0232 (8)−0.0008 (6)0.0065 (6)−0.0032 (6)
N10.0169 (6)0.0286 (7)0.0188 (6)−0.0017 (5)0.0055 (5)0.0004 (5)
N20.0180 (6)0.0403 (8)0.0199 (7)−0.0037 (6)0.0054 (5)0.0032 (6)
N30.0145 (6)0.0272 (7)0.0174 (6)−0.0024 (5)0.0040 (5)0.0001 (5)
O10.0164 (5)0.0294 (6)0.0218 (6)−0.0021 (4)0.0005 (4)−0.0002 (5)
O20.0201 (6)0.0497 (8)0.0257 (6)−0.0113 (5)0.0070 (5)−0.0001 (5)
Mn10.01246 (16)0.01903 (17)0.01757 (17)0.0000.00386 (12)0.000
O1W0.0300 (6)0.0310 (7)0.0296 (6)0.0080 (5)0.0173 (5)0.0054 (5)
O2W0.0204 (8)0.0201 (8)0.0269 (9)0.000−0.0017 (7)0.000
O3W0.0310 (10)0.0205 (9)0.0420 (11)0.000−0.0100 (8)0.000
O4W0.0209 (6)0.0408 (7)0.0226 (6)0.0057 (5)0.0092 (5)0.0024 (5)
O5W0.0345 (7)0.0308 (6)0.0286 (6)0.0019 (5)0.0161 (5)−0.0011 (5)
O6W0.0335 (7)0.0381 (8)0.0489 (9)−0.0018 (6)0.0070 (6)−0.0009 (7)
O7W0.0291 (7)0.0362 (7)0.0402 (7)−0.0020 (6)0.0092 (6)0.0045 (6)
O8W0.0277 (7)0.0374 (7)0.0319 (7)−0.0053 (5)0.0131 (5)−0.0047 (6)
Geometric parameters (Å, °) top
C1—N11.3049 (19)N1—N21.3877 (17)
C1—N31.3549 (19)Mn1—N12.2652 (12)
C1—H10.9500Mn1—O3W2.1438 (17)
C2—N21.304 (2)Mn1—O1W2.1534 (11)
C2—N31.365 (2)Mn1—O2W2.1598 (16)
C2—H20.9500O1W—H1A0.82 (2)
C3—C41.385 (2)O1W—H1B0.85 (2)
C3—C81.385 (2)O2W—H2A0.84 (1)
C3—N31.4363 (18)O3W—H3A0.85 (2)
C4—C51.384 (2)O4W—H4A0.85 (2)
C4—H40.9500O4W—H4B0.82 (2)
C5—C61.391 (2)O5W—H5A0.85 (2)
C5—H50.9500O5W—H5B0.83 (2)
C6—C71.390 (2)O6W—H6A0.86 (2)
C6—C91.509 (2)O6W—H6B0.83 (2)
C7—C81.387 (2)O7W—H7A0.84 (2)
C7—H70.9500O7W—H7B0.83 (2)
C8—H80.9500O8W—H8A0.84 (2)
C9—O21.2466 (18)O8W—H8B0.86 (2)
C9—O11.2715 (18)
N1—C1—N3110.81 (13)C2—N2—N1106.54 (12)
N1—C1—H1124.6C1—N3—C2104.28 (12)
N3—C1—H1124.6C1—N3—C3127.81 (12)
N2—C2—N3111.04 (14)C2—N3—C3127.91 (13)
N2—C2—H2124.5O3W—Mn1—O1W95.00 (3)
N3—C2—H2124.5O3W—Mn1—O1Wi95.00 (3)
C4—C3—C8121.02 (13)O1W—Mn1—O1Wi170.01 (7)
C4—C3—N3119.36 (13)O3W—Mn1—O2W180.000 (1)
C8—C3—N3119.61 (13)O1W—Mn1—O2W85.00 (3)
C5—C4—C3119.19 (14)O1Wi—Mn1—O2W85.00 (3)
C5—C4—H4120.4O3W—Mn1—N189.51 (3)
C3—C4—H4120.4O1W—Mn1—N187.64 (4)
C4—C5—C6121.04 (14)O1Wi—Mn1—N192.44 (4)
C4—C5—H5119.5O2W—Mn1—N190.49 (3)
C6—C5—H5119.5O3W—Mn1—N1i89.51 (3)
C7—C6—C5118.62 (13)O1W—Mn1—N1i92.44 (4)
C7—C6—C9120.75 (13)O1Wi—Mn1—N1i87.64 (4)
C5—C6—C9120.59 (13)O2W—Mn1—N1i90.49 (3)
C8—C7—C6121.12 (14)N1—Mn1—N1i179.02 (7)
C8—C7—H7119.4Mn1—O1W—H1A115.8 (14)
C6—C7—H7119.4Mn1—O1W—H1B127.7 (14)
C3—C8—C7118.98 (14)H1A—O1W—H1B107.0 (19)
C3—C8—H8120.5Mn1—O2W—H2A127.0 (13)
C7—C8—H8120.5Mn1—O3W—H3A125.0 (15)
O2—C9—O1123.96 (14)H4A—O4W—H4B109.8 (19)
O2—C9—C6119.03 (13)H5A—O5W—H5B107 (2)
O1—C9—C6116.98 (13)H6A—O6W—H6B108 (2)
C1—N1—N2107.33 (12)H7A—O7W—H7B110 (2)
C1—N1—Mn1125.78 (10)H8A—O8W—H8B108 (2)
N2—N1—Mn1126.61 (9)
C8—C3—C4—C5−0.3 (2)Mn1—N1—N2—C2−174.12 (11)
N3—C3—C4—C5178.76 (14)N1—C1—N3—C20.07 (18)
C3—C4—C5—C6−1.0 (2)N1—C1—N3—C3−179.24 (14)
C4—C5—C6—C71.2 (2)N2—C2—N3—C1−0.05 (18)
C4—C5—C6—C9−176.69 (14)N2—C2—N3—C3179.26 (14)
C5—C6—C7—C8−0.1 (2)C4—C3—N3—C118.3 (2)
C9—C6—C7—C8177.78 (14)C8—C3—N3—C1−162.65 (15)
C4—C3—C8—C71.3 (2)C4—C3—N3—C2−160.86 (16)
N3—C3—C8—C7−177.70 (14)C8—C3—N3—C218.2 (2)
C6—C7—C8—C3−1.2 (2)C1—N1—Mn1—O3W109.92 (13)
C7—C6—C9—O2171.81 (15)N2—N1—Mn1—O3W−76.98 (12)
C5—C6—C9—O2−10.4 (2)C1—N1—Mn1—O1W14.90 (13)
C7—C6—C9—O1−10.1 (2)N2—N1—Mn1—O1W−172.00 (12)
C5—C6—C9—O1167.71 (14)C1—N1—Mn1—O1Wi−155.10 (13)
N3—C1—N1—N2−0.06 (18)N2—N1—Mn1—O1Wi18.00 (12)
N3—C1—N1—Mn1174.15 (10)C1—N1—Mn1—O2W−70.08 (13)
N3—C2—N2—N10.02 (19)N2—N1—Mn1—O2W103.02 (12)
C1—N1—N2—C20.02 (17)
Symmetry codes: (i) −x, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O4W0.82 (2)1.94 (2)2.7602 (17)171 (2)
O1W—H1B···O5W0.85 (2)1.83 (2)2.6724 (16)169 (2)
O2W—H2A···O1ii0.84 (1)1.87 (1)2.6936 (15)164 (2)
O3W—H3A···O1iii0.85 (2)1.91 (2)2.7445 (15)166 (2)
O4W—H4A···O2iv0.85 (2)1.95 (2)2.7985 (15)176 (2)
O4W—H4B···N2v0.82 (2)2.17 (2)2.9369 (17)154 (2)
O5W—H5A···O2vi0.85 (2)1.83 (2)2.6765 (16)171 (2)
O5W—H5B···O8Wiii0.83 (2)1.90 (2)2.7299 (18)172 (2)
O6W—H6A···O7Wvii0.86 (2)1.89 (2)2.754 (2)177 (2)
O6W—H6B···O5Wiii0.83 (2)1.95 (2)2.7828 (18)173 (2)
O7W—H7A···O6W0.84 (2)1.89 (2)2.7256 (19)171 (2)
O7W—H7B···O8Wvii0.83 (2)1.94 (2)2.7605 (18)171 (2)
O8W—H8A···O10.84 (2)1.92 (2)2.7564 (16)173 (2)
O8W—H8B···O4Wii0.86 (2)1.91 (2)2.7616 (17)172 (2)
Symmetry codes: (ii) −x+1/2, −y+3/2, −z+2; (iii) −x+1/2, −y+1/2, −z+2; (iv) x−1/2, −y+3/2, z−1/2; (v) x, −y+1, z−1/2; (vi) −x+1/2, y−1/2, −z+3/2; (vii) −x+1/2, y−1/2, −z+5/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1A···O4W0.82 (2)1.94 (2)2.7602 (17)171 (2)
O1W—H1B···O5W0.85 (2)1.83 (2)2.6724 (16)169 (2)
O2W—H2A···O1i0.84 (1)1.87 (1)2.6936 (15)164 (2)
O3W—H3A···O1ii0.85 (2)1.91 (2)2.7445 (15)166 (2)
O4W—H4A···O2iii0.85 (2)1.95 (2)2.7985 (15)176 (2)
O4W—H4B···N2iv0.82 (2)2.17 (2)2.9369 (17)154 (2)
O5W—H5A···O2v0.85 (2)1.83 (2)2.6765 (16)171 (2)
O5W—H5B···O8Wii0.83 (2)1.90 (2)2.7299 (18)172 (2)
O6W—H6A···O7Wvi0.86 (2)1.89 (2)2.754 (2)177 (2)
O6W—H6B···O5Wii0.83 (2)1.95 (2)2.7828 (18)173 (2)
O7W—H7A···O6W0.84 (2)1.89 (2)2.7256 (19)171 (2)
O7W—H7B···O8Wvi0.83 (2)1.94 (2)2.7605 (18)171 (2)
O8W—H8A···O10.84 (2)1.92 (2)2.7564 (16)173 (2)
O8W—H8B···O4Wi0.86 (2)1.91 (2)2.7616 (17)172 (2)
Symmetry codes: (i) −x+1/2, −y+3/2, −z+2; (ii) −x+1/2, −y+1/2, −z+2; (iii) x−1/2, −y+3/2, z−1/2; (iv) x, −y+1, z−1/2; (v) −x+1/2, y−1/2, −z+3/2; (vi) −x+1/2, y−1/2, −z+5/2.
Acknowledgements top

The authors thank Yanbian University for supporting this work.

references
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