Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807021563/lh2379sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807021563/lh2379Isup2.hkl |
CCDC reference: 650585
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.021
- wR factor = 0.058
- Data-to-parameter ratio = 11.2
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.12 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 9
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For background information, see: Batten & Robson (1998); Munakata et al., (1996); Lemoine et al., (2006); Baitalik et al. (2004).
A methanol solution (15 ml) of L (0.7 mmol) was slowly added to an aqueous solution (10 ml) of MnCl26H2O (0.7 mmol). The resulting solution was stirred and refluxed for 3 h at room temperature. The resulting solution was filtered. After 14 days white prism crystals suitable for x-ray diffraction were obtained from the filtrate. elemental analysis, calculated for C4H7MnN3O7: C 18.19, H 2.67, N 15.91%; found: C 18.30, H 2.69, N 15.84%.
H atoms were placed in calculated positions with O—H = 0.85 and N—H = 0.86 Å. They were included in the riding-motion approximation with Uiso(H) = 1.2Ueq(N) and Uiso(H) = 1.5Ueq(O).
In the past few decades metal organic coordination compounds have received great interest not only because of their wide application in materials science but also their interesting structural motifs (Batten & Robson, 1998; Munakata et al., 1996). In the rational design and synthesis of these coordiantion polymers, serveral important tuning factors should be considered, such as the ligand functional groups, the metal(II) centers preference and weak but highly directed secondary hydrogen bond interactions. Ligands simultaneously containing O– and N– donor groups are favored e.g. pyridine-polycarboxylic acid ligands, imidazole-polycarboxylic acid ligands. These types of ligands have exhibited numerous different coordination modes and form novel coordination polymers with novel properties (Lemoine et al., 2006). Compared to those ligands above, complexes of 1,2,4-triazole-3,5-dicarboxylic acid ligands have been less investigated but a study of these types of complexes has been carried out by Baitalik et al. (2004). Mn(II) compounds are also interesting because many Mn(II) compounds exhbit mangnetic properties such as single molecule magnets (SMMS). In this paper, a new one-dimensional complex [Mn(L)(H3O)]n (1), where L = 3,5-dicarboxylic acid-1,2,4-triazole has been isolated and its single-crystal structure has been determined.
Part of the structure of (I) is shown in Fig. 1. The MnII ion is in a slightly distorted octahedral coordination geometry formed by three coordinated water molecules, one N atom, one carboxylate O atom in a bidentate mode from one L ligand and one carboxylate O atom from a symmetry related L Ligand in a monodentate mode. Hence, the L ligands adopts a tridentate bridging mode to MnII ions forming a one-dimensional linear chain structure (Fig. 2). Due to the functional groups of L, numerous hydrogen bond interactions are present. In the crystal structure intermolecular N—H···O and O—H···O hydrogen bonds involving carboxylate O atoms, triazole groups and coordinated water molecules form a three-dimensional network.
For background information, see: Batten & Robson (1998); Munakata et al., (1996); Lemoine et al., (2006); Baitalik et al. (2004).
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
[Mn(C4HN3O4)(H2O)3] | F(000) = 532 |
Mr = 264.07 | Dx = 2.003 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2564 reflections |
a = 10.8389 (9) Å | θ = 3.0–27.7° |
b = 6.7367 (6) Å | µ = 1.53 mm−1 |
c = 12.5802 (11) Å | T = 293 K |
β = 107.546 (1)° | Prism, colorless |
V = 875.85 (13) Å3 | 0.32 × 0.10 × 0.08 mm |
Z = 4 |
Bruker APEXII diffractometer | 1528 independent reflections |
Radiation source: fine-focus sealed tube | 1386 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 25.0°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→12 |
Tmin = 0.861, Tmax = 0.882 | k = −7→8 |
4544 measured reflections | l = −9→14 |
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)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.058 | w = 1/[σ2(Fo2) + (0.0302P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
1528 reflections | Δρmax = 0.32 e Å−3 |
136 parameters | Δρmin = −0.25 e Å−3 |
9 restraints | Extinction correction: SHELXL97 |
Primary atom site location: constr | Extinction coefficient: 0.257 (15) |
[Mn(C4HN3O4)(H2O)3] | V = 875.85 (13) Å3 |
Mr = 264.07 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.8389 (9) Å | µ = 1.53 mm−1 |
b = 6.7367 (6) Å | T = 293 K |
c = 12.5802 (11) Å | 0.32 × 0.10 × 0.08 mm |
β = 107.546 (1)° |
Bruker APEXII diffractometer | 1528 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1386 reflections with I > 2σ(I) |
Tmin = 0.861, Tmax = 0.882 | Rint = 0.018 |
4544 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 9 restraints |
wR(F2) = 0.058 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.32 e Å−3 |
1528 reflections | Δρmin = −0.25 e Å−3 |
136 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 | ||
Mn1 | 0.82891 (2) | 0.18703 (4) | 0.54821 (2) | 0.01986 (11) | |
O1 | 0.71670 (11) | 0.14416 (19) | 0.66411 (10) | 0.0239 (3) | |
O2 | 0.51740 (12) | 0.1395 (2) | 0.68205 (10) | 0.0291 (3) | |
O3 | 0.49076 (11) | 0.44584 (19) | 0.16752 (9) | 0.0255 (3) | |
O4 | 0.69816 (12) | 0.3869 (3) | 0.25424 (11) | 0.0382 (4) | |
O5 | 0.88499 (15) | 0.4806 (2) | 0.61302 (11) | 0.0391 (4) | |
H5A | 0.9132 | 0.5107 | 0.6817 | 0.059* | |
H5B | 0.9115 | 0.5538 | 0.5693 | 0.059* | |
O6 | 0.91075 (12) | 0.26752 (19) | 0.41689 (10) | 0.0241 (3) | |
H6A | 0.8465 | 0.3112 | 0.3650 | 0.036* | |
H6B | 0.9509 | 0.1723 | 0.3977 | 0.036* | |
O7 | 0.79141 (12) | −0.1105 (2) | 0.47093 (10) | 0.0274 (3) | |
H7A | 0.7348 | −0.1811 | 0.4875 | 0.041* | |
H7B | 0.7905 | −0.1167 | 0.4032 | 0.041* | |
N1 | 0.62527 (13) | 0.2778 (2) | 0.45004 (11) | 0.0180 (3) | |
N2 | 0.42098 (14) | 0.2723 (2) | 0.45785 (11) | 0.0197 (3) | |
N3 | 0.42449 (13) | 0.3315 (2) | 0.35623 (11) | 0.0200 (3) | |
H3 | 0.3578 | 0.3638 | 0.3019 | 0.024* | |
C1 | 0.59476 (16) | 0.1698 (2) | 0.63011 (14) | 0.0191 (4) | |
C2 | 0.54429 (15) | 0.2424 (2) | 0.51157 (13) | 0.0169 (3) | |
C3 | 0.54639 (16) | 0.3330 (2) | 0.35194 (14) | 0.0175 (4) | |
C4 | 0.58276 (16) | 0.3916 (3) | 0.25006 (14) | 0.0214 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.01684 (16) | 0.02659 (18) | 0.01511 (16) | −0.00047 (10) | 0.00324 (11) | −0.00061 (10) |
O1 | 0.0167 (6) | 0.0371 (7) | 0.0158 (6) | 0.0002 (5) | 0.0017 (5) | 0.0041 (5) |
O2 | 0.0247 (7) | 0.0450 (8) | 0.0201 (6) | 0.0023 (6) | 0.0106 (5) | 0.0097 (6) |
O3 | 0.0212 (6) | 0.0360 (7) | 0.0157 (6) | −0.0045 (5) | 0.0000 (5) | 0.0057 (5) |
O4 | 0.0223 (7) | 0.0673 (10) | 0.0258 (7) | 0.0048 (7) | 0.0086 (6) | 0.0159 (7) |
O5 | 0.0610 (10) | 0.0352 (8) | 0.0237 (7) | −0.0218 (7) | 0.0168 (7) | −0.0089 (6) |
O6 | 0.0228 (6) | 0.0284 (7) | 0.0216 (6) | 0.0018 (5) | 0.0073 (5) | 0.0003 (5) |
O7 | 0.0273 (7) | 0.0319 (7) | 0.0253 (7) | −0.0069 (6) | 0.0117 (5) | −0.0038 (6) |
N1 | 0.0174 (7) | 0.0212 (7) | 0.0147 (7) | −0.0010 (6) | 0.0039 (6) | 0.0011 (6) |
N2 | 0.0198 (7) | 0.0242 (8) | 0.0152 (7) | 0.0004 (6) | 0.0053 (6) | 0.0022 (6) |
N3 | 0.0175 (7) | 0.0253 (8) | 0.0145 (7) | 0.0012 (6) | 0.0010 (6) | 0.0030 (6) |
C1 | 0.0222 (9) | 0.0184 (9) | 0.0152 (8) | −0.0011 (7) | 0.0035 (7) | −0.0003 (6) |
C2 | 0.0189 (8) | 0.0170 (8) | 0.0146 (8) | −0.0006 (7) | 0.0046 (6) | −0.0014 (7) |
C3 | 0.0172 (8) | 0.0188 (8) | 0.0155 (8) | −0.0001 (6) | 0.0032 (7) | −0.0004 (6) |
C4 | 0.0212 (9) | 0.0252 (9) | 0.0170 (9) | −0.0018 (7) | 0.0047 (7) | 0.0013 (7) |
Mn1—O3i | 2.1317 (12) | O6—H6A | 0.8501 |
Mn1—O5 | 2.1557 (14) | O6—H6B | 0.8502 |
Mn1—O6 | 2.1665 (12) | O7—H7A | 0.8499 |
Mn1—O1 | 2.1812 (12) | O7—H7B | 0.8499 |
Mn1—O7 | 2.2115 (13) | N1—C3 | 1.325 (2) |
Mn1—N1 | 2.2644 (14) | N1—C2 | 1.355 (2) |
O1—C1 | 1.272 (2) | N2—C2 | 1.319 (2) |
O2—C1 | 1.225 (2) | N2—N3 | 1.3507 (19) |
O3—C4 | 1.258 (2) | N3—C3 | 1.339 (2) |
O3—Mn1ii | 2.1317 (12) | N3—H3 | 0.8600 |
O4—C4 | 1.236 (2) | C1—C2 | 1.507 (2) |
O5—H5A | 0.8500 | C3—C4 | 1.503 (2) |
O5—H5B | 0.8501 | ||
O3i—Mn1—O5 | 92.32 (5) | Mn1—O7—H7A | 116.7 |
O3i—Mn1—O6 | 101.70 (5) | Mn1—O7—H7B | 115.5 |
O5—Mn1—O6 | 85.71 (5) | H7A—O7—H7B | 115.3 |
O3i—Mn1—O1 | 88.86 (5) | C3—N1—C2 | 103.55 (13) |
O5—Mn1—O1 | 91.09 (5) | C3—N1—Mn1 | 146.39 (12) |
O6—Mn1—O1 | 169.07 (5) | C2—N1—Mn1 | 109.49 (10) |
O3i—Mn1—O7 | 86.11 (5) | C2—N2—N3 | 102.52 (13) |
O5—Mn1—O7 | 172.49 (5) | C3—N3—N2 | 110.49 (13) |
O6—Mn1—O7 | 87.42 (5) | C3—N3—H3 | 124.8 |
O1—Mn1—O7 | 96.21 (5) | N2—N3—H3 | 124.8 |
O3i—Mn1—N1 | 163.21 (5) | O2—C1—O1 | 127.34 (16) |
O5—Mn1—N1 | 94.36 (6) | O2—C1—C2 | 118.63 (15) |
O6—Mn1—N1 | 94.15 (5) | O1—C1—C2 | 114.02 (15) |
O1—Mn1—N1 | 75.64 (5) | N2—C2—N1 | 114.30 (14) |
O7—Mn1—N1 | 89.15 (5) | N2—C2—C1 | 124.48 (15) |
C1—O1—Mn1 | 119.30 (11) | N1—C2—C1 | 121.21 (14) |
C4—O3—Mn1ii | 137.63 (12) | N1—C3—N3 | 109.14 (15) |
Mn1—O5—H5A | 125.3 | N1—C3—C4 | 127.34 (15) |
Mn1—O5—H5B | 113.5 | N3—C3—C4 | 123.51 (15) |
H5A—O5—H5B | 115.5 | O4—C4—O3 | 125.64 (16) |
Mn1—O6—H6A | 104.1 | O4—C4—C3 | 118.63 (15) |
Mn1—O6—H6B | 113.0 | O3—C4—C3 | 115.71 (15) |
H6A—O6—H6B | 114.5 | ||
O3i—Mn1—O1—C1 | −168.50 (13) | C3—N1—C2—N2 | −0.03 (19) |
O5—Mn1—O1—C1 | 99.19 (13) | Mn1—N1—C2—N2 | −173.78 (12) |
O6—Mn1—O1—C1 | 26.4 (3) | C3—N1—C2—C1 | 178.38 (15) |
O7—Mn1—O1—C1 | −82.55 (12) | Mn1—N1—C2—C1 | 4.63 (19) |
N1—Mn1—O1—C1 | 4.98 (12) | O2—C1—C2—N2 | −1.5 (3) |
O3i—Mn1—N1—C3 | −150.53 (19) | O1—C1—C2—N2 | 177.48 (16) |
O5—Mn1—N1—C3 | 96.3 (2) | O2—C1—C2—N1 | −179.79 (16) |
O6—Mn1—N1—C3 | 10.3 (2) | O1—C1—C2—N1 | −0.8 (2) |
O1—Mn1—N1—C3 | −173.7 (2) | C2—N1—C3—N3 | 0.49 (18) |
O7—Mn1—N1—C3 | −77.0 (2) | Mn1—N1—C3—N3 | 169.80 (15) |
O3i—Mn1—N1—C2 | 18.4 (2) | C2—N1—C3—C4 | 179.80 (16) |
O5—Mn1—N1—C2 | −94.71 (11) | Mn1—N1—C3—C4 | −10.9 (3) |
O6—Mn1—N1—C2 | 179.28 (11) | N2—N3—C3—N1 | −0.79 (19) |
O1—Mn1—N1—C2 | −4.70 (10) | N2—N3—C3—C4 | 179.86 (15) |
O7—Mn1—N1—C2 | 91.93 (11) | Mn1ii—O3—C4—O4 | 111.0 (2) |
C2—N2—N3—C3 | 0.72 (18) | Mn1ii—O3—C4—C3 | −70.5 (2) |
Mn1—O1—C1—O2 | 174.89 (14) | N1—C3—C4—O4 | 1.2 (3) |
Mn1—O1—C1—C2 | −4.03 (19) | N3—C3—C4—O4 | −179.56 (17) |
N3—N2—C2—N1 | −0.42 (19) | N1—C3—C4—O3 | −177.38 (16) |
N3—N2—C2—C1 | −178.77 (15) | N3—C3—C4—O3 | 1.8 (2) |
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 |
N3—H3···O1ii | 0.86 | 1.94 | 2.7674 (18) | 162 |
O5—H5A···O2iii | 0.85 | 1.87 | 2.6958 (18) | 165 |
O5—H5B···O6iv | 0.85 | 2.23 | 2.903 (2) | 136 |
O6—H6A···O4 | 0.85 | 1.85 | 2.7019 (19) | 175 |
O6—H6B···O3v | 0.85 | 1.93 | 2.7653 (18) | 169 |
O7—H7A···N2vi | 0.85 | 2.10 | 2.921 (2) | 163 |
O7—H7B···O4v | 0.85 | 2.02 | 2.8688 (18) | 175 |
Symmetry codes: (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+3/2, y+1/2, −z+3/2; (iv) −x+2, −y+1, −z+1; (v) −x+3/2, y−1/2, −z+1/2; (vi) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C4HN3O4)(H2O)3] |
Mr | 264.07 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 10.8389 (9), 6.7367 (6), 12.5802 (11) |
β (°) | 107.546 (1) |
V (Å3) | 875.85 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.53 |
Crystal size (mm) | 0.32 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Bruker APEXII |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.861, 0.882 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4544, 1528, 1386 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.058, 1.05 |
No. of reflections | 1528 |
No. of parameters | 136 |
No. of restraints | 9 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.25 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1i | 0.86 | 1.94 | 2.7674 (18) | 162 |
O5—H5A···O2ii | 0.85 | 1.87 | 2.6958 (18) | 165 |
O5—H5B···O6iii | 0.85 | 2.23 | 2.903 (2) | 136 |
O6—H6A···O4 | 0.85 | 1.85 | 2.7019 (19) | 175 |
O6—H6B···O3iv | 0.85 | 1.93 | 2.7653 (18) | 169 |
O7—H7A···N2v | 0.85 | 2.10 | 2.921 (2) | 163 |
O7—H7B···O4iv | 0.85 | 2.02 | 2.8688 (18) | 175 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y−1/2, −z+1/2; (v) −x+1, −y, −z+1. |
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In the past few decades metal organic coordination compounds have received great interest not only because of their wide application in materials science but also their interesting structural motifs (Batten & Robson, 1998; Munakata et al., 1996). In the rational design and synthesis of these coordiantion polymers, serveral important tuning factors should be considered, such as the ligand functional groups, the metal(II) centers preference and weak but highly directed secondary hydrogen bond interactions. Ligands simultaneously containing O– and N– donor groups are favored e.g. pyridine-polycarboxylic acid ligands, imidazole-polycarboxylic acid ligands. These types of ligands have exhibited numerous different coordination modes and form novel coordination polymers with novel properties (Lemoine et al., 2006). Compared to those ligands above, complexes of 1,2,4-triazole-3,5-dicarboxylic acid ligands have been less investigated but a study of these types of complexes has been carried out by Baitalik et al. (2004). Mn(II) compounds are also interesting because many Mn(II) compounds exhbit mangnetic properties such as single molecule magnets (SMMS). In this paper, a new one-dimensional complex [Mn(L)(H3O)]n (1), where L = 3,5-dicarboxylic acid-1,2,4-triazole has been isolated and its single-crystal structure has been determined.
Part of the structure of (I) is shown in Fig. 1. The MnII ion is in a slightly distorted octahedral coordination geometry formed by three coordinated water molecules, one N atom, one carboxylate O atom in a bidentate mode from one L ligand and one carboxylate O atom from a symmetry related L Ligand in a monodentate mode. Hence, the L ligands adopts a tridentate bridging mode to MnII ions forming a one-dimensional linear chain structure (Fig. 2). Due to the functional groups of L, numerous hydrogen bond interactions are present. In the crystal structure intermolecular N—H···O and O—H···O hydrogen bonds involving carboxylate O atoms, triazole groups and coordinated water molecules form a three-dimensional network.