catena-Poly[[triaqua­manganese(II)]-μ-1,2,4-triazole-3,5-dicarboxyl­ato-κ³O³:N⁴,O⁵]

In the title compound, [Mn(C₄HN₃O₄)(H₂O)₃]_n, 1,2,4-triazole-3,5-dicarboxyl­ate ligand adopts a tridentate bridging mode, linking Mn^II ions into one-dimensional linear chains. In the crystal structure, inter­molecular N—H...O, O—H...N and O—H...O hydrogen bonds involving carboxyl­ate O atoms, triazole groups and water mol­ecules form a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](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

---

S1. Comment

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 Mn^II 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 Mn^II 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.

Related literature

For background information, see: Batten & Robson (1998); Munakata et al., (1996); Lemoine et al., (2006); Baitalik et al. (2004).

S2. Experimental

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%.

S3. Refinement

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 U_iso(H) = 1.2U_eq(N) and U_iso(H) = 1.5U_eq(O).

Computing details

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.

Figures

	Fig. 1. Part of the one-dimensional chain structure of (I). Displacement ellipsoids are drawn at the 30% probability level. Symmetry code: (A) x + 1/2, -y + 1/2, z + 1/2.
	Fig. 2. A section of the one-dimenional chain structure of (I).
	Fig. 3. Part of the crystal structure of (I). Red dashed lines represent O—H···O hydrogen bonds and purple dashed lines represent N—H···O hydrogen bonds.

catena-Poly[[triaquamanganese(II)]-µ-1,2,4-triazole-3,5-dicarboxylato- κ³O³:N⁴,O⁵]

Crystal data

[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) Å^3	0.32 × 0.10 × 0.08 mm
Z = 4

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.021	H-atom parameters constrained
wR(F^2) = 0.058	w = 1/[σ^2(Fo^2) + (0.0302P)^2] where P = (Fo^2 + 2Fc^2)/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)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Mn1—O3^i	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—Mn1^ii	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
O3^i—Mn1—O5	92.32 (5)	Mn1—O7—H7A	116.7
O3^i—Mn1—O6	101.70 (5)	Mn1—O7—H7B	115.5
O5—Mn1—O6	85.71 (5)	H7A—O7—H7B	115.3
O3^i—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)
O3^i—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
O3^i—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—Mn1^ii	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
O3^i—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)
O3^i—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)
O3^i—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)	Mn1^ii—O3—C4—O4	111.0 (2)
C2—N2—N3—C3	0.72 (18)	Mn1^ii—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1^ii	0.86	1.94	2.7674 (18)	162
O5—H5A···O2^iii	0.85	1.87	2.6958 (18)	165
O5—H5B···O6^iv	0.85	2.23	2.903 (2)	136
O6—H6A···O4	0.85	1.85	2.7019 (19)	175
O6—H6B···O3^v	0.85	1.93	2.7653 (18)	169
O7—H7A···N2^vi	0.85	2.10	2.921 (2)	163
O7—H7B···O4^v	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.