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Acta Cryst. (2009). E65, m487-m488    [ doi:10.1107/S1600536809011982 ]

Tetraaquabis(3,5-di-4-pyridyl-1,2,4-triazolato-[kappa]N)cobalt(II) dihydrate

L. Y. Dong

Abstract top

The CoII atom in the title compound, [Co(C12H8N5)2(H2O)4]·2H2O, lies on a center of inversion and is bonded to two N-heterocycles and to four water molecules in a slightly distorted octahedral coordination. The coordinated and lattice water molecules interact with the N-heterocycles through O-H...N hydrogen bonds, generating a three-dimensional supramolecular architecture.

Comment top

Transition metal complexes with 1,2,4-triazole derivatives as ligands are of great interest as they are the subject of magnetic studies (Haasnoot, 2000). Some complexes containing substituted 1,2,4-triazole ligands have spin-crossover properties, which could be used in molecular-based memory devices, displays and optical switches (Kahn & Martinez, 1998). The ligand 3,5-di(4-pyridine)-1,2,4-triazole (L) is of special interest as it contains multi-dentate donor atoms and shows diverse coordination modes.. Especially only a few examples about the coordinaiton chemistry of L are reported. Some unusual coordination modes of L also have been reported forming interesting supramolecular isomerism systems (Zhang et al., 2006). On the other hand, water is quite important for our common life (Tajkhorshid et al., 2002). It has been the focus of intense research interests for their unusual properties in biological system and also plays an important role in biological self-assembly processes (Sreenivasulu & Vittal, 2004).

In this work, we synthesized a new compound [Co(L)2(H2O)4](H2O)2 (I) (L = 3,5-di(4-pyridine)-1,2,4-triazole). 1 is composed of one cobalt(II) cation, two L ligand, four coordinated and two lattice water molecules. The cobalt(II) cation is six-coordinated in the octahedral geometry. The equatorial site of Cobalt cation is occupied by four aqua molecules while the axial site is occupied by two nitrogen atoms of two mono-dentate L ligands. The mono-dentate coordination mode of L is different from previously reported di-, tri- or tetra-dentate coordination modes of L.

O1, O2 from coordination water molecules and O3 from lattice water molecules generate strong intermolecular hydrogen bondings and construct trinuclear water clusters, in which O3 acts as the hydrogen acceptors and O1, O2 act as hydrogen bonding donors. The hydrogen-bonding distances are 2.791 (4) Å (O1—H1B···O3) and 2.801 (4) Å(O2—H2A···O3), respectively. The average O···O distance is 2.796 (4) Å, which is similar to that(2.75 Å) in the structure of ice (König, 1944).

strong N—H···O hydrogen bonds generated from water molecules and nitrogen atoms of pyridine or triazole groups are also observed rusulting in the three-dimensional supramolecular network(Table 2). π-π stacking interactions between two neighboring triazole groups further consolidating the architecture centroid-centroid distance 3.677 (4) Å]

Perspective drawing with the atomic numbering scheme is illustrated in figure 1. Selected geometric parameters (Å, °) for 1 are listed in table 1. Selected hydrogen-bonding geometric parameters (Å, °) for 1 are listed in table 2. The trinuclear water clusters, corresponding N—H···O hydrogen bonds and π-π stacking are shown in figure 2. The three-dimensional supramolecular packing architecture of (I) is shown in figure 3.

Related literature top

For magnetic studies of transition metal complexes with 1,2,4-triazole derivatives, see: Haasnoot (2000). For the potential applications of complexes containing substituted 1,2,4-triazole ligands with spin-crossover properties in molecular-based memory devices, displays and optical switches, see: Kahn & Martinez (1998). For 3,5-di(4-pyridine)-1,2,4-triazole, see: Zhang et al. (2006); Sreenivasulu & Vittal (2004). For water, see: Tajkhorshid et al. (2002). For the synthesis, see: Basu & Dutta (1964). For related literature, see: König (1944).

Experimental top

The ligand was prepared according to the previous literature (Basu & Dutta, (1964)). [Co(L)2(H2O)4](H2O) (1) (L = 3,5-di(4-pyridine)-1,2,4-triazole) was prepared under the hydrotheraml conditions. [Co(ClO4)2].6H2O (0.2 mmol), L (0.2 mmol) and 18 ml water was added to a 25 ml reaction vessel. the reaction vessel was then sealed and subsequently placed in an oven for 140 h at 160°C. well shaped red block crystals were obtained and washed with ethanol.

Refinement top

The carbon-bound H atoms were positioned geometrically and were allowed to ride on their parent C atoms. The water H atoms were located from a difference density map and were refined with distance restraints of O—H = 0.85±0.01 Å.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure and atom-labeling scheme of (I).
[Figure 2] Fig. 2. The trinuclear water clusters stabling the packing structure of 1.
Tetraaquabis(3,5-di-4-pyridyl-1,2,4-triazolato-κN)cobalt(II) dihydrate top
Crystal data top
[Co(C12H8N5)2(H2O)4]·2(H2O)F(000) = 634
Mr = 611.49Dx = 1.556 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 556 reflections
a = 7.3660 (15) Åθ = 1.5–25.5°
b = 15.654 (3) ŵ = 0.72 mm−1
c = 11.857 (2) ÅT = 293 K
β = 107.34 (3)°Block, red
V = 1305.1 (5) Å30.40 × 0.20 × 0.12 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		2423 independent reflections
Radiation source: fine-focus sealed tube2009 reflections with I > 2σ(I)
graphiteRint = 0.065
φ and ω scansθmax = 25.5°, θmin = 3.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.842, Tmax = 0.917k = −18→18
11054 measured reflectionsl = −14→14
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.054 w = 1/[σ2(Fo2) + (0.0298P)2 + 0.2298P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.108(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.29 e Å−3
2420 reflectionsΔρmin = −0.41 e Å−3
243 parameters
Crystal data top
[Co(C12H8N5)2(H2O)4]·2(H2O)V = 1305.1 (5) Å3
Mr = 611.49Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.3660 (15) ŵ = 0.72 mm−1
b = 15.654 (3) ÅT = 293 K
c = 11.857 (2) Å0.40 × 0.20 × 0.12 mm
β = 107.34 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		2423 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2009 reflections with I > 2σ(I)
Tmin = 0.842, Tmax = 0.917Rint = 0.065
11054 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.108Δρmax = 0.29 e Å−3
S = 1.07Δρmin = −0.41 e Å−3
2420 reflectionsAbsolute structure: ?
243 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3827 (5)0.6826 (2)−0.0776 (3)0.0306 (8)
C20.3536 (5)0.7690 (2)−0.0713 (3)0.0299 (8)
C30.3919 (4)0.80864 (19)0.0377 (3)0.0218 (7)
C40.4634 (5)0.7565 (2)0.1360 (3)0.0290 (8)
C50.4886 (5)0.6711 (2)0.1224 (3)0.0294 (8)
C60.3518 (5)0.8987 (2)0.0514 (3)0.0229 (7)
C70.2496 (5)1.02433 (19)0.0220 (3)0.0241 (7)
C80.1690 (5)1.1049 (2)−0.0324 (3)0.0244 (7)
C90.1117 (5)1.1170 (2)−0.1528 (3)0.0330 (9)
C100.0440 (6)1.1952 (2)−0.1990 (3)0.0368 (9)
C110.0861 (6)1.2510 (3)−0.0181 (4)0.0450 (11)
C120.1540 (6)1.1751 (2)0.0357 (4)0.0403 (10)
Co10.50000.50000.00000.02203 (19)
H10.363 (5)0.657 (2)−0.147 (3)0.033 (10)*
H20.313 (5)0.799 (3)−0.138 (3)0.046 (12)*
H40.495 (5)0.781 (2)0.209 (3)0.034 (10)*
H50.532 (5)0.637 (2)0.187 (3)0.036 (10)*
H90.118 (5)1.075 (2)−0.199 (3)0.028 (10)*
H100.013 (6)1.203 (3)−0.278 (4)0.052 (13)*
H110.078 (6)1.299 (3)0.026 (4)0.057 (13)*
H120.188 (6)1.170 (3)0.116 (4)0.051 (12)*
H1A0.261 (5)0.484 (3)−0.2116 (18)0.069 (16)*
H2A0.276 (4)0.5057 (16)0.135 (3)0.031 (10)*
H3A0.163 (5)0.571 (2)0.2816 (10)0.041 (12)*
H1B0.143 (3)0.475 (3)−0.140 (3)0.077 (17)*
H2B0.416 (6)0.446 (3)0.1861 (19)0.084 (18)*
H3B0.081 (6)0.6269 (11)0.194 (4)0.069 (16)*
N10.4483 (4)0.63277 (16)0.0175 (2)0.0262 (6)
N20.2624 (4)0.95193 (16)−0.0378 (2)0.0229 (6)
N30.3929 (4)0.93481 (17)0.1575 (2)0.0295 (7)
N40.3253 (4)1.01645 (17)0.1389 (2)0.0308 (7)
N50.0298 (4)1.26290 (18)−0.1346 (3)0.0371 (8)
O10.2504 (3)0.49368 (17)−0.1431 (2)0.0334 (6)
O20.3487 (4)0.46767 (16)0.1212 (2)0.0302 (6)
O30.1157 (4)0.57516 (16)0.2069 (2)0.0329 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.047 (2)0.0220 (18)0.0201 (18)0.0038 (16)0.0054 (16)−0.0033 (15)
C20.044 (2)0.0184 (17)0.0245 (19)0.0057 (15)0.0057 (16)0.0020 (15)
C30.0241 (18)0.0184 (16)0.0231 (17)0.0017 (13)0.0074 (14)−0.0003 (13)
C40.043 (2)0.0239 (18)0.0188 (18)0.0052 (16)0.0075 (16)−0.0032 (15)
C50.043 (2)0.0200 (18)0.0232 (19)0.0050 (15)0.0065 (16)0.0043 (14)
C60.0277 (18)0.0182 (16)0.0224 (17)−0.0006 (14)0.0066 (14)0.0000 (13)
C70.0297 (18)0.0194 (17)0.0227 (17)−0.0001 (13)0.0072 (14)0.0002 (13)
C80.0247 (18)0.0211 (17)0.0269 (18)−0.0023 (14)0.0067 (14)−0.0009 (14)
C90.044 (2)0.0231 (19)0.028 (2)0.0046 (16)0.0043 (17)−0.0031 (16)
C100.044 (2)0.033 (2)0.027 (2)0.0034 (17)0.0023 (18)0.0073 (17)
C110.067 (3)0.024 (2)0.045 (3)0.013 (2)0.017 (2)−0.0019 (18)
C120.065 (3)0.027 (2)0.028 (2)0.0129 (18)0.011 (2)0.0002 (16)
Co10.0282 (4)0.0162 (3)0.0206 (3)0.0025 (3)0.0055 (2)0.0004 (3)
N10.0358 (17)0.0170 (14)0.0251 (15)0.0032 (12)0.0081 (12)−0.0001 (11)
N20.0283 (15)0.0154 (14)0.0241 (15)0.0011 (11)0.0063 (12)−0.0011 (11)
N30.0398 (18)0.0213 (15)0.0255 (16)0.0099 (13)0.0065 (13)0.0017 (12)
N40.0461 (18)0.0213 (16)0.0221 (15)0.0069 (13)0.0057 (13)−0.0013 (11)
N50.044 (2)0.0223 (16)0.044 (2)0.0079 (14)0.0115 (16)0.0055 (14)
O10.0312 (14)0.0408 (15)0.0264 (14)−0.0029 (13)0.0058 (10)−0.0009 (12)
O20.0346 (15)0.0295 (13)0.0296 (14)0.0062 (11)0.0142 (12)0.0021 (11)
O30.0436 (16)0.0239 (14)0.0286 (15)0.0017 (12)0.0067 (12)0.0018 (11)
Geometric parameters (Å, °) top
C1—N11.337 (4)C10—N51.328 (5)
C1—C21.376 (5)C10—H100.90 (4)
C1—H10.89 (4)C11—N51.331 (5)
C2—C31.385 (5)C11—C121.370 (5)
C2—H20.89 (4)C11—H110.93 (4)
C3—C41.392 (5)C12—H120.92 (4)
C3—C61.459 (4)Co1—O1i2.100 (2)
C4—C51.365 (5)Co1—O12.100 (2)
C4—H40.91 (4)Co1—O2i2.126 (2)
C5—N11.332 (4)Co1—O22.126 (2)
C5—H50.91 (4)Co1—N1i2.134 (3)
C6—N31.329 (4)Co1—N12.134 (3)
C6—N21.354 (4)N3—N41.365 (4)
C7—N41.336 (4)O1—H1A0.851 (10)
C7—N21.355 (4)O1—H1B0.852 (10)
C7—C81.459 (4)O2—H2A0.851 (10)
C8—C91.377 (5)O2—H2B0.850 (10)
C8—C121.387 (5)O3—H3A0.852 (10)
C9—C101.373 (5)O3—H3B0.849 (10)
C9—H90.87 (4)
N1—C1—C2123.4 (3)C11—C12—C8119.8 (4)
N1—C1—H1116 (2)C11—C12—H12121 (3)
C2—C1—H1121 (2)C8—C12—H12120 (3)
C1—C2—C3120.0 (3)O1i—Co1—O1180.0
C1—C2—H2119 (3)O1i—Co1—O2i91.47 (10)
C3—C2—H2121 (3)O1—Co1—O2i88.53 (10)
C2—C3—C4116.1 (3)O1i—Co1—O288.53 (10)
C2—C3—C6123.0 (3)O1—Co1—O291.47 (10)
C4—C3—C6120.8 (3)O2i—Co1—O2180.0
C5—C4—C3120.4 (3)O1i—Co1—N1i89.19 (10)
C5—C4—H4122 (2)O1—Co1—N1i90.81 (10)
C3—C4—H4118 (2)O2i—Co1—N1i91.23 (10)
N1—C5—C4123.5 (3)O2—Co1—N1i88.77 (10)
N1—C5—H5116 (2)O1i—Co1—N190.81 (10)
C4—C5—H5120 (2)O1—Co1—N189.19 (10)
N3—C6—N2113.4 (3)O2i—Co1—N188.77 (10)
N3—C6—C3121.3 (3)O2—Co1—N191.23 (10)
N2—C6—C3125.1 (3)N1i—Co1—N1180.0
N4—C7—N2113.1 (3)C5—N1—C1116.7 (3)
N4—C7—C8121.8 (3)C5—N1—Co1122.2 (2)
N2—C7—C8125.0 (3)C1—N1—Co1121.0 (2)
C9—C8—C12116.1 (3)C6—N2—C7101.5 (3)
C9—C8—C7122.5 (3)C6—N3—N4106.0 (2)
C12—C8—C7121.3 (3)C7—N4—N3105.8 (2)
C10—C9—C8120.0 (3)C10—N5—C11115.6 (3)
C10—C9—H9120 (2)Co1—O1—H1A118 (3)
C8—C9—H9120 (2)Co1—O1—H1B126 (3)
N5—C10—C9124.3 (4)H1A—O1—H1B109.1 (17)
N5—C10—H10117 (3)Co1—O2—H2A117 (2)
C9—C10—H10119 (3)Co1—O2—H2B115 (3)
N5—C11—C12124.2 (4)H2A—O2—H2B109.4 (15)
N5—C11—H11115 (3)H3A—O3—H3B106 (4)
C12—C11—H11121 (3)
N1—C1—C2—C3−0.3 (6)C2—C1—N1—Co1−177.5 (3)
C1—C2—C3—C41.4 (5)O1i—Co1—N1—C5−36.4 (3)
C1—C2—C3—C6−175.5 (3)O1—Co1—N1—C5143.6 (3)
C2—C3—C4—C5−1.3 (5)O2i—Co1—N1—C5−127.9 (3)
C6—C3—C4—C5175.6 (3)O2—Co1—N1—C552.1 (3)
C3—C4—C5—N10.1 (6)N1i—Co1—N1—C5−122 (27)
C2—C3—C6—N3−179.1 (3)O1i—Co1—N1—C1140.0 (3)
C4—C3—C6—N34.2 (5)O1—Co1—N1—C1−40.0 (3)
C2—C3—C6—N24.7 (5)O2i—Co1—N1—C148.5 (3)
C4—C3—C6—N2−172.0 (3)O2—Co1—N1—C1−131.5 (3)
N4—C7—C8—C9171.9 (3)N1i—Co1—N1—C155 (27)
N2—C7—C8—C9−5.8 (5)N3—C6—N2—C7−0.6 (4)
N4—C7—C8—C12−5.0 (5)C3—C6—N2—C7175.9 (3)
N2—C7—C8—C12177.3 (3)N4—C7—N2—C60.0 (4)
C12—C8—C9—C10−0.2 (6)C8—C7—N2—C6177.9 (3)
C7—C8—C9—C10−177.4 (3)N2—C6—N3—N40.8 (4)
C8—C9—C10—N50.5 (6)C3—C6—N3—N4−175.7 (3)
N5—C11—C12—C80.6 (7)N2—C7—N4—N30.5 (4)
C9—C8—C12—C11−0.3 (6)C8—C7—N4—N3−177.5 (3)
C7—C8—C12—C11176.9 (4)C6—N3—N4—C7−0.8 (4)
C4—C5—N1—C11.1 (5)C9—C10—N5—C11−0.2 (6)
C4—C5—N1—Co1177.6 (3)C12—C11—N5—C10−0.3 (6)
C2—C1—N1—C5−1.0 (5)
Symmetry codes: (i) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N3ii0.85 (1)2.42 (3)3.070 (4)134 (3)
O1—H1A···N4ii0.85 (1)1.97 (1)2.803 (4)167 (4)
O1—H1B···O3iii0.85 (1)1.99 (2)2.791 (4)155 (3)
O2—H2A···O30.85 (1)1.97 (1)2.801 (4)164 (3)
O2—H2B···N3iv0.85 (1)1.97 (2)2.792 (4)161 (5)
O2—H2B···N4iv0.85 (1)2.60 (4)3.220 (4)130 (4)
O3—H3A···N2v0.85 (1)2.08 (1)2.926 (4)174 (4)
O3—H3B···N5vi0.85 (1)1.95 (1)2.786 (4)168 (5)
Symmetry codes: (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+3/2, z+1/2; (vi) −x, −y+2, −z.
Table 1
Selected geometric parameters (Å, °) top
Co1—O1i2.100 (2)Co1—O22.126 (2)
Co1—O12.100 (2)Co1—N1i2.134 (3)
Co1—O2i2.126 (2)Co1—N12.134 (3)
O1i—Co1—O1180.0O2i—Co1—N1i91.23 (10)
O1i—Co1—O2i91.47 (10)O2—Co1—N1i88.77 (10)
O1—Co1—O2i88.53 (10)O1i—Co1—N190.81 (10)
O1i—Co1—O288.53 (10)O1—Co1—N189.19 (10)
O1—Co1—O291.47 (10)O2i—Co1—N188.77 (10)
O2i—Co1—O2180.0O2—Co1—N191.23 (10)
O1i—Co1—N1i89.19 (10)N1i—Co1—N1180.0
O1—Co1—N1i90.81 (10)
Symmetry codes: (i) −x+1, −y+1, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N3ii0.85 (1)2.42 (3)3.070 (4)134 (3)
O1—H1A···N4ii0.85 (1)1.97 (1)2.803 (4)167 (4)
O1—H1B···O3iii0.85 (1)1.99 (2)2.791 (4)155 (3)
O2—H2A···O30.85 (1)1.97 (1)2.801 (4)164 (3)
O2—H2B···N3iv0.85 (1)1.97 (2)2.792 (4)161 (5)
O2—H2B···N4iv0.85 (1)2.60 (4)3.220 (4)130 (4)
O3—H3A···N2v0.85 (1)2.08 (1)2.926 (4)174 (4)
O3—H3B···N5vi0.85 (1)1.95 (1)2.786 (4)168 (5)
Symmetry codes: (ii) x, −y+3/2, z−1/2; (iii) −x, −y+1, −z; (iv) −x+1, y−1/2, −z+1/2; (v) x, −y+3/2, z+1/2; (vi) −x, −y+2, −z.
references
References top

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