Tetra­aqua­bis(3,5-di-4-pyridyl-1,2,4-triazolato-κN)cobalt(II) dihydrate

Dong, L.Y.

doi:10.1107/S1600536809011982

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages m487-m488

doi:10.1107/S1600536809011982

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Tetraaquabis(3,5-di-4-pyridyl-1,2,4-triazolato-κN)cobalt(II) dihydrate

Lin Yi Dong ^a ^*

^aSchool of Pharmacy, Tianjin Medical University, Tianjin 300070, People's Republic of China
^*Correspondence e-mail: pass2009_good@126.com

(Received 26 March 2009; accepted 31 March 2009; online 8 April 2009)

The Co^II 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.

Related literature

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 the structure of water, see: Tajkhorshid et al. (2002 ). For the synthesis, see: Basu & Dutta (1964 ). For a trinuclear water cluster, see: König (1944 ).

Experimental

Crystal data

[Co(C₁₂H₈N₅)₂(H₂O)₄]·2H₂O
M_r = 611.49
Monoclinic, P 2₁ /c
a = 7.3660 (15) Å
b = 15.654 (3) Å
c = 11.857 (2) Å
β = 107.34 (3)°
V = 1305.1 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 293 K
0.40 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.842, T_max = 0.917
11054 measured reflections
2423 independent reflections
2009 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.108
S = 1.07
2420 reflections
243 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—O1	2.100 (2)
Co1—O2	2.126 (2)
Co1—N1	2.134 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N3ⁱⁱ	0.851 (10)	2.42 (3)	3.070 (4)	134 (3)
O1—H1A⋯N4ⁱⁱ	0.851 (10)	1.966 (12)	2.803 (4)	167 (4)
O1—H1B⋯O3ⁱⁱⁱ	0.852 (10)	1.99 (2)	2.791 (4)	155 (3)
O2—H2A⋯O3	0.851 (10)	1.973 (14)	2.801 (4)	164 (3)
O2—H2B⋯N3^iv	0.850 (10)	1.973 (19)	2.792 (4)	161 (5)
O2—H2B⋯N4^iv	0.850 (10)	2.60 (4)	3.220 (4)	130 (4)
O3—H3A⋯N2^v	0.852 (10)	2.077 (12)	2.926 (4)	174 (4)
O3—H3B⋯N5^vi	0.849 (10)	1.950 (14)	2.786 (4)	168 (5)
Symmetry codes: (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vi) -x, -y+2, -z.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809011982/ng2566sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809011982/ng2566Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure and atom-labeling scheme of (I).
	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
M_r = 611.49	D_x = 1.556 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 556 reflections
a = 7.3660 (15) Å	θ = 1.5–25.5°
b = 15.654 (3) Å	µ = 0.72 mm⁻¹
c = 11.857 (2) Å	T = 293 K
β = 107.34 (3)°	Block, red
V = 1305.1 (5) Å³	0.40 × 0.20 × 0.12 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	2423 independent reflections
Radiation source: fine-focus sealed tube	2009 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
ϕ and ω scans	θ_max = 25.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.842, T_max = 0.917	k = −18→18
11054 measured reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.054	w = 1/[σ²(F_o²) + (0.0298P)² + 0.2298P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.108	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.29 e Å⁻³
2420 reflections	Δρ_min = −0.41 e Å⁻³
243 parameters

Crystal data top

[Co(C₁₂H₈N₅)₂(H₂O)₄]·2(H₂O)	V = 1305.1 (5) Å³
M_r = 611.49	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3660 (15) Å	µ = 0.72 mm⁻¹
b = 15.654 (3) Å	T = 293 K
c = 11.857 (2) Å	0.40 × 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)
T_min = 0.842, T_max = 0.917	R_int = 0.065
11054 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.29 e Å⁻³
2420 reflections	Δρ_min = −0.41 e Å⁻³
243 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3827 (5)	0.6826 (2)	−0.0776 (3)	0.0306 (8)
C2	0.3536 (5)	0.7690 (2)	−0.0713 (3)	0.0299 (8)
C3	0.3919 (4)	0.80864 (19)	0.0377 (3)	0.0218 (7)
C4	0.4634 (5)	0.7565 (2)	0.1360 (3)	0.0290 (8)
C5	0.4886 (5)	0.6711 (2)	0.1224 (3)	0.0294 (8)
C6	0.3518 (5)	0.8987 (2)	0.0514 (3)	0.0229 (7)
C7	0.2496 (5)	1.02433 (19)	0.0220 (3)	0.0241 (7)
C8	0.1690 (5)	1.1049 (2)	−0.0324 (3)	0.0244 (7)
C9	0.1117 (5)	1.1170 (2)	−0.1528 (3)	0.0330 (9)
C10	0.0440 (6)	1.1952 (2)	−0.1990 (3)	0.0368 (9)
C11	0.0861 (6)	1.2510 (3)	−0.0181 (4)	0.0450 (11)
C12	0.1540 (6)	1.1751 (2)	0.0357 (4)	0.0403 (10)
Co1	0.5000	0.5000	0.0000	0.02203 (19)
H1	0.363 (5)	0.657 (2)	−0.147 (3)	0.033 (10)*
H2	0.313 (5)	0.799 (3)	−0.138 (3)	0.046 (12)*
H4	0.495 (5)	0.781 (2)	0.209 (3)	0.034 (10)*
H5	0.532 (5)	0.637 (2)	0.187 (3)	0.036 (10)*
H9	0.118 (5)	1.075 (2)	−0.199 (3)	0.028 (10)*
H10	0.013 (6)	1.203 (3)	−0.278 (4)	0.052 (13)*
H11	0.078 (6)	1.299 (3)	0.026 (4)	0.057 (13)*
H12	0.188 (6)	1.170 (3)	0.116 (4)	0.051 (12)*
H1A	0.261 (5)	0.484 (3)	−0.2116 (18)	0.069 (16)*
H2A	0.276 (4)	0.5057 (16)	0.135 (3)	0.031 (10)*
H3A	0.163 (5)	0.571 (2)	0.2816 (10)	0.041 (12)*
H1B	0.143 (3)	0.475 (3)	−0.140 (3)	0.077 (17)*
H2B	0.416 (6)	0.446 (3)	0.1861 (19)	0.084 (18)*
H3B	0.081 (6)	0.6269 (11)	0.194 (4)	0.069 (16)*
N1	0.4483 (4)	0.63277 (16)	0.0175 (2)	0.0262 (6)
N2	0.2624 (4)	0.95193 (16)	−0.0378 (2)	0.0229 (6)
N3	0.3929 (4)	0.93481 (17)	0.1575 (2)	0.0295 (7)
N4	0.3253 (4)	1.01645 (17)	0.1389 (2)	0.0308 (7)
N5	0.0298 (4)	1.26290 (18)	−0.1346 (3)	0.0371 (8)
O1	0.2504 (3)	0.49368 (17)	−0.1431 (2)	0.0334 (6)
O2	0.3487 (4)	0.46767 (16)	0.1212 (2)	0.0302 (6)
O3	0.1157 (4)	0.57516 (16)	0.2069 (2)	0.0329 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.047 (2)	0.0220 (18)	0.0201 (18)	0.0038 (16)	0.0054 (16)	−0.0033 (15)
C2	0.044 (2)	0.0184 (17)	0.0245 (19)	0.0057 (15)	0.0057 (16)	0.0020 (15)
C3	0.0241 (18)	0.0184 (16)	0.0231 (17)	0.0017 (13)	0.0074 (14)	−0.0003 (13)
C4	0.043 (2)	0.0239 (18)	0.0188 (18)	0.0052 (16)	0.0075 (16)	−0.0032 (15)
C5	0.043 (2)	0.0200 (18)	0.0232 (19)	0.0050 (15)	0.0065 (16)	0.0043 (14)
C6	0.0277 (18)	0.0182 (16)	0.0224 (17)	−0.0006 (14)	0.0066 (14)	0.0000 (13)
C7	0.0297 (18)	0.0194 (17)	0.0227 (17)	−0.0001 (13)	0.0072 (14)	0.0002 (13)
C8	0.0247 (18)	0.0211 (17)	0.0269 (18)	−0.0023 (14)	0.0067 (14)	−0.0009 (14)
C9	0.044 (2)	0.0231 (19)	0.028 (2)	0.0046 (16)	0.0043 (17)	−0.0031 (16)
C10	0.044 (2)	0.033 (2)	0.027 (2)	0.0034 (17)	0.0023 (18)	0.0073 (17)
C11	0.067 (3)	0.024 (2)	0.045 (3)	0.013 (2)	0.017 (2)	−0.0019 (18)
C12	0.065 (3)	0.027 (2)	0.028 (2)	0.0129 (18)	0.011 (2)	0.0002 (16)
Co1	0.0282 (4)	0.0162 (3)	0.0206 (3)	0.0025 (3)	0.0055 (2)	0.0004 (3)
N1	0.0358 (17)	0.0170 (14)	0.0251 (15)	0.0032 (12)	0.0081 (12)	−0.0001 (11)
N2	0.0283 (15)	0.0154 (14)	0.0241 (15)	0.0011 (11)	0.0063 (12)	−0.0011 (11)
N3	0.0398 (18)	0.0213 (15)	0.0255 (16)	0.0099 (13)	0.0065 (13)	0.0017 (12)
N4	0.0461 (18)	0.0213 (16)	0.0221 (15)	0.0069 (13)	0.0057 (13)	−0.0013 (11)
N5	0.044 (2)	0.0223 (16)	0.044 (2)	0.0079 (14)	0.0115 (16)	0.0055 (14)
O1	0.0312 (14)	0.0408 (15)	0.0264 (14)	−0.0029 (13)	0.0058 (10)	−0.0009 (12)
O2	0.0346 (15)	0.0295 (13)	0.0296 (14)	0.0062 (11)	0.0142 (12)	0.0021 (11)
O3	0.0436 (16)	0.0239 (14)	0.0286 (15)	0.0017 (12)	0.0067 (12)	0.0018 (11)

Geometric parameters (Å, º) top

C1—N1	1.337 (4)	C10—N5	1.328 (5)
C1—C2	1.376 (5)	C10—H10	0.90 (4)
C1—H1	0.89 (4)	C11—N5	1.331 (5)
C2—C3	1.385 (5)	C11—C12	1.370 (5)
C2—H2	0.89 (4)	C11—H11	0.93 (4)
C3—C4	1.392 (5)	C12—H12	0.92 (4)
C3—C6	1.459 (4)	Co1—O1ⁱ	2.100 (2)
C4—C5	1.365 (5)	Co1—O1	2.100 (2)
C4—H4	0.91 (4)	Co1—O2ⁱ	2.126 (2)
C5—N1	1.332 (4)	Co1—O2	2.126 (2)
C5—H5	0.91 (4)	Co1—N1ⁱ	2.134 (3)
C6—N3	1.329 (4)	Co1—N1	2.134 (3)
C6—N2	1.354 (4)	N3—N4	1.365 (4)
C7—N4	1.336 (4)	O1—H1A	0.851 (10)
C7—N2	1.355 (4)	O1—H1B	0.852 (10)
C7—C8	1.459 (4)	O2—H2A	0.851 (10)
C8—C9	1.377 (5)	O2—H2B	0.850 (10)
C8—C12	1.387 (5)	O3—H3A	0.852 (10)
C9—C10	1.373 (5)	O3—H3B	0.849 (10)
C9—H9	0.87 (4)

N1—C1—C2	123.4 (3)	C11—C12—C8	119.8 (4)
N1—C1—H1	116 (2)	C11—C12—H12	121 (3)
C2—C1—H1	121 (2)	C8—C12—H12	120 (3)
C1—C2—C3	120.0 (3)	O1ⁱ—Co1—O1	180.0
C1—C2—H2	119 (3)	O1ⁱ—Co1—O2ⁱ	91.47 (10)
C3—C2—H2	121 (3)	O1—Co1—O2ⁱ	88.53 (10)
C2—C3—C4	116.1 (3)	O1ⁱ—Co1—O2	88.53 (10)
C2—C3—C6	123.0 (3)	O1—Co1—O2	91.47 (10)
C4—C3—C6	120.8 (3)	O2ⁱ—Co1—O2	180.0
C5—C4—C3	120.4 (3)	O1ⁱ—Co1—N1ⁱ	89.19 (10)
C5—C4—H4	122 (2)	O1—Co1—N1ⁱ	90.81 (10)
C3—C4—H4	118 (2)	O2ⁱ—Co1—N1ⁱ	91.23 (10)
N1—C5—C4	123.5 (3)	O2—Co1—N1ⁱ	88.77 (10)
N1—C5—H5	116 (2)	O1ⁱ—Co1—N1	90.81 (10)
C4—C5—H5	120 (2)	O1—Co1—N1	89.19 (10)
N3—C6—N2	113.4 (3)	O2ⁱ—Co1—N1	88.77 (10)
N3—C6—C3	121.3 (3)	O2—Co1—N1	91.23 (10)
N2—C6—C3	125.1 (3)	N1ⁱ—Co1—N1	180.0
N4—C7—N2	113.1 (3)	C5—N1—C1	116.7 (3)
N4—C7—C8	121.8 (3)	C5—N1—Co1	122.2 (2)
N2—C7—C8	125.0 (3)	C1—N1—Co1	121.0 (2)
C9—C8—C12	116.1 (3)	C6—N2—C7	101.5 (3)
C9—C8—C7	122.5 (3)	C6—N3—N4	106.0 (2)
C12—C8—C7	121.3 (3)	C7—N4—N3	105.8 (2)
C10—C9—C8	120.0 (3)	C10—N5—C11	115.6 (3)
C10—C9—H9	120 (2)	Co1—O1—H1A	118 (3)
C8—C9—H9	120 (2)	Co1—O1—H1B	126 (3)
N5—C10—C9	124.3 (4)	H1A—O1—H1B	109.1 (17)
N5—C10—H10	117 (3)	Co1—O2—H2A	117 (2)
C9—C10—H10	119 (3)	Co1—O2—H2B	115 (3)
N5—C11—C12	124.2 (4)	H2A—O2—H2B	109.4 (15)
N5—C11—H11	115 (3)	H3A—O3—H3B	106 (4)
C12—C11—H11	121 (3)

N1—C1—C2—C3	−0.3 (6)	C2—C1—N1—Co1	−177.5 (3)
C1—C2—C3—C4	1.4 (5)	O1ⁱ—Co1—N1—C5	−36.4 (3)
C1—C2—C3—C6	−175.5 (3)	O1—Co1—N1—C5	143.6 (3)
C2—C3—C4—C5	−1.3 (5)	O2ⁱ—Co1—N1—C5	−127.9 (3)
C6—C3—C4—C5	175.6 (3)	O2—Co1—N1—C5	52.1 (3)
C3—C4—C5—N1	0.1 (6)	N1ⁱ—Co1—N1—C5	−122 (27)
C2—C3—C6—N3	−179.1 (3)	O1ⁱ—Co1—N1—C1	140.0 (3)
C4—C3—C6—N3	4.2 (5)	O1—Co1—N1—C1	−40.0 (3)
C2—C3—C6—N2	4.7 (5)	O2ⁱ—Co1—N1—C1	48.5 (3)
C4—C3—C6—N2	−172.0 (3)	O2—Co1—N1—C1	−131.5 (3)
N4—C7—C8—C9	171.9 (3)	N1ⁱ—Co1—N1—C1	55 (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—C7	175.9 (3)
N2—C7—C8—C12	177.3 (3)	N4—C7—N2—C6	0.0 (4)
C12—C8—C9—C10	−0.2 (6)	C8—C7—N2—C6	177.9 (3)
C7—C8—C9—C10	−177.4 (3)	N2—C6—N3—N4	0.8 (4)
C8—C9—C10—N5	0.5 (6)	C3—C6—N3—N4	−175.7 (3)
N5—C11—C12—C8	0.6 (7)	N2—C7—N4—N3	0.5 (4)
C9—C8—C12—C11	−0.3 (6)	C8—C7—N4—N3	−177.5 (3)
C7—C8—C12—C11	176.9 (4)	C6—N3—N4—C7	−0.8 (4)
C4—C5—N1—C1	1.1 (5)	C9—C10—N5—C11	−0.2 (6)
C4—C5—N1—Co1	177.6 (3)	C12—C11—N5—C10	−0.3 (6)
C2—C1—N1—C5	−1.0 (5)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3ⁱⁱ	0.85 (1)	2.42 (3)	3.070 (4)	134 (3)
O1—H1A···N4ⁱⁱ	0.85 (1)	1.97 (1)	2.803 (4)	167 (4)
O1—H1B···O3ⁱⁱⁱ	0.85 (1)	1.99 (2)	2.791 (4)	155 (3)
O2—H2A···O3	0.85 (1)	1.97 (1)	2.801 (4)	164 (3)
O2—H2B···N3^iv	0.85 (1)	1.97 (2)	2.792 (4)	161 (5)
O2—H2B···N4^iv	0.85 (1)	2.60 (4)	3.220 (4)	130 (4)
O3—H3A···N2^v	0.85 (1)	2.08 (1)	2.926 (4)	174 (4)
O3—H3B···N5^vi	0.85 (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.

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₈N₅)₂(H₂O)₄]·2(H₂O)
M_r	611.49
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.3660 (15), 15.654 (3), 11.857 (2)
β (°)	107.34 (3)
V (Å³)	1305.1 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.40 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.842, 0.917
No. of measured, independent and observed [I > 2σ(I)] reflections	11054, 2423, 2009
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.108, 1.07
No. of reflections	2420
No. of parameters	243
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.41

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2009).

Selected geometric parameters (Å, º) top

Co1—O1ⁱ	2.100 (2)	Co1—O2	2.126 (2)
Co1—O1	2.100 (2)	Co1—N1ⁱ	2.134 (3)
Co1—O2ⁱ	2.126 (2)	Co1—N1	2.134 (3)

O1ⁱ—Co1—O1	180.0	O2ⁱ—Co1—N1ⁱ	91.23 (10)
O1ⁱ—Co1—O2ⁱ	91.47 (10)	O2—Co1—N1ⁱ	88.77 (10)
O1—Co1—O2ⁱ	88.53 (10)	O1ⁱ—Co1—N1	90.81 (10)
O1ⁱ—Co1—O2	88.53 (10)	O1—Co1—N1	89.19 (10)
O1—Co1—O2	91.47 (10)	O2ⁱ—Co1—N1	88.77 (10)
O2ⁱ—Co1—O2	180.0	O2—Co1—N1	91.23 (10)
O1ⁱ—Co1—N1ⁱ	89.19 (10)	N1ⁱ—Co1—N1	180.0
O1—Co1—N1ⁱ	90.81 (10)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3ⁱⁱ	0.851 (10)	2.42 (3)	3.070 (4)	134 (3)
O1—H1A···N4ⁱⁱ	0.851 (10)	1.966 (12)	2.803 (4)	167 (4)
O1—H1B···O3ⁱⁱⁱ	0.852 (10)	1.99 (2)	2.791 (4)	155 (3)
O2—H2A···O3	0.851 (10)	1.973 (14)	2.801 (4)	164 (3)
O2—H2B···N3^iv	0.850 (10)	1.973 (19)	2.792 (4)	161 (5)
O2—H2B···N4^iv	0.850 (10)	2.60 (4)	3.220 (4)	130 (4)
O3—H3A···N2^v	0.852 (10)	2.077 (12)	2.926 (4)	174 (4)
O3—H3B···N5^vi	0.849 (10)	1.950 (14)	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

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Volume 65| Part 5| May 2009| Pages m487-m488

doi:10.1107/S1600536809011982

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