(Adipato-κ2O,O′)di­aqua­[bis­(pyridin-2-yl-κN)amine]­cobalt(II) trihydrate

Setifi, Z.; Setifi, F.; Smith, G.; El-Ghozzi, M.; Rouag, D.-A.; Avignant, D.; Merazig, H.

doi:10.1107/S1600536813012981

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 6| June 2013| Pages m335-m336

doi:10.1107/S1600536813012981

Open

access

(Adipato-κ²O,O′)diaqua[bis(pyridin-2-yl-κN)amine]cobalt(II) trihydrate

Zouaoui Setifi,^a,^b Fatima Setifi,^c,^b ^* Graham Smith,^d ^* Malika El-Ghozzi,^e,^f Djamil-Azzeddine Rouag,^b Daniel Avignant ^e,^f and Hocine Merazig ^b

^aDépartement de Technologie, Faculté de Technologie, Université 20 Août 1955 de Skikda, 21000 Skikda, Algeria, ^bUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale (CHEMS), Université Constantine I, 25000 Constantine, Algeria, ^cLaboratoire de Chimie, Ingénierie Moléculaire et Nanostructures (LCIMN), Université Ferhat Abbas, Sétif I, 19000 Sétif, Algeria, ^dScience and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane 4001, Australia, ^eClermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, 63000 Clermont-Ferrand, France, and ^fCNRS UMR 6296, ICCF, BP 80026, 63171 Aubière, France
^*Correspondence e-mail: fat_setifi@yahoo.fr, g.smith@qut.edu.au

(Received 11 May 2013; accepted 12 May 2013; online 22 May 2013)

In the monomeric title complex, [Co(C₆H₈O₄)(C₁₀H₉N₃)(H₂O)₂]·3H₂O, the distorted octahedral CoN₂O₄ coordination environment comprises two N-atom donors from the bidentate dipyridyldiamine ligand, two O-atom donors from one of the carboxylate groups of the bidentate chelating adipate ligand and two water molecules. In addition, there are three solvent water molecules which are involved in both intra- and inter-unit O—H⋯O hydrogen-bonding interactions, which together with an amine–water N—H⋯O hydrogen bond produce a three-dimensional framework.

Related literature

For the background to metal-dicarboxylate complexes, see: Rao et al. (2004 ); Setifi et al. (2006 , 2007 ); Wen et al. (2010 ).

Experimental

Crystal data

[Co(C₆H₈O₄)(C₁₀H₉N₃)(H₂O)₂]·3H₂O
M_r = 464.34
Triclinic, $[P \overline 1]$
a = 9.9587 (3) Å
b = 10.5458 (3) Å
c = 11.0885 (3) Å
α = 100.887 (1)°
β = 105.891 (1)°
γ = 107.889 (1)°
V = 1017.38 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.90 mm⁻¹
T = 296 K
0.26 × 0.21 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.800, T_max = 0.855
28998 measured reflections
8197 independent reflections
6984 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.097
S = 0.99
8197 reflections
306 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.0680 (10)
Co1—O2	2.3079 (9)
Co1—O5	2.0877 (12)
Co1—O6	2.1336 (9)
Co1—N1	2.0781 (9)
Co1—N2	2.0596 (10)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O9ⁱ	0.78 (2)	2.05 (2)	2.8228 (17)	172 (2)
O5—H51⋯O7ⁱⁱ	0.775 (19)	1.923 (19)	2.6933 (15)	172.7 (19)
O5—H52⋯O3ⁱⁱⁱ	0.80 (2)	1.97 (2)	2.7706 (17)	173 (2)
O6—H61⋯O2^iv	0.83 (2)	2.00 (2)	2.8278 (12)	178 (4)
O6—H62⋯O8	0.77 (2)	1.94 (2)	2.7056 (16)	170 (2)
O7—H71⋯O3^v	0.74 (3)	2.56 (3)	3.2596 (18)	160 (3)
O7—H72⋯O1	0.89 (2)	1.86 (2)	2.7543 (16)	175 (2)
O8—H81⋯O4^v	0.88 (3)	1.97 (3)	2.8221 (19)	163 (2)
O8—H82⋯O4^vi	0.79 (3)	2.05 (3)	2.832 (2)	175 (3)
O9—H91⋯O3^vii	0.77 (2)	2.12 (2)	2.8670 (17)	164 (2)
O9—H92⋯O3^v	0.79 (3)	1.99 (3)	2.7452 (17)	160 (3)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x+2, -y+1, -z; (iii) -x+3, -y+1, -z+1; (iv) -x+2, -y+1, -z+1; (v) -x+3, -y+2, -z+1; (vi) x-1, y, z; (vii) x-1, y, z-1.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813012981/sj5322sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813012981/sj5322Isup2.hkl

checkCIF report

Comment top

Dicarboxylates have been widely used as ligands in metal coordination chemistry because they possess interesting features, such as: (i) the presence of two carboxylato groups capable of bidentate and monodentate linking modes, (ii) the possibility of obtaining mono- or dianionic forms, (iii) the probability of triply coordinated oxygen atoms and (iv) the possibility of forming secondary building blocks (Rao et al., 2004). Their use as bridging ligands has generated metal-organic coordination polymers with diverse and interesting structural features (Setifi et al., 2006, 2007; Wen et al., 2010). Given the rich coordination chemistry and the flexibility of these anionic ligands, we are interested in using them in combination with other chelating co-ligands to explore their structural features and properties in the large field of molecular materials. This led us to the synthesis of the parent coordination compound, the title complex [Co(dpa)(adip)(H₂O)₂]. 3H₂O, (where dpa is 2,2'-dipyridylamine and adip is the adipate dianion), and the structure is described herein.

In this monomeric complex, the distorted octahedral MN₂O₄ coordination sphere comprises two N-donors from the bidentate chelate dpa ligand, two carboxyl O-donors (O1, O2) from one of the carboxyl groups of the adipate ligand and two water molecules (O5, O6). In addition, there are three water molecules of solvation (O7–O9) (Fig. 1). The (N,N') interaction is essentially symmetric [Co—N, 2.0596 (10), 2.0781 (9) Å] (Table 1) but the (O,O') interaction is asymmetric [Co—O, 2.0680 (10), 2.3079 (9) Å], with a 'bite' angle of 59.68 (3)°. The second adipate carboxyl group is not involved in coordination.

In the crystal, both the coordinated water molecules and the solvent water molecules are involved in both intra- and inter-unit O—H···O hydrogen-bonding interactions. The amine N-atom of the dpa ligand is also hydrogen-bonded to a water molecule (O9) (Table 2), giving an overall three-dimensional framework structure (Fig. 2).

Related literature top

For the background tp metal-dicarboxylate complexes, see: Rao et al. (2004); Setifi et al. (2006, 2007); Wen et al. (2010).

Experimental top

All reagents were purchased from commercial sources and used as received. Under aerobic conditions, an ethanolic solution of 2,2'-dipyridylamine (0.017 g, 5 ml) was added, with stirring at room temperature to an ethanolic solution of CoCl₂.6H₂O (0.024 g, 5 ml), resulting in a pink suspension. Adipic acid was dissolved in water (0.015 g, 10 ml) and added quickly to the mixture. The final solution was filtered and the filtrate allowed to evaporate in air for two weeks, giving brown crystals of the title compound suitable for X-ray diffraction analysis.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.
	Fig. 2. The crystal packing of the title compound in the unit cell viewed down a, showing hydrogen bonds as dashed lines. Non-associative H-atoms are omitted.

(Adipato-κ²O,O')diaqua[bis(pyridin-2-yl-κN)amine]cobalt(II) trihydrate top

Crystal data top

[Co(C₆H₈O₄)(C₁₀H₉N₃)(H₂O)₂]·3H₂O	Z = 2
M_r = 464.34	F(000) = 486
Triclinic, P1	D_x = 1.516 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.9587 (3) Å	Cell parameters from 9938 reflections
b = 10.5458 (3) Å	θ = 2.5–33.9°
c = 11.0885 (3) Å	µ = 0.90 mm⁻¹
α = 100.887 (1)°	T = 296 K
β = 105.891 (1)°	Prism, brown
γ = 107.889 (1)°	0.26 × 0.21 × 0.18 mm
V = 1017.38 (5) Å³

Data collection top

Bruker APEXII CCD diffractometer	8197 independent reflections
Radiation source: fine-focus sealed tube	6984 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 33.9°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→15
T_min = 0.800, T_max = 0.855	k = −16→16
28998 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0677P)² + 0.048P] where P = (F_o² + 2F_c²)/3
8197 reflections	(Δ/σ)_max = 0.001
306 parameters	Δρ_max = 0.37 e Å⁻³
1 restraint	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Co(C₆H₈O₄)(C₁₀H₉N₃)(H₂O)₂]·3H₂O	γ = 107.889 (1)°
M_r = 464.34	V = 1017.38 (5) Å³
Triclinic, P1	Z = 2
a = 9.9587 (3) Å	Mo Kα radiation
b = 10.5458 (3) Å	µ = 0.90 mm⁻¹
c = 11.0885 (3) Å	T = 296 K
α = 100.887 (1)°	0.26 × 0.21 × 0.18 mm
β = 105.891 (1)°

Data collection top

Bruker APEXII CCD diffractometer	8197 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	6984 reflections with I > 2σ(I)
T_min = 0.800, T_max = 0.855	R_int = 0.024
28998 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.37 e Å⁻³
8197 reflections	Δρ_min = −0.34 e Å⁻³
306 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 > 2σ(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
Co1	0.87882 (1)	0.40987 (1)	0.21923 (1)	0.0256 (1)
O1	1.05309 (9)	0.59199 (9)	0.24329 (8)	0.0346 (2)
O2	1.10712 (9)	0.48396 (9)	0.38874 (8)	0.0334 (2)
O3	1.92943 (11)	0.90473 (12)	0.80972 (9)	0.0509 (3)
O4	1.88720 (12)	0.95610 (12)	0.62266 (12)	0.0579 (3)
O5	0.97049 (11)	0.29574 (11)	0.11448 (10)	0.0401 (3)
O6	0.80952 (9)	0.52897 (9)	0.35009 (8)	0.0318 (2)
N1	0.71591 (9)	0.40327 (9)	0.05172 (8)	0.0259 (2)
N2	0.73045 (10)	0.22973 (9)	0.22883 (9)	0.0289 (2)
N3	0.51381 (10)	0.22666 (11)	0.06928 (10)	0.0338 (2)
C1	1.14696 (10)	0.58243 (11)	0.34175 (9)	0.0274 (2)
C2	1.30419 (11)	0.69271 (12)	0.39566 (11)	0.0329 (3)
C3	1.42382 (11)	0.66497 (12)	0.49212 (11)	0.0347 (3)
C4	1.57881 (11)	0.77823 (11)	0.53102 (11)	0.0315 (3)
C5	1.69945 (12)	0.76076 (12)	0.63591 (12)	0.0365 (3)
C6	1.84988 (11)	0.88359 (11)	0.69272 (11)	0.0305 (2)
C7	0.76159 (12)	0.49385 (12)	−0.01408 (11)	0.0332 (3)
C8	0.66587 (14)	0.50906 (13)	−0.12028 (11)	0.0374 (3)
C9	0.51360 (13)	0.42605 (14)	−0.16405 (10)	0.0367 (3)
C10	0.46425 (12)	0.33147 (12)	−0.10088 (10)	0.0329 (3)
C11	0.58275 (11)	0.17043 (10)	0.15844 (10)	0.0274 (2)
C12	0.56943 (10)	0.32248 (10)	0.00812 (9)	0.0255 (2)
C13	0.78977 (14)	0.16797 (14)	0.31479 (14)	0.0401 (3)
C14	0.70567 (18)	0.05002 (16)	0.33525 (17)	0.0495 (5)
C15	0.55197 (17)	−0.01009 (13)	0.26316 (16)	0.0469 (4)
C16	0.48925 (14)	0.04862 (12)	0.17371 (13)	0.0387 (3)
O7	1.14682 (14)	0.81433 (12)	0.14879 (11)	0.0492 (3)
O8	0.88888 (16)	0.80611 (12)	0.38293 (15)	0.0613 (4)
O9	0.80392 (11)	0.89324 (14)	0.01315 (13)	0.0604 (4)
H2A	1.29990	0.77980	0.43830	0.0390*
H2B	1.33620	0.70600	0.32230	0.0390*
H3	0.426 (2)	0.1928 (19)	0.0392 (18)	0.050 (5)*
H3A	1.42590	0.57550	0.45290	0.0420*
H3B	1.39850	0.66010	0.57000	0.0420*
H4A	1.60690	0.77760	0.45390	0.0380*
H4B	1.57380	0.86830	0.56270	0.0380*
H5A	1.71530	0.67790	0.59900	0.0440*
H5B	1.66320	0.74550	0.70680	0.0440*
H7	0.86380	0.54890	0.01450	0.0400*
H8	0.70200	0.57340	−0.16210	0.0450*
H9	0.44560	0.43450	−0.23560	0.0440*
H10	0.36270	0.27410	−0.12970	0.0400*
H13	0.89300	0.20800	0.36220	0.0480*
H14	0.75020	0.01120	0.39570	0.0590*
H15	0.49160	−0.08990	0.27540	0.0560*
H16	0.38660	0.00850	0.12400	0.0460*
H51	0.932 (2)	0.2581 (19)	0.0397 (19)	0.046 (5)*
H52	1.002 (2)	0.242 (2)	0.143 (2)	0.065 (6)*
H61	0.836 (3)	0.526 (3)	0.427 (2)	0.083 (7)*
H62	0.838 (2)	0.607 (2)	0.3537 (19)	0.057 (5)*
H71	1.117 (3)	0.868 (3)	0.168 (3)	0.107 (10)*
H72	1.122 (2)	0.745 (2)	0.184 (2)	0.063 (6)*
H81	0.958 (3)	0.868 (3)	0.367 (2)	0.075 (6)*
H82	0.884 (3)	0.849 (3)	0.447 (3)	0.085 (8)*
H91	0.833 (2)	0.880 (2)	−0.044 (2)	0.067 (6)*
H92	0.870 (3)	0.949 (3)	0.077 (3)	0.085 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0168 (1)	0.0288 (1)	0.0261 (1)	0.0034 (1)	0.0039 (1)	0.0117 (1)
O1	0.0216 (3)	0.0398 (4)	0.0325 (4)	0.0018 (3)	0.0020 (3)	0.0170 (3)
O2	0.0243 (3)	0.0370 (4)	0.0328 (3)	0.0047 (3)	0.0054 (3)	0.0156 (3)
O3	0.0306 (4)	0.0617 (6)	0.0328 (4)	−0.0007 (4)	−0.0034 (3)	0.0056 (4)
O4	0.0370 (5)	0.0520 (6)	0.0595 (6)	−0.0090 (4)	0.0017 (4)	0.0276 (5)
O5	0.0393 (5)	0.0504 (5)	0.0350 (4)	0.0211 (4)	0.0143 (4)	0.0141 (4)
O6	0.0328 (4)	0.0307 (4)	0.0303 (4)	0.0101 (3)	0.0098 (3)	0.0113 (3)
N1	0.0198 (3)	0.0288 (4)	0.0253 (3)	0.0054 (3)	0.0050 (3)	0.0103 (3)
N2	0.0245 (4)	0.0270 (4)	0.0352 (4)	0.0075 (3)	0.0106 (3)	0.0133 (3)
N3	0.0188 (4)	0.0360 (4)	0.0377 (4)	0.0013 (3)	0.0047 (3)	0.0144 (4)
C1	0.0182 (4)	0.0318 (4)	0.0265 (4)	0.0041 (3)	0.0052 (3)	0.0090 (3)
C2	0.0187 (4)	0.0328 (5)	0.0356 (5)	0.0015 (3)	0.0020 (3)	0.0100 (4)
C3	0.0201 (4)	0.0371 (5)	0.0347 (5)	0.0003 (4)	0.0015 (4)	0.0138 (4)
C4	0.0194 (4)	0.0324 (5)	0.0322 (4)	0.0017 (3)	0.0021 (3)	0.0109 (4)
C5	0.0228 (4)	0.0311 (5)	0.0409 (5)	0.0000 (4)	−0.0019 (4)	0.0148 (4)
C6	0.0198 (4)	0.0281 (4)	0.0342 (4)	0.0045 (3)	0.0035 (3)	0.0052 (4)
C7	0.0251 (4)	0.0388 (5)	0.0314 (4)	0.0058 (4)	0.0064 (4)	0.0171 (4)
C8	0.0370 (5)	0.0444 (6)	0.0326 (5)	0.0150 (5)	0.0096 (4)	0.0205 (4)
C9	0.0350 (5)	0.0473 (6)	0.0264 (4)	0.0204 (5)	0.0035 (4)	0.0111 (4)
C10	0.0223 (4)	0.0386 (5)	0.0288 (4)	0.0097 (4)	0.0010 (3)	0.0051 (4)
C11	0.0257 (4)	0.0227 (4)	0.0309 (4)	0.0045 (3)	0.0117 (3)	0.0068 (3)
C12	0.0198 (4)	0.0265 (4)	0.0247 (4)	0.0059 (3)	0.0046 (3)	0.0050 (3)
C13	0.0338 (5)	0.0419 (6)	0.0522 (7)	0.0166 (5)	0.0152 (5)	0.0269 (5)
C14	0.0541 (8)	0.0447 (7)	0.0679 (9)	0.0250 (6)	0.0285 (7)	0.0362 (7)
C15	0.0548 (8)	0.0299 (5)	0.0661 (9)	0.0130 (5)	0.0331 (7)	0.0243 (6)
C16	0.0340 (5)	0.0280 (5)	0.0469 (6)	0.0008 (4)	0.0168 (5)	0.0103 (4)
O7	0.0603 (7)	0.0403 (5)	0.0440 (5)	0.0140 (5)	0.0175 (5)	0.0159 (4)
O8	0.0727 (8)	0.0345 (5)	0.0813 (9)	0.0112 (5)	0.0427 (7)	0.0201 (5)
O9	0.0245 (4)	0.0761 (8)	0.0492 (6)	−0.0076 (5)	0.0069 (4)	0.0033 (5)

Geometric parameters (Å, º) top

Co1—O1	2.0680 (10)	C2—C3	1.5111 (17)
Co1—O2	2.3079 (9)	C3—C4	1.5177 (17)
Co1—O5	2.0877 (12)	C4—C5	1.5106 (17)
Co1—O6	2.1336 (9)	C5—C6	1.5172 (17)
Co1—N1	2.0781 (9)	C7—C8	1.3681 (17)
Co1—N2	2.0596 (10)	C8—C9	1.387 (2)
O1—C1	1.2715 (13)	C9—C10	1.3705 (18)
O2—C1	1.2537 (14)	C10—C12	1.4064 (15)
O3—C6	1.2569 (15)	C11—C16	1.4070 (17)
O4—C6	1.2387 (17)	C13—C14	1.368 (2)
O5—H51	0.775 (19)	C14—C15	1.388 (3)
O5—H52	0.80 (2)	C15—C16	1.374 (2)
O6—H62	0.77 (2)	C2—H2A	0.9700
O6—H61	0.83 (2)	C2—H2B	0.9700
O7—H71	0.74 (3)	C3—H3A	0.9700
O7—H72	0.89 (2)	C3—H3B	0.9700
O8—H81	0.88 (3)	C4—H4B	0.9700
O8—H82	0.79 (3)	C4—H4A	0.9700
O9—H92	0.79 (3)	C5—H5A	0.9700
O9—H91	0.77 (2)	C5—H5B	0.9700
N1—C12	1.3350 (14)	C7—H7	0.9300
N1—C7	1.3527 (15)	C8—H8	0.9300
N2—C11	1.3363 (15)	C9—H9	0.9300
N2—C13	1.3580 (17)	C10—H10	0.9300
N3—C12	1.3815 (15)	C13—H13	0.9300
N3—C11	1.3785 (15)	C14—H14	0.9300
N3—H3	0.78 (2)	C15—H15	0.9300
C1—C2	1.5059 (16)	C16—H16	0.9300

O1—Co1—O2	59.68 (3)	C9—C10—C12	119.02 (11)
O1—Co1—O5	89.56 (4)	N3—C11—C16	116.66 (11)
O1—Co1—O6	88.57 (4)	N2—C11—N3	121.87 (10)
O1—Co1—N1	100.35 (4)	N2—C11—C16	121.46 (10)
O1—Co1—N2	169.33 (4)	N1—C12—N3	121.29 (9)
O2—Co1—O5	84.94 (4)	N3—C12—C10	116.80 (10)
O2—Co1—O6	87.44 (3)	N1—C12—C10	121.92 (10)
O2—Co1—N1	159.98 (4)	N2—C13—C14	123.44 (14)
O2—Co1—N2	109.79 (4)	C13—C14—C15	118.04 (15)
O5—Co1—O6	172.04 (4)	C14—C15—C16	119.82 (14)
O5—Co1—N1	94.09 (4)	C11—C16—C15	118.94 (13)
O5—Co1—N2	91.18 (4)	C1—C2—H2B	108.00
O6—Co1—N1	93.86 (4)	H2A—C2—H2B	107.00
O6—Co1—N2	89.24 (4)	C3—C2—H2A	108.00
N1—Co1—N2	90.21 (4)	C3—C2—H2B	108.00
Co1—O1—C1	95.33 (7)	C1—C2—H2A	108.00
Co1—O2—C1	84.88 (6)	C4—C3—H3B	109.00
Co1—O5—H51	122.6 (16)	H3A—C3—H3B	108.00
Co1—O5—H52	120.3 (15)	C4—C3—H3A	109.00
H51—O5—H52	104 (2)	C2—C3—H3A	109.00
Co1—O6—H61	116 (2)	C2—C3—H3B	109.00
Co1—O6—H62	112.1 (15)	C3—C4—H4A	109.00
H61—O6—H62	107 (3)	C3—C4—H4B	109.00
H71—O7—H72	112 (3)	C5—C4—H4A	109.00
H81—O8—H82	103 (3)	C5—C4—H4B	109.00
H91—O9—H92	111 (3)	H4A—C4—H4B	108.00
C7—N1—C12	117.69 (9)	C6—C5—H5A	109.00
Co1—N1—C12	125.38 (7)	H5A—C5—H5B	108.00
Co1—N1—C7	116.84 (8)	C4—C5—H5B	109.00
Co1—N2—C13	116.29 (9)	C6—C5—H5B	109.00
C11—N2—C13	118.28 (10)	C4—C5—H5A	109.00
Co1—N2—C11	125.44 (7)	N1—C7—H7	118.00
C11—N3—C12	132.59 (11)	C8—C7—H7	118.00
C12—N3—H3	110.7 (14)	C9—C8—H8	121.00
C11—N3—H3	116.2 (14)	C7—C8—H8	121.00
O1—C1—C2	116.83 (10)	C10—C9—H9	120.00
O2—C1—C2	123.13 (10)	C8—C9—H9	120.00
O1—C1—O2	120.04 (10)	C9—C10—H10	120.00
C1—C2—C3	116.75 (10)	C12—C10—H10	121.00
C2—C3—C4	111.55 (10)	N2—C13—H13	118.00
C3—C4—C5	113.16 (10)	C14—C13—H13	118.00
C4—C5—C6	114.59 (10)	C15—C14—H14	121.00
O4—C6—C5	119.03 (11)	C13—C14—H14	121.00
O3—C6—O4	124.09 (12)	C14—C15—H15	120.00
O3—C6—C5	116.88 (11)	C16—C15—H15	120.00
N1—C7—C8	123.70 (12)	C11—C16—H16	120.00
C7—C8—C9	118.30 (12)	C15—C16—H16	121.00
C8—C9—C10	119.36 (11)

O2—Co1—O1—C1	1.54 (6)	C12—N1—C7—C8	1.49 (17)
O5—Co1—O1—C1	−82.85 (7)	Co1—N1—C12—N3	−4.11 (15)
O6—Co1—O1—C1	89.41 (7)	Co1—N1—C12—C10	175.23 (8)
N1—Co1—O1—C1	−176.92 (7)	C7—N1—C12—N3	179.59 (10)
O1—Co1—O2—C1	−1.56 (6)	C7—N1—C12—C10	−1.07 (16)
O5—Co1—O2—C1	90.90 (7)	Co1—N2—C11—N3	0.16 (15)
O6—Co1—O2—C1	−91.40 (7)	Co1—N2—C11—C16	−178.58 (9)
N1—Co1—O2—C1	2.85 (14)	C13—N2—C11—N3	179.90 (11)
N2—Co1—O2—C1	−179.67 (7)	C13—N2—C11—C16	1.16 (17)
O1—Co1—N1—C7	11.20 (9)	Co1—N2—C13—C14	178.23 (13)
O1—Co1—N1—C12	−165.14 (9)	C11—N2—C13—C14	−1.5 (2)
O2—Co1—N1—C7	7.33 (16)	C12—N3—C11—N2	17.69 (19)
O2—Co1—N1—C12	−169.01 (9)	C12—N3—C11—C16	−163.51 (12)
O5—Co1—N1—C7	−79.11 (9)	C11—N3—C12—N1	−15.42 (19)
O5—Co1—N1—C12	104.56 (9)	C11—N3—C12—C10	165.21 (12)
O6—Co1—N1—C7	100.44 (9)	O1—C1—C2—C3	−167.09 (10)
O6—Co1—N1—C12	−75.89 (9)	O2—C1—C2—C3	12.39 (16)
N2—Co1—N1—C7	−170.31 (9)	C1—C2—C3—C4	175.72 (9)
N2—Co1—N1—C12	13.36 (9)	C2—C3—C4—C5	175.19 (10)
O2—Co1—N2—C11	169.49 (9)	C3—C4—C5—C6	−170.72 (10)
O2—Co1—N2—C13	−10.25 (10)	C4—C5—C6—O3	150.64 (12)
O5—Co1—N2—C11	−105.46 (10)	C4—C5—C6—O4	−29.52 (17)
O5—Co1—N2—C13	74.80 (10)	N1—C7—C8—C9	−0.72 (19)
O6—Co1—N2—C11	82.49 (9)	C7—C8—C9—C10	−0.50 (19)
O6—Co1—N2—C13	−97.25 (9)	C8—C9—C10—C12	0.87 (18)
N1—Co1—N2—C11	−11.37 (9)	C9—C10—C12—N1	−0.08 (16)
N1—Co1—N2—C13	168.89 (9)	C9—C10—C12—N3	179.29 (11)
Co1—O1—C1—O2	−2.83 (11)	N2—C11—C16—C15	0.00 (19)
Co1—O1—C1—C2	176.67 (8)	N3—C11—C16—C15	−178.80 (13)
Co1—O2—C1—O1	2.54 (10)	N2—C13—C14—C15	0.7 (2)
Co1—O2—C1—C2	−176.93 (10)	C13—C14—C15—C16	0.5 (2)
Co1—N1—C7—C8	−175.13 (10)	C14—C15—C16—C11	−0.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O9ⁱ	0.78 (2)	2.05 (2)	2.8228 (17)	172 (2)
O5—H51···O7ⁱⁱ	0.775 (19)	1.923 (19)	2.6933 (15)	172.7 (19)
O5—H52···O3ⁱⁱⁱ	0.80 (2)	1.97 (2)	2.7706 (17)	173 (2)
O6—H61···O2^iv	0.83 (2)	2.00 (2)	2.8278 (12)	178 (4)
O6—H62···O8	0.77 (2)	1.94 (2)	2.7056 (16)	170 (2)
O7—H71···O3^v	0.74 (3)	2.56 (3)	3.2596 (18)	160 (3)
O7—H72···O1	0.89 (2)	1.86 (2)	2.7543 (16)	175 (2)
O8—H81···O4^v	0.88 (3)	1.97 (3)	2.8221 (19)	163 (2)
O8—H82···O4^vi	0.79 (3)	2.05 (3)	2.832 (2)	175 (3)
O9—H91···O3^vii	0.77 (2)	2.12 (2)	2.8670 (17)	164 (2)
O9—H92···O3^v	0.79 (3)	1.99 (3)	2.7452 (17)	160 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z; (iii) −x+3, −y+1, −z+1; (iv) −x+2, −y+1, −z+1; (v) −x+3, −y+2, −z+1; (vi) x−1, y, z; (vii) x−1, y, z−1.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₈O₄)(C₁₀H₉N₃)(H₂O)₂]·3H₂O
M_r	464.34
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.9587 (3), 10.5458 (3), 11.0885 (3)
α, β, γ (°)	100.887 (1), 105.891 (1), 107.889 (1)
V (Å³)	1017.38 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.26 × 0.21 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.800, 0.855
No. of measured, independent and observed [I > 2σ(I)] reflections	28998, 8197, 6984
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.785

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.097, 0.99
No. of reflections	8197
No. of parameters	306
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.34

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Co1—O1	2.0680 (10)	Co1—O6	2.1336 (9)
Co1—O2	2.3079 (9)	Co1—N1	2.0781 (9)
Co1—O5	2.0877 (12)	Co1—N2	2.0596 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O9ⁱ	0.78 (2)	2.05 (2)	2.8228 (17)	172 (2)
O5—H51···O7ⁱⁱ	0.775 (19)	1.923 (19)	2.6933 (15)	172.7 (19)
O5—H52···O3ⁱⁱⁱ	0.80 (2)	1.97 (2)	2.7706 (17)	173 (2)
O6—H61···O2^iv	0.83 (2)	2.00 (2)	2.8278 (12)	178 (4)
O6—H62···O8	0.77 (2)	1.94 (2)	2.7056 (16)	170 (2)
O7—H71···O3^v	0.74 (3)	2.56 (3)	3.2596 (18)	160 (3)
O7—H72···O1	0.89 (2)	1.86 (2)	2.7543 (16)	175 (2)
O8—H81···O4^v	0.88 (3)	1.97 (3)	2.8221 (19)	163 (2)
O8—H82···O4^vi	0.79 (3)	2.05 (3)	2.832 (2)	175 (3)
O9—H91···O3^vii	0.77 (2)	2.12 (2)	2.8670 (17)	164 (2)
O9—H92···O3^v	0.79 (3)	1.99 (3)	2.7452 (17)	160 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z; (iii) −x+3, −y+1, −z+1; (iv) −x+2, −y+1, −z+1; (v) −x+3, −y+2, −z+1; (vi) x−1, y, z; (vii) x−1, y, z−1.

Acknowledgements

We are grateful for financial assistance from the DG–RSDT and ANDRU (Diretion Générale de la Recherche Scientifique et du Développement Technologique et l^'Agence Nationale pour le Développement de la Recherche Universitaire, Algéria) through the PNR project.

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Rao, C. N. R., Natarajan, S. & Vaidhyanathan, R. (2004). Angew. Chem. Int. Ed. Engl. 43, 1466–1496. Web of Science CrossRef PubMed CAS Google Scholar
Setifi, F., Benmansour, S., Triki, S., Gómez-García, C. J., Marchivie, M., Salaün, J.-Y. & Maamache, M. (2007). Inorg. Chim. Acta, 360, 3879–3886. Web of Science CSD CrossRef CAS Google Scholar
Setifi, F., Bouchama, A., Sala-Pala, J., Salaün, J.-Y. & Triki, S. (2006). Inorg. Chim. Acta, 359, 3269–3274. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wen, G.-L., Wang, Y.-Y., Zhang, W.-H., Ren, C., Liu, R.-T. & Shi, Q.-Z. (2010). CrystEngComm, 12, 1238–1251. Web of Science CSD CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar