Intra- and supra­molecular inter­actions in cis,mer-diaqua­tris­(1H-imidazole-κN3)(terephthalato-κO)cobalt(II) monohydrate

Benkanoun, A.; Balegroune, F.; Guehria-Laïdoudi, A.; Dahaoui, S.; Lecomte, C.

doi:10.1107/S1600536812011993

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m480-m481

doi:10.1107/S1600536812011993

Open

access

Intra- and supramolecular interactions in cis,mer-diaquatris(1H-imidazole-κN³)(terephthalato-κO)cobalt(II) monohydrate

Aouaouche Benkanoun,^a Fadila Balegroune,^a Achoura Guehria-Laïdoudi,^a ^* Slimane Dahaoui ^b and Claude Lecomte ^b

^aLaboratoire de Cristallographie-Thermodynamique, Faculté de Chimie, U.S.T.H.B., BP 32 El-Alia, Bab-Ezzouar 16111, Alger, Algeria, and ^bCRM 2,CNRS-UPRESA 7036, Université Henry Poincaré, Faculté des Sciences et Techniques, BP 70239, 54506 Vandoeuvres, Les Nancy Cedex, France
^*Correspondence e-mail: guehria_laidoudi@yahoo.fr

(Received 28 February 2012; accepted 20 March 2012; online 24 March 2012)

In the title compound, [Co(C₈H₄O₄)(C₃H₄N₂)₃(H₂O)₂]·H₂O, the cisoid angles are in the range 85.59 (5)–93.56 (5)°, while two equal transoid angles deviate significantly from the ideal linear angle, the third being almost linear. One carboxylate group is almost coplanar [1.23 (13)°] with the plane of its parent aromatic ring, although it has one O-atom donor involved in one coordination and one hydrogen bond as acceptor. The other carboxylate group does not coordinate and is rotated out of this plane with a torsional twist of 17.27 (20)°. The coordination neutral entity, based on aqua ligands and two cyclic co-ligands seems, at first sight, monomeric. Strongly tight, via one intramolecular hydrogen bond between aqua and carboxylate O atoms, it brings out a quasi-planar six-membered ring around the Co^II atom, turning the CoN₃O₃ coordination octahedron into a new building block. The rigidity of this feature associated with several hydrogen-bonded arrays yields an extended structure. In the resulting supramolecular packing, a binuclear hydrated Co^II assembly, built up from triple strands driven by different heterosynthons, embodies the synergy of coordination, covalent and hydrogen bonds.

Related literature

For general background to important structural features inducing some interesting properties, see: Chen et al. (1996 ); Yang et al. (2002 ); Ye & Chen (2003 ); Xie et al. (2009 ); Baca et al. (2003 ). For related compounds or structures, see: Niu et al. (2004 ); Tong et al. (2002 ); Liu et al. (2001 , 2003 ); Zeng et al. (1997 ).

Experimental

Crystal data

[Co(C₈H₄O₄)(C₃H₄N₂)₃(H₂O)₂]·H₂O
M_r = 481.34
Monoclinic, P 2₁ /n
a = 7.65363 (8) Å
b = 10.45169 (13) Å
c = 24.7538 (3) Å
β = 90.227 (1)°
V = 1980.12 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.92 mm⁻¹
T = 291 K
0.21 × 0.14 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995 )] T_min = 0.871, T_max = 0.935
86135 measured reflections
4760 independent reflections
4153 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.071
S = 1.08
4760 reflections
316 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co—O2W	2.1064 (11)
Co—N3	2.1076 (13)
Co—N5	2.1124 (13)
Co—N1	2.1347 (13)
Co—O1	2.1442 (10)
Co—O1W	2.1680 (11)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O1ⁱ	0.86 (2)	2.09 (2)	2.9204 (17)	162 (2)
N4—H4N⋯O3Wⁱⁱ	0.85 (2)	2.18 (2)	2.9842 (18)	157.0 (19)
N4—H4N⋯O4ⁱⁱⁱ	0.85 (2)	2.50 (2)	2.9521 (18)	114.5 (17)
N6—H6N⋯O3^iv	0.84 (2)	2.02 (2)	2.8249 (18)	162 (2)
O1W—H1W⋯O2	0.85 (3)	1.79 (3)	2.6160 (16)	163 (3)
O1W—H2W⋯O4^v	0.85 (3)	1.85 (3)	2.6606 (16)	161 (2)
O2W—H3W⋯O3^vi	0.82 (3)	1.95 (3)	2.7516 (16)	168 (2)
O2W—H4W⋯O3W^vii	0.82 (2)	2.00 (2)	2.8118 (17)	172 (2)
O3W—H5W⋯O1W	0.81 (2)	2.08 (2)	2.8632 (16)	164 (2)
O3W—H6W⋯O3^vi	0.82 (3)	1.95 (3)	2.7528 (17)	167 (2)
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z; (iii) -x, -y+1, -z+1; (iv) -x, -y, -z+1; (v) -x+1, -y+1, -z+1; (vi) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; 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, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812011993/ds2181sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812011993/ds2181Isup2.hkl

checkCIF report

Comment top

This Cobalt-based compound, is the first isomer evidenced, with two aqua ligands cis and three N-coordinated imidazole ligands meridional, relative to the Co^II centre (Fig.1). Although it is built up from monomeric entity, it exhibits a packing with a relatively interesting metal-metal separation. As shown in Table 1, the Co-Ocarboxylate and the average Co—Ow distances are very closed and are comparable to those observed in related compounds (Niu et al., 2004; Tong et al., 2002). The three independent imidazole groups, and the single terephthalate dianion, both unidentate, participate respectively as donor and acceptor, in strong to moderate hydrogen bonds, and allow the recognition of supramolecular dimensionality (Table 2). The backbone of the architecture is the helical hydrogen-bonded ladder running along b axis, composed of alternating R⁴₄(10) and R³₃(8) heterosynthons (Fig.2), which are developed in turn, in bicyclic sheets, both of them containing a six-membered ring, and connected to imidazole ligands via secondary N atom. The former is associated with a crossed R²₂(6) and involves one bifurcated intermolecular H-bond. The latter shares a common Co—O(aqua) bond with a cycle formed of two coordination and three covalent bondings, beside one intramolecular H-bond (Table 2). The resulting quasi-planar six-membered ring, is responsible of environment's rigidity around the metal centre and changes the coordination octahedron in a new building block. The three imidazoles participate as donor with oxygen atom of adjacent carboxylates, and they bring about polymeric chain which mimics the carboxylate-histidine-zinc triad systems (Chen et al., 1996; Yang et al., 2002; Ye et al., 2003; Xie et al., 2009). As seen in Fig.2 and Fig.3, all these overlapping subnetworks lead to the formation of cross-linked supramolecular layers where additional single H-bonds provided by secondary N atom of the imidazoles in one hand, and the spacer of the dicarboxylate on other hand, achieve a well organized three-dimensional packing. Within this three-dimensional framework, the binuclear Co^II assembly showing the shortest and probably interesting (Baca et al., 2003) separation metal-metal of 7.6536 (1) Å is built up from triple strand driven by R³₃(14), R⁴₄(16) and R⁵₅(18) heterosynthons (Fig.4). A comparison with the two chemically similar Co^II compounds [Co(C₃H₄N₂)₄(H₂O)₂](C₈H₄0₄), and [Co(C₃H₄N₂)](C₈H₄0₄).4H₂O (Tong et al., 2002), as well as their isostructural compounds obtained with Mn(II) (Liu et al., 2001;2003) and Cu(II) (Zeng et al., 1997), reveals that their building blocks are mononuclear, and the terephthalate dianion doesn't get involved in coordination. With this study, we may confirm that in this structure, a competition takes place between terephthalate and water and it is probably the presence of both coordinated and uncoordinated water molecules, which builts a new building block, by enhancing the dicarboxylato ligand ability to get involved in coordination sphere.

Related literature top

For general background to important structural features inducing some interesting properties see: Chen et al. (1996); Yang et al. (2002); Ye et al. (2003); Xie et al. (2009); Baca et al. (2003). For related compounds or structures, see: Niu et al. (2004); Tong et al. (2002); Liu et al. (2001, 2003); Zeng et al. (1997).

Experimental top

A mixture of CoCl₂,6H₂O (0.24 g, 1 mmol), terephthalic acid (0.17 g,1 mmol), imidazole (0.14 g, 2 mmol) NaOH (0.08 g, 2 mmol) and water (15 ml) was stirred for 30 min at room temperature, then transferred in a 25 ml Teflon-lined stainless steel reactor, then sealed and heated at 120°C for 72 h. Upon cooling to room temperature, light-pink crystals of title compound suitable for X-ray crystallographic analysis were obtained.

Structure description top

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. : The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. : Helical hydrogen-bonded ladder composed of R³₃(8) and R⁴₄(10). Symmetry codes: i: x + 1,y,z; ii: x - 1,y,z; v: -x + 1,-y + 1,-z + 1; vii: -x + 3/2,y - 1/2,-z + 3/2; viii: x - 1/2,-y - 1/2,-z - 1/2; ix: -x + 3/2,y + 1/2,-z + 3/2; x: -x + 1/2,y - 1/2,-z + 3/2 xi: -x + 1/2,y + 1/2,-z + 3/2, xii: x + 1, y + 1,z; xiii: x,y + 1,z; xiv: -x + 5/2,y + 1/2,-z + 3/2, xv: x - 1/2,-y + 1/2,z - 1/2
	Fig. 3. : Packing diagram viewed along [100] showing hydrogen bonds and ladder's layers.
	Fig. 4. : Binuclear Co^II assembly with triple strand. Symmetry codes: ii: x - 1,y,z; iii: -x,-y + 1,-z + 1; iv: -x,-y,-z + 1; x: -x + 1/2,y - 1/2,-z + 3/2

cis,mer-diaquatris(1H-imidazole- κN³)(terephthalato-κO)cobalt(II) monohydrate top

Crystal data top

[Co(C₈H₄O₄)(C₃H₄N₂)₃(H₂O)₂]·H₂O	F(000) = 996
M_r = 481.34	D_x = 1.615 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 35056 reflections
a = 7.65363 (8) Å	θ = 3.3–32.9°
b = 10.45169 (13) Å	µ = 0.92 mm⁻¹
c = 24.7538 (3) Å	T = 291 K
β = 90.227 (1)°	Prism, pink
V = 1980.12 (4) Å³	0.21 × 0.14 × 0.08 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer	4760 independent reflections
Radiation source: fine-focus sealed tube	4153 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
Detector resolution: 10.4508 pixels mm^-1	θ_max = 28.0°, θ_min = 3.4°
wσcans	h = −10→10
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	k = −13→13
T_min = 0.871, T_max = 0.935	l = −32→32
86135 measured reflections

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0265P)² + 1.5429P] where P = (F_o² + 2F_c²)/3
4760 reflections	(Δ/σ)_max = 0.003
316 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Co(C₈H₄O₄)(C₃H₄N₂)₃(H₂O)₂]·H₂O	V = 1980.12 (4) Å³
M_r = 481.34	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.65363 (8) Å	µ = 0.92 mm⁻¹
b = 10.45169 (13) Å	T = 291 K
c = 24.7538 (3) Å	0.21 × 0.14 × 0.08 mm
β = 90.227 (1)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	4760 independent reflections
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2009), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]	4153 reflections with I > 2σ(I)
T_min = 0.871, T_max = 0.935	R_int = 0.066
86135 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.40 e Å⁻³
4760 reflections	Δρ_min = −0.33 e Å⁻³
316 parameters

Special details top

Experimental. Absorption correction: CrysAlis RED, Oxford Diffraction (2009) Analytical numerical absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995).

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. CrysAlis RED, Oxford Diffraction Ltd 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
Co	0.44254 (2)	0.144772 (19)	0.652633 (8)	0.00874 (6)
O1W	0.52240 (15)	0.33528 (11)	0.67705 (4)	0.0123 (2)
O2W	0.60355 (16)	0.07515 (12)	0.71527 (5)	0.0147 (2)
O3W	0.66608 (15)	0.36561 (12)	0.78325 (5)	0.0149 (2)
O1	0.29257 (14)	0.22971 (10)	0.58868 (4)	0.0115 (2)
O2	0.31457 (15)	0.43979 (11)	0.60544 (4)	0.0165 (2)
O3	0.05014 (14)	0.36582 (10)	0.32226 (4)	0.0130 (2)
O4	0.16128 (14)	0.56111 (11)	0.33113 (4)	0.0134 (2)
C1	0.28701 (19)	0.34725 (15)	0.57476 (6)	0.0116 (3)
C2	0.24336 (19)	0.37422 (15)	0.51627 (6)	0.0115 (3)
C3	0.21121 (19)	0.27458 (15)	0.48037 (6)	0.0115 (3)
H3	0.2188	0.1885	0.4925	0.014*
C4	0.16812 (19)	0.30000 (15)	0.42695 (6)	0.0117 (3)
H4	0.1412	0.2315	0.4031	0.014*
C5	0.16416 (19)	0.42578 (15)	0.40819 (6)	0.0106 (3)
C6	0.2013 (2)	0.52539 (15)	0.44372 (6)	0.0154 (3)
H6	0.2019	0.6111	0.4310	0.018*
C7	0.2375 (2)	0.49999 (16)	0.49776 (6)	0.0160 (3)
H7	0.2584	0.5686	0.5221	0.019*
C8	0.12281 (19)	0.45417 (14)	0.34977 (6)	0.0101 (3)
N1	0.66337 (16)	0.13362 (12)	0.60043 (5)	0.0113 (3)
N2	0.93656 (18)	0.13617 (13)	0.57266 (6)	0.0143 (3)
C9	0.8290 (2)	0.13727 (15)	0.61550 (6)	0.0128 (3)
H9	0.8674	0.1403	0.6520	0.015*
C10	0.8336 (2)	0.13227 (16)	0.52700 (6)	0.0155 (3)
H10	0.8722	0.1310	0.4906	0.019*
C11	0.6653 (2)	0.13062 (15)	0.54460 (6)	0.0143 (3)
H11	0.5647	0.1278	0.5220	0.017*
N3	0.23535 (16)	0.16873 (12)	0.70755 (5)	0.0115 (3)
N4	−0.00080 (18)	0.25190 (14)	0.74341 (5)	0.0145 (3)
C12	0.1779 (2)	0.09015 (16)	0.74877 (6)	0.0146 (3)
H12	0.2327	0.0129	0.7599	0.017*
C13	0.0312 (2)	0.14045 (16)	0.77079 (6)	0.0152 (3)
H13	−0.0359	0.1054	0.7994	0.018*
C14	0.12406 (19)	0.26542 (15)	0.70594 (6)	0.0127 (3)
H14	0.1315	0.3352	0.6815	0.015*
N5	0.36196 (16)	−0.04089 (12)	0.62981 (5)	0.0120 (3)
N6	0.23014 (18)	−0.22776 (14)	0.63208 (6)	0.0157 (3)
C15	0.4649 (2)	−0.13139 (15)	0.60470 (6)	0.0141 (3)
H15	0.5754	−0.1150	0.5888	0.017*
C16	0.3850 (2)	−0.24738 (16)	0.60607 (6)	0.0159 (3)
H16	0.4278	−0.3258	0.5919	0.019*
C17	0.2212 (2)	−0.10428 (16)	0.64582 (6)	0.0147 (3)
H17	0.1262	−0.0667	0.6647	0.018*
H2N	1.048 (3)	0.147 (2)	0.5743 (9)	0.030 (6)*
H4N	−0.088 (3)	0.301 (2)	0.7480 (8)	0.022 (5)*
H6N	0.156 (3)	−0.283 (2)	0.6416 (9)	0.026 (6)*
H1W	0.454 (3)	0.381 (3)	0.6584 (10)	0.043 (7)*
H2W	0.623 (3)	0.360 (2)	0.6673 (9)	0.034 (6)*
H3W	0.576 (3)	0.085 (2)	0.7469 (10)	0.036 (7)*
H4W	0.670 (3)	0.014 (2)	0.7123 (9)	0.029 (6)*
H5W	0.610 (3)	0.365 (2)	0.7556 (9)	0.025 (6)*
H6W	0.639 (3)	0.301 (2)	0.7995 (9)	0.031 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.00883 (10)	0.00915 (11)	0.00823 (10)	−0.00041 (7)	0.00022 (7)	0.00042 (7)
O1W	0.0120 (5)	0.0125 (6)	0.0125 (5)	−0.0014 (4)	−0.0014 (4)	0.0007 (4)
O2W	0.0183 (6)	0.0166 (6)	0.0093 (5)	0.0060 (5)	−0.0001 (4)	0.0001 (4)
O3W	0.0167 (6)	0.0158 (6)	0.0120 (5)	−0.0031 (5)	−0.0020 (5)	0.0025 (5)
O1	0.0127 (5)	0.0111 (5)	0.0107 (5)	−0.0006 (4)	−0.0015 (4)	0.0024 (4)
O2	0.0244 (6)	0.0126 (5)	0.0125 (5)	−0.0002 (5)	−0.0050 (5)	−0.0009 (4)
O3	0.0158 (5)	0.0130 (5)	0.0101 (5)	−0.0024 (4)	−0.0015 (4)	−0.0003 (4)
O4	0.0146 (5)	0.0124 (5)	0.0134 (5)	−0.0022 (4)	−0.0017 (4)	0.0038 (4)
C1	0.0094 (6)	0.0142 (7)	0.0113 (7)	−0.0001 (6)	0.0001 (5)	0.0019 (6)
C2	0.0114 (7)	0.0137 (7)	0.0093 (7)	0.0006 (6)	−0.0007 (5)	0.0011 (6)
C3	0.0116 (7)	0.0103 (7)	0.0127 (7)	0.0001 (5)	−0.0008 (6)	0.0022 (6)
C4	0.0113 (7)	0.0116 (7)	0.0121 (7)	0.0003 (6)	0.0005 (5)	−0.0013 (6)
C5	0.0095 (6)	0.0125 (7)	0.0098 (7)	−0.0001 (5)	0.0000 (5)	0.0006 (6)
C6	0.0218 (8)	0.0101 (7)	0.0141 (7)	−0.0013 (6)	−0.0020 (6)	0.0015 (6)
C7	0.0230 (8)	0.0117 (8)	0.0131 (7)	−0.0015 (6)	−0.0037 (6)	−0.0015 (6)
C8	0.0079 (6)	0.0130 (7)	0.0095 (7)	0.0012 (5)	0.0011 (5)	−0.0006 (6)
N1	0.0120 (6)	0.0118 (6)	0.0101 (6)	−0.0012 (5)	0.0007 (5)	−0.0010 (5)
N2	0.0108 (6)	0.0168 (7)	0.0153 (7)	−0.0009 (5)	0.0021 (5)	0.0002 (5)
C9	0.0120 (7)	0.0138 (7)	0.0126 (7)	−0.0012 (6)	0.0009 (6)	0.0000 (6)
C10	0.0157 (7)	0.0194 (8)	0.0114 (7)	−0.0020 (6)	0.0029 (6)	−0.0007 (6)
C11	0.0153 (7)	0.0173 (8)	0.0105 (7)	−0.0021 (6)	0.0004 (6)	0.0002 (6)
N3	0.0116 (6)	0.0126 (6)	0.0104 (6)	0.0004 (5)	0.0008 (5)	0.0002 (5)
N4	0.0121 (6)	0.0157 (7)	0.0158 (7)	0.0017 (5)	0.0021 (5)	−0.0027 (5)
C12	0.0169 (7)	0.0143 (8)	0.0124 (7)	0.0000 (6)	0.0009 (6)	0.0024 (6)
C13	0.0151 (7)	0.0182 (8)	0.0123 (7)	−0.0036 (6)	0.0023 (6)	0.0010 (6)
C14	0.0127 (7)	0.0118 (7)	0.0135 (7)	0.0002 (6)	−0.0009 (6)	−0.0001 (6)
N5	0.0121 (6)	0.0115 (6)	0.0124 (6)	−0.0016 (5)	0.0011 (5)	−0.0002 (5)
N6	0.0172 (7)	0.0139 (7)	0.0161 (7)	−0.0062 (6)	−0.0014 (5)	0.0019 (5)
C15	0.0156 (7)	0.0131 (7)	0.0135 (7)	−0.0001 (6)	0.0019 (6)	−0.0009 (6)
C16	0.0200 (8)	0.0130 (8)	0.0147 (7)	−0.0010 (6)	−0.0015 (6)	−0.0014 (6)
C17	0.0131 (7)	0.0158 (8)	0.0151 (7)	−0.0023 (6)	0.0008 (6)	−0.0004 (6)

Geometric parameters (Å, º) top

Co—O2W	2.1064 (11)	N1—C9	1.3204 (19)
Co—N3	2.1076 (13)	N1—C11	1.3825 (19)
Co—N5	2.1124 (13)	N2—C9	1.345 (2)
Co—N1	2.1347 (13)	N2—C10	1.376 (2)
Co—O1	2.1442 (10)	N2—H2N	0.86 (2)
Co—O1W	2.1680 (11)	C9—H9	0.9500
O1W—H1W	0.85 (3)	C10—C11	1.362 (2)
O1W—H2W	0.85 (3)	C10—H10	0.9500
O2W—H3W	0.82 (3)	C11—H11	0.9500
O2W—H4W	0.82 (2)	N3—C14	1.322 (2)
O3W—H5W	0.81 (2)	N3—C12	1.383 (2)
O3W—H6W	0.82 (3)	N4—C14	1.342 (2)
O1—C1	1.2765 (19)	N4—C13	1.369 (2)
O2—C1	1.2471 (19)	N4—H4N	0.85 (2)
O3—C8	1.2738 (18)	C12—C13	1.356 (2)
O4—C8	1.2450 (19)	C12—H12	0.9500
C1—C2	1.511 (2)	C13—H13	0.9500
C2—C3	1.390 (2)	C14—H14	0.9500
C2—C7	1.393 (2)	N5—C17	1.327 (2)
C3—C4	1.387 (2)	N5—C15	1.380 (2)
C3—H3	0.9500	N6—C17	1.337 (2)
C4—C5	1.395 (2)	N6—C16	1.366 (2)
C4—H4	0.9500	N6—H6N	0.84 (2)
C5—C6	1.391 (2)	C15—C16	1.358 (2)
C5—C8	1.509 (2)	C15—H15	0.9500
C6—C7	1.391 (2)	C16—H16	0.9500
C6—H6	0.9500	C17—H17	0.9500
C7—H7	0.9500

O2W—Co—N3	90.33 (5)	O3—C8—C5	117.34 (13)
O2W—Co—N5	92.80 (5)	C9—N1—C11	105.60 (13)
N3—Co—N5	93.56 (5)	C9—N1—Co	126.08 (10)
O2W—Co—N1	87.96 (5)	C11—N1—Co	128.17 (10)
N3—Co—N1	175.12 (5)	C9—N2—C10	107.31 (13)
N5—Co—N1	91.09 (5)	C9—N2—H2N	124.9 (15)
O2W—Co—O1	175.14 (5)	C10—N2—H2N	127.3 (15)
N3—Co—O1	91.44 (4)	N1—C9—N2	111.54 (14)
N5—Co—O1	91.60 (5)	N1—C9—H9	124.2
N1—Co—O1	89.91 (5)	N2—C9—H9	124.2
O2W—Co—O1W	87.05 (5)	C11—C10—N2	106.07 (14)
N3—Co—O1W	85.59 (5)	C11—C10—H10	127.0
N5—Co—O1W	179.13 (5)	N2—C10—H10	127.0
N1—Co—O1W	89.76 (5)	C10—C11—N1	109.48 (14)
O1—Co—O1W	88.57 (4)	C10—C11—H11	125.3
Co—O1W—H1W	101.0 (18)	N1—C11—H11	125.3
Co—O1W—H2W	117.2 (16)	C14—N3—C12	105.64 (13)
H1W—O1W—H2W	104 (2)	C14—N3—Co	123.89 (11)
Co—O2W—H3W	120.8 (17)	C12—N3—Co	130.35 (11)
Co—O2W—H4W	124.3 (16)	C14—N4—C13	107.78 (14)
H3W—O2W—H4W	110 (2)	C14—N4—H4N	126.4 (14)
H5W—O3W—H6W	106 (2)	C13—N4—H4N	125.7 (14)
C1—O1—Co	127.94 (10)	C13—C12—N3	109.42 (14)
O2—C1—O1	125.22 (14)	C13—C12—H12	125.3
O2—C1—C2	118.35 (14)	N3—C12—H12	125.3
O1—C1—C2	116.43 (13)	C12—C13—N4	106.11 (14)
C3—C2—C7	119.42 (14)	C12—C13—H13	126.9
C3—C2—C1	120.70 (14)	N4—C13—H13	126.9
C7—C2—C1	119.87 (14)	N3—C14—N4	111.05 (14)
C4—C3—C2	120.44 (14)	N3—C14—H14	124.5
C4—C3—H3	119.8	N4—C14—H14	124.5
C2—C3—H3	119.8	C17—N5—C15	104.94 (13)
C3—C4—C5	120.18 (14)	C17—N5—Co	127.98 (11)
C3—C4—H4	119.9	C15—N5—Co	125.69 (10)
C5—C4—H4	119.9	C17—N6—C16	108.07 (14)
C6—C5—C4	119.39 (14)	C17—N6—H6N	123.5 (15)
C6—C5—C8	120.01 (14)	C16—N6—H6N	128.1 (15)
C4—C5—C8	120.59 (13)	C16—C15—N5	110.03 (14)
C7—C6—C5	120.30 (15)	C16—C15—H15	125.0
C7—C6—H6	119.9	N5—C15—H15	125.0
C5—C6—H6	119.9	C15—C16—N6	105.63 (14)
C6—C7—C2	120.18 (15)	C15—C16—H16	127.2
C6—C7—H7	119.9	N6—C16—H16	127.2
C2—C7—H7	119.9	N5—C17—N6	111.33 (14)
O4—C8—O3	123.78 (14)	N5—C17—H17	124.3
O4—C8—C5	118.87 (13)	N6—C17—H17	124.3

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1ⁱ	0.86 (2)	2.09 (2)	2.9204 (17)	162 (2)
N4—H4N···O3Wⁱⁱ	0.85 (2)	2.18 (2)	2.9842 (18)	157.0 (19)
N4—H4N···O4ⁱⁱⁱ	0.85 (2)	2.50 (2)	2.9521 (18)	114.5 (17)
N6—H6N···O3^iv	0.84 (2)	2.02 (2)	2.8249 (18)	162 (2)
O1W—H1W···O2	0.85 (3)	1.79 (3)	2.6160 (16)	163 (3)
O1W—H2W···O4^v	0.85 (3)	1.85 (3)	2.6606 (16)	161 (2)
O2W—H3W···O3^vi	0.82 (3)	1.95 (3)	2.7516 (16)	168 (2)
O2W—H4W···O3W^vii	0.82 (2)	2.00 (2)	2.8118 (17)	172 (2)
O3W—H5W···O1W	0.81 (2)	2.08 (2)	2.8632 (16)	164 (2)
O3W—H6W···O3^vi	0.82 (3)	1.95 (3)	2.7528 (17)	167 (2)

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

Experimental details

Crystal data
Chemical formula	[Co(C₈H₄O₄)(C₃H₄N₂)₃(H₂O)₂]·H₂O
M_r	481.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	7.65363 (8), 10.45169 (13), 24.7538 (3)
β (°)	90.227 (1)
V (Å³)	1980.12 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.92
Crystal size (mm)	0.21 × 0.14 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur
Absorption correction	Analytical [CrysAlis RED (Oxford Diffraction, 2009), using a multi-faceted crystal model based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.871, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	86135, 4760, 4153
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.071, 1.08
No. of reflections	4760
No. of parameters	316
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.33

Computer programs: CrysAlis CCD (Oxford Diffraction, 2009), CrysAlis RED (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

Co—O2W	2.1064 (11)	Co—N1	2.1347 (13)
Co—N3	2.1076 (13)	Co—O1	2.1442 (10)
Co—N5	2.1124 (13)	Co—O1W	2.1680 (11)

O2W—Co—N3	90.33 (5)	N1—Co—O1	89.91 (5)
O2W—Co—N5	92.80 (5)	O2W—Co—O1W	87.05 (5)
N3—Co—N5	93.56 (5)	N3—Co—O1W	85.59 (5)
O2W—Co—N1	87.96 (5)	N5—Co—O1W	179.13 (5)
N3—Co—N1	175.12 (5)	N1—Co—O1W	89.76 (5)
N5—Co—N1	91.09 (5)	O1—Co—O1W	88.57 (4)
O2W—Co—O1	175.14 (5)	O2—C1—O1	125.22 (14)
N3—Co—O1	91.44 (4)	O4—C8—O3	123.78 (14)
N5—Co—O1	91.60 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O1ⁱ	0.86 (2)	2.09 (2)	2.9204 (17)	162 (2)
N4—H4N···O3Wⁱⁱ	0.85 (2)	2.18 (2)	2.9842 (18)	157.0 (19)
N4—H4N···O4ⁱⁱⁱ	0.85 (2)	2.50 (2)	2.9521 (18)	114.5 (17)
N6—H6N···O3^iv	0.84 (2)	2.02 (2)	2.8249 (18)	162 (2)
O1W—H1W···O2	0.85 (3)	1.79 (3)	2.6160 (16)	163 (3)
O1W—H2W···O4^v	0.85 (3)	1.85 (3)	2.6606 (16)	161 (2)
O2W—H3W···O3^vi	0.82 (3)	1.95 (3)	2.7516 (16)	168 (2)
O2W—H4W···O3W^vii	0.82 (2)	2.00 (2)	2.8118 (17)	172 (2)
O3W—H5W···O1W	0.81 (2)	2.08 (2)	2.8632 (16)	164 (2)
O3W—H6W···O3^vi	0.82 (3)	1.95 (3)	2.7528 (17)	167 (2)

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

References

Baca, S. G., Filippova, I. G., Gerbeleu, N. V., Simonov, Y. A., Gdaniec, M., Timco, G. A., Gherco, O. A. & Malaestean, Y. L. (2003). Inorg. Chim. Acta, 344, 109–116. Web of Science CSD CrossRef CAS Google Scholar
Chen, X. M., Ye, B. H., Huang, X. C. & Xu, Z. T. (1996). J. Chem. Soc. Dalton Trans. pp. 3465–3468. CSD CrossRef Web of Science Google Scholar
Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Liu, Y., Xu, D. J. & Liu, J. (2001). J. Coord. Chem. 54, 175–181. Web of Science CrossRef CAS Google Scholar
Liu, Y., Xu, D. J., Nie, J. J., Wu, J. Y. & Chiang, M. Y. (2003). J. Coord. Chem. 56, 155–159. Web of Science CSD CrossRef CAS Google Scholar
Niu, S.-Y., Zhang, S.-S., Li, X.-M., Wen, Y.-H. & Jiao, K. (2004). Acta Cryst. E60, m209–m211. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tong, M.-L., Li, W., Chen, X.-M. & Ng, S. W. (2002). Acta Cryst. E58, m186–m188. Web of Science CSD CrossRef IUCr Journals Google Scholar
Xie, Q.-A., Dong, G.-Y., Yu, Y.-M. & Wang, Y.-G. (2009). Acta Cryst. E65, m576. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yang, J. H., Zheng, S. L., Jim, T., Liu, G. F. & Chen, X. M. (2002). Aust. J. Chem. 55, 741–744. Web of Science CSD CrossRef CAS Google Scholar
Ye, B. H. & Chen, X. M. (2003). Chin. J. Chem. 21, 531–536. CAS Google Scholar
Zeng, H., Yang, M., Huang, X. & Chen, X. (1997). Cryst. Res. Technol. 32, 467–473. CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m480-m481

doi:10.1107/S1600536812011993

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)