Piperazine-1,4-diium bis­(pyridine-2,6-dicarboxyl­ato-κ3O2,N,O6)cobaltate(II) tetra­hydrate

Raissi Shabari, A.; Ghoddoosi, N.; Pourayoubi, M.; Moradi, S.

doi:10.1107/S1600536811023518

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m985-m986

doi:10.1107/S1600536811023518

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Piperazine-1,4-diium bis(pyridine-2,6-dicarboxylato-κ³O²,N,O⁶)cobaltate(II) tetrahydrate

Akbar Raissi Shabari,^a ^* Nazanin Ghoddoosi,^a Mehrdad Pourayoubi ^b and Shahram Moradi ^a

^aFaculty of Chemistry, North Tehran Branch, Islamic Azad University, Tehran, Iran, and ^bDepartment of Chemistry, Ferdowsi University of Mashhad, Mashhad, 91779, Iran
^*Correspondence e-mail: a.raissi_shabari@yahoo.com

(Received 5 June 2011; accepted 16 June 2011; online 25 June 2011)

The asymmetric unit of the title complex, (C₄H₁₂N₂)[Co(C₇H₃NO₄)₂]·4H₂O, consists of one piperazinediium dication, one [Co(py-2,6-dc)₂]²⁻ dianion (where py-2,6-dc is pyridine-2,6-dicarboxylate) and four water molecules. The piperazinediium cation adopts a chair conformation and the Co^II ion is six-coordinated in an N₂O₄ environment, having a distorted octahedral geometry. In the crystal, intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds link the components, forming a three-dimensional network.

Related literature

The structure determination of title compound was performed as a part of our project on the synthesis of new proton-transfer compounds, see: Raissi Shabari et al. (2010 ). For bond lengths in a related cobaltate(II) complex, see: Pasdar et al. (2011 ). For bond lengths and angles in the piperazinediium dication, see: Sutherland & Harrison (2009 ); Allen et al. (1995 ). For positive-charge-assisted hydrogen bonds, see: Gilli et al. (1994 ).

Experimental

Crystal data

(C₄H₁₂N₂)[Co(C₇H₃NO₄)₂]·4H₂O
M_r = 549.36
Monoclinic, P 2₁ /n
a = 7.9537 (16) Å
b = 13.420 (3) Å
c = 21.004 (4) Å
β = 90.55 (3)°
V = 2241.8 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 150 K
0.5 × 0.40 × 0.15 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: numerical [shape of crystal determined optically (X-RED and X-SHAPE; Stoe & Cie, 2005 )] T_min = 0.670, T_max = 0.878
15339 measured reflections
6018 independent reflections
5226 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.077
S = 1.07
6018 reflections
364 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O12—H12B⋯O3ⁱ	0.79 (3)	2.06 (3)	2.8428 (18)	174 (3)
O11—H11B⋯O5	0.83 (3)	2.00 (3)	2.8290 (18)	177 (3)
O11—H11A⋯O1ⁱⁱ	0.81 (3)	2.02 (3)	2.8173 (19)	170 (3)
O10—H10B⋯O7	0.79 (3)	2.15 (3)	2.9213 (19)	165 (3)
O10—H10A⋯O11ⁱⁱⁱ	0.87 (3)	1.99 (3)	2.854 (2)	172 (3)
O9—H9B⋯O8	0.79 (3)	1.96 (3)	2.7521 (18)	175 (2)
O9—H9A⋯O12^iv	0.83 (3)	2.01 (3)	2.840 (2)	173 (3)
N4—H4B⋯O3^v	0.89 (2)	1.92 (2)	2.7973 (18)	165 (2)
N4—H4A⋯O6ⁱⁱⁱ	0.91 (2)	1.89 (2)	2.7592 (17)	161 (2)
N3—H3B⋯O9^vi	0.91 (2)	1.86 (2)	2.6958 (18)	152 (2)
N3—H3A⋯O2	0.91 (2)	2.50 (2)	3.1126 (19)	124.5 (18)
N3—H3A⋯O1	0.91 (2)	1.88 (2)	2.7957 (18)	176 (2)
C18—H18B⋯O10^vii	0.97	2.58	3.457 (2)	151
C17—H17B⋯O7^vii	0.97	2.36	3.127 (2)	135
C16—H16B⋯O12^iv	0.97	2.52	3.293 (2)	137
C15—H15B⋯O10^vi	0.97	2.60	3.261 (2)	126
C15—H15A⋯O2	0.97	2.54	3.140 (2)	120
Symmetry codes: (i) x, y-1, z; (ii) -x+2, -y+2, -z+1; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (vi) x+1, y, z; (vii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; 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 ) and enCIFer (Allen et al., 2004 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811023518/lh5266sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023518/lh5266Isup2.hkl

checkCIF report

Comment top

The structure determination of title compound was performed as a part of a project on the synthesis of new proton-transfer compounds (Raissi Shabari et al., 2010).

The Co atom in title compound adopts a distorted octahedral coordination arising from four oxygen and two nitrogen atoms of two pyridine-2,6-dicarboxylato ligands, Fig. 1. The Co—O and Co—N bond lengths are similar to those in a recently published bis(pyridine-2,6-dicarboxylato)cobaltate(II) complex, (C₆H₁₀N₂)[Co(C₇H₃NO₄)₂].5H₂O (Pasdar et al., 2011). The organic dication adopts a typical chair geometry with normal bond lengths and angles (Sutherland & Harrison, 2009; Allen et al., 1995).

The protonated piperazine nitrogen atoms are involved in positive charge assisted (Gilli et al., 1994) N—H···O hydrogen bonds, atom N3 is involved with the O atoms of an adjacent carbonyl of one pyridine-2,6-dicarboxylato ligand and a neighbouring H₂O molecule and atom N4 with two pyridine-2,6-dicarboxylato ligands in two neighbouring complexes.

Cations, anions and four crystallographically independent H₂O molecules are hydrogen bonded in a three-dimensional network through N—H···O, O—H···O and weak C—H···O hydrogen bonds (Table 1).

Related literature top

The structure determination of title compound was performed as a part of our

project on the synthesis of new proton-transfer compounds, see: Raissi Shabari et al. (2010). For bond lengths in a related cobaltate(II) complex, see: Pasdar et al. (2011). For bond lengths and angles in piperazinediium dications, see: Sutherland & Harrison (2009); Allen et al. (1995). For positive-charge-assisted hydrogen bonds, see: Gilli et al. (1994).

Experimental top

A solution of Co(NO₃)₂.6H₂O (2 mmol) in H₂O was added to a solution of pyridine-2,6-dicarboxylic acid (4 mmol) in H₂O and stirred (45 minutes) at room temperature. To the resulting solution, a solution of piperazine (4 mmol) in H₂O was added and stirred (4 h) at 323 K. Suitable single crystals for X-ray analysis were obtained after slow evaporation at room temperature. IR (KBr, ν, cm^-1): 3425, 3240, 3013, 3001, 2725, 2467, 1608, 1568, 1425, 1371, 1279, 1182, 1074, 1036, 914, 824, 760, 733, 692, 677, 592, 534.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); 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) and enCIFer (Allen et al., 2004).

Figures top

Fig. 1. Molecular structure and atom labeling scheme for title complex with displacement ellipsoids drawn at the 50% probability level.

Piperazine-1,4-diium bis(pyridine-2,6-dicarboxylato- κ³O²,N,O⁶)cobaltate(II) tetrahydrate top

Crystal data top

(C₄H₁₂N₂)[Co(C₇H₃NO₄)₂]·4H₂O	F(000) = 1140
M_r = 549.36	D_x = 1.628 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6018 reflections
a = 7.9537 (16) Å	θ = 2.5–29.1°
b = 13.420 (3) Å	µ = 0.84 mm⁻¹
c = 21.004 (4) Å	T = 150 K
β = 90.55 (3)°	Plate, pink
V = 2241.8 (8) Å³	0.5 × 0.4 × 0.15 mm
Z = 4

Data collection top

Stoe IPDS 2T diffractometer	6018 independent reflections
Radiation source: fine-focus sealed tube	5226 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 0.15 mm pixels mm^-1	θ_max = 29.1°, θ_min = 2.5°
rotation method scans	h = −10→10
Absorption correction: numerical shape of crystal determined optically	k = −16→18
T_min = 0.670, T_max = 0.878	l = −24→28
15339 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0326P)² + 1.2111P] where P = (F_o² + 2F_c²)/3
6018 reflections	(Δ/σ)_max = 0.001
364 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

(C₄H₁₂N₂)[Co(C₇H₃NO₄)₂]·4H₂O	V = 2241.8 (8) Å³
M_r = 549.36	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.9537 (16) Å	µ = 0.84 mm⁻¹
b = 13.420 (3) Å	T = 150 K
c = 21.004 (4) Å	0.5 × 0.4 × 0.15 mm
β = 90.55 (3)°

Data collection top

Stoe IPDS 2T diffractometer	6018 independent reflections
Absorption correction: numerical shape of crystal determined optically	5226 reflections with I > 2σ(I)
T_min = 0.670, T_max = 0.878	R_int = 0.038
15339 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.48 e Å⁻³
6018 reflections	Δρ_min = −0.33 e Å⁻³
364 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
O10	0.26226 (16)	0.55638 (11)	0.28084 (7)	0.0288 (3)
Co1	0.73056 (2)	0.745668 (14)	0.504511 (9)	0.01278 (6)
C18	1.08242 (19)	0.81672 (13)	0.23202 (8)	0.0195 (3)
H18A	1.1280	0.7659	0.2043	0.023*
H18B	1.1624	0.8712	0.2344	0.023*
C16	0.76380 (18)	0.73170 (12)	0.26866 (7)	0.0173 (3)
H16A	0.6828	0.6777	0.2667	0.021*
H16B	0.7185	0.7836	0.2957	0.021*
C15	0.92728 (19)	0.69397 (11)	0.29675 (7)	0.0176 (3)
H15A	0.9091	0.6714	0.3400	0.021*
H15B	0.9670	0.6378	0.2720	0.021*
C17	0.9172 (2)	0.85410 (12)	0.20509 (8)	0.0197 (3)
H17A	0.8759	0.9083	0.2311	0.024*
H17B	0.9339	0.8793	0.1623	0.024*
N4	0.79141 (16)	0.77200 (10)	0.20359 (6)	0.0165 (2)
N3	1.05640 (16)	0.77441 (11)	0.29680 (6)	0.0175 (3)
O5	0.91680 (15)	0.73565 (8)	0.58111 (5)	0.0206 (2)
N1	0.71594 (14)	0.89536 (9)	0.51050 (6)	0.0128 (2)
O4	0.53764 (14)	0.77007 (8)	0.57578 (5)	0.0188 (2)
O2	0.89349 (14)	0.79723 (8)	0.43015 (5)	0.0191 (2)
O8	0.57909 (14)	0.68290 (8)	0.42961 (5)	0.0187 (2)
C7	0.53098 (18)	0.85856 (11)	0.59591 (7)	0.0145 (3)
C6	0.62806 (17)	0.93522 (11)	0.55788 (7)	0.0132 (3)
C9	0.86203 (17)	0.56523 (11)	0.56247 (7)	0.0128 (3)
C13	0.69018 (17)	0.53516 (11)	0.47424 (7)	0.0124 (3)
O3	0.44917 (14)	0.88780 (9)	0.64298 (5)	0.0190 (2)
O1	0.95932 (14)	0.93309 (8)	0.37446 (5)	0.0188 (2)
O7	0.51331 (14)	0.53761 (9)	0.38257 (6)	0.0218 (2)
N2	0.76472 (14)	0.59801 (9)	0.51494 (6)	0.0116 (2)
C14	0.58397 (18)	0.58788 (11)	0.42379 (7)	0.0148 (3)
C8	0.94256 (18)	0.64790 (11)	0.60154 (7)	0.0149 (3)
C2	0.80213 (17)	0.95197 (11)	0.46993 (7)	0.0128 (3)
C5	0.62615 (19)	1.03742 (11)	0.56736 (7)	0.0159 (3)
H5	0.5664	1.0652	0.6008	0.019*
C12	0.71303 (17)	0.43292 (11)	0.47966 (7)	0.0147 (3)
H12	0.6622	0.3892	0.4510	0.018*
C10	0.88885 (18)	0.46439 (11)	0.57169 (7)	0.0163 (3)
H10	0.9551	0.4417	0.6054	0.020*
C1	0.89276 (17)	0.89032 (11)	0.42059 (7)	0.0147 (3)
C3	0.80328 (18)	1.05509 (11)	0.47560 (7)	0.0151 (3)
H3	0.8610	1.0946	0.4468	0.018*
C11	0.81438 (18)	0.39770 (11)	0.52927 (7)	0.0169 (3)
H11	0.8322	0.3296	0.5340	0.020*
C4	0.71541 (19)	1.09736 (11)	0.52577 (8)	0.0172 (3)
H4	0.7165	1.1661	0.5315	0.021*
O9	0.37881 (15)	0.76948 (10)	0.33746 (7)	0.0244 (3)
O6	1.02757 (14)	0.62407 (9)	0.64909 (6)	0.0223 (2)
O11	0.9680 (2)	0.87887 (11)	0.67821 (7)	0.0312 (3)
O12	0.46115 (18)	0.06341 (10)	0.71858 (6)	0.0260 (3)
H3B	1.157 (3)	0.7514 (16)	0.3122 (11)	0.029 (6)*
H4B	0.828 (3)	0.7228 (18)	0.1787 (11)	0.029 (6)*
H3A	1.022 (3)	0.8243 (18)	0.3232 (11)	0.031 (6)*
H4A	0.694 (3)	0.7923 (19)	0.1846 (11)	0.034 (6)*
H9B	0.437 (3)	0.7419 (18)	0.3625 (12)	0.031 (6)*
H10B	0.324 (4)	0.561 (2)	0.3103 (15)	0.050 (8)*
H10A	0.321 (3)	0.582 (2)	0.2501 (14)	0.051 (8)*
H9A	0.432 (4)	0.815 (2)	0.3200 (14)	0.052 (8)*
H12A	0.508 (3)	0.050 (2)	0.7517 (14)	0.051 (8)*
H12B	0.464 (3)	0.013 (2)	0.6991 (14)	0.045 (8)*
H11B	0.950 (3)	0.838 (2)	0.6492 (14)	0.046 (7)*
H11A	0.989 (3)	0.929 (2)	0.6591 (13)	0.046 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O10	0.0222 (6)	0.0391 (8)	0.0252 (7)	−0.0005 (5)	−0.0045 (5)	0.0017 (6)
Co1	0.01592 (9)	0.00943 (9)	0.01298 (10)	0.00047 (7)	−0.00079 (6)	0.00003 (7)
C18	0.0185 (7)	0.0244 (8)	0.0158 (7)	−0.0038 (6)	0.0021 (5)	−0.0007 (6)
C16	0.0154 (6)	0.0188 (7)	0.0177 (7)	0.0008 (5)	0.0014 (5)	−0.0008 (5)
C15	0.0211 (7)	0.0161 (7)	0.0156 (7)	0.0040 (5)	−0.0001 (5)	0.0027 (5)
C17	0.0262 (8)	0.0165 (7)	0.0165 (7)	−0.0008 (6)	−0.0016 (6)	0.0040 (6)
N4	0.0158 (6)	0.0190 (6)	0.0147 (6)	0.0039 (5)	−0.0044 (5)	0.0003 (5)
N3	0.0149 (6)	0.0247 (7)	0.0128 (6)	0.0044 (5)	−0.0024 (5)	−0.0024 (5)
O5	0.0275 (6)	0.0138 (5)	0.0202 (5)	−0.0027 (4)	−0.0086 (4)	−0.0010 (4)
N1	0.0126 (5)	0.0118 (5)	0.0140 (6)	0.0001 (4)	0.0003 (4)	0.0004 (4)
O4	0.0240 (5)	0.0130 (5)	0.0194 (5)	−0.0025 (4)	0.0056 (4)	−0.0011 (4)
O2	0.0243 (5)	0.0142 (5)	0.0188 (5)	0.0013 (4)	0.0063 (4)	−0.0001 (4)
O8	0.0235 (5)	0.0147 (5)	0.0177 (5)	0.0013 (4)	−0.0082 (4)	0.0011 (4)
C7	0.0156 (6)	0.0153 (7)	0.0126 (6)	−0.0003 (5)	−0.0003 (5)	0.0021 (5)
C6	0.0149 (6)	0.0127 (6)	0.0120 (6)	0.0004 (5)	0.0000 (5)	0.0002 (5)
C9	0.0113 (6)	0.0143 (6)	0.0129 (6)	−0.0016 (5)	−0.0012 (5)	0.0005 (5)
C13	0.0113 (6)	0.0139 (6)	0.0120 (6)	0.0000 (5)	−0.0007 (5)	−0.0011 (5)
O3	0.0236 (5)	0.0180 (5)	0.0154 (5)	−0.0002 (4)	0.0067 (4)	0.0003 (4)
O1	0.0230 (5)	0.0181 (5)	0.0154 (5)	−0.0018 (4)	0.0053 (4)	0.0013 (4)
O7	0.0243 (6)	0.0231 (6)	0.0179 (5)	0.0034 (4)	−0.0092 (4)	−0.0060 (4)
N2	0.0111 (5)	0.0121 (5)	0.0117 (5)	−0.0002 (4)	−0.0005 (4)	0.0004 (4)
C14	0.0140 (6)	0.0180 (7)	0.0123 (6)	0.0026 (5)	−0.0014 (5)	0.0002 (5)
C8	0.0137 (6)	0.0170 (7)	0.0139 (6)	−0.0036 (5)	−0.0013 (5)	−0.0015 (5)
C2	0.0120 (6)	0.0138 (6)	0.0124 (6)	0.0002 (5)	−0.0004 (5)	0.0012 (5)
C5	0.0191 (6)	0.0145 (7)	0.0141 (6)	0.0000 (5)	0.0005 (5)	−0.0031 (5)
C12	0.0143 (6)	0.0124 (6)	0.0173 (7)	−0.0019 (5)	−0.0009 (5)	−0.0031 (5)
C10	0.0152 (6)	0.0163 (7)	0.0174 (7)	0.0002 (5)	−0.0033 (5)	0.0045 (5)
C1	0.0133 (6)	0.0168 (7)	0.0142 (6)	−0.0007 (5)	−0.0003 (5)	−0.0014 (5)
C3	0.0160 (6)	0.0126 (6)	0.0168 (7)	−0.0020 (5)	−0.0004 (5)	0.0018 (5)
C11	0.0178 (6)	0.0109 (6)	0.0221 (7)	0.0002 (5)	−0.0009 (6)	0.0024 (5)
C4	0.0204 (7)	0.0109 (6)	0.0202 (7)	−0.0016 (5)	−0.0003 (6)	−0.0007 (5)
O9	0.0182 (5)	0.0233 (6)	0.0315 (7)	0.0007 (5)	−0.0089 (5)	0.0059 (5)
O6	0.0243 (5)	0.0227 (6)	0.0196 (6)	−0.0062 (4)	−0.0116 (4)	0.0031 (5)
O11	0.0541 (9)	0.0202 (6)	0.0195 (6)	−0.0074 (6)	0.0038 (6)	−0.0005 (5)
O12	0.0400 (7)	0.0204 (6)	0.0175 (6)	0.0034 (5)	−0.0031 (5)	−0.0012 (5)

Geometric parameters (Å, º) top

O10—H10B	0.79 (3)	O8—C14	1.2817 (19)
O10—H10A	0.87 (3)	C7—O3	1.2518 (19)
Co1—N2	2.0117 (13)	C7—C6	1.518 (2)
Co1—N1	2.0162 (13)	C6—C5	1.386 (2)
Co1—O8	2.1446 (12)	C9—N2	1.3321 (18)
Co1—O2	2.1532 (13)	C9—C10	1.383 (2)
Co1—O4	2.1787 (13)	C9—C8	1.518 (2)
Co1—O5	2.1807 (13)	C13—N2	1.3357 (18)
C18—N3	1.491 (2)	C13—C12	1.389 (2)
C18—C17	1.511 (2)	C13—C14	1.5229 (19)
C18—H18A	0.9700	O1—C1	1.2485 (19)
C18—H18B	0.9700	O7—C14	1.2293 (18)
C16—N4	1.488 (2)	C8—O6	1.2426 (18)
C16—C15	1.510 (2)	C2—C3	1.389 (2)
C16—H16A	0.9700	C2—C1	1.514 (2)
C16—H16B	0.9700	C5—C4	1.388 (2)
C15—N3	1.490 (2)	C5—H5	0.9300
C15—H15A	0.9700	C12—C11	1.394 (2)
C15—H15B	0.9700	C12—H12	0.9300
C17—N4	1.488 (2)	C10—C11	1.391 (2)
C17—H17A	0.9700	C10—H10	0.9300
C17—H17B	0.9700	C3—C4	1.391 (2)
N4—H4B	0.89 (2)	C3—H3	0.9300
N4—H4A	0.91 (2)	C11—H11	0.9300
N3—H3B	0.91 (2)	C4—H4	0.9300
N3—H3A	0.91 (2)	O9—H9B	0.79 (3)
O5—C8	1.2692 (19)	O9—H9A	0.83 (3)
N1—C6	1.3335 (19)	O11—H11B	0.83 (3)
N1—C2	1.3358 (19)	O11—H11A	0.81 (3)
O4—C7	1.2619 (18)	O12—H12A	0.80 (3)
O2—C1	1.2652 (19)	O12—H12B	0.79 (3)

H10B—O10—H10A	103 (3)	C6—N1—Co1	118.50 (10)
N2—Co1—N1	169.23 (5)	C2—N1—Co1	119.77 (10)
N2—Co1—O8	76.55 (5)	C7—O4—Co1	113.82 (10)
N1—Co1—O8	113.87 (5)	C1—O2—Co1	115.50 (10)
N2—Co1—O2	108.30 (5)	C14—O8—Co1	116.32 (9)
N1—Co1—O2	76.15 (5)	O3—C7—O4	125.69 (14)
O8—Co1—O2	86.10 (5)	O3—C7—C6	118.30 (13)
N2—Co1—O4	99.70 (5)	O4—C7—C6	115.99 (13)
N1—Co1—O4	76.46 (5)	N1—C6—C5	120.71 (14)
O8—Co1—O4	99.71 (5)	N1—C6—C7	113.19 (12)
O2—Co1—O4	151.99 (4)	C5—C6—C7	126.06 (13)
N2—Co1—O5	76.63 (4)	N2—C9—C10	121.04 (13)
N1—Co1—O5	93.13 (4)	N2—C9—C8	113.76 (13)
O8—Co1—O5	152.85 (4)	C10—C9—C8	125.15 (13)
O2—Co1—O5	98.38 (5)	N2—C13—C12	120.96 (13)
O4—Co1—O5	88.87 (5)	N2—C13—C14	113.07 (12)
N3—C18—C17	109.89 (13)	C12—C13—C14	125.97 (13)
N3—C18—H18A	109.7	C9—N2—C13	121.49 (13)
C17—C18—H18A	109.7	C9—N2—Co1	118.93 (10)
N3—C18—H18B	109.7	C13—N2—Co1	119.58 (10)
C17—C18—H18B	109.7	O7—C14—O8	126.80 (14)
H18A—C18—H18B	108.2	O7—C14—C13	118.81 (13)
N4—C16—C15	110.28 (12)	O8—C14—C13	114.39 (12)
N4—C16—H16A	109.6	O6—C8—O5	126.53 (14)
C15—C16—H16A	109.6	O6—C8—C9	118.02 (13)
N4—C16—H16B	109.6	O5—C8—C9	115.43 (13)
C15—C16—H16B	109.6	N1—C2—C3	120.99 (14)
H16A—C16—H16B	108.1	N1—C2—C1	112.12 (12)
N3—C15—C16	110.38 (12)	C3—C2—C1	126.89 (13)
N3—C15—H15A	109.6	C6—C5—C4	118.47 (14)
C16—C15—H15A	109.6	C6—C5—H5	120.8
N3—C15—H15B	109.6	C4—C5—H5	120.8
C16—C15—H15B	109.6	C13—C12—C11	118.08 (13)
H15A—C15—H15B	108.1	C13—C12—H12	121.0
N4—C17—C18	110.13 (13)	C11—C12—H12	121.0
N4—C17—H17A	109.6	C9—C10—C11	118.40 (13)
C18—C17—H17A	109.6	C9—C10—H10	120.8
N4—C17—H17B	109.6	C11—C10—H10	120.8
C18—C17—H17B	109.6	O1—C1—O2	125.15 (14)
H17A—C17—H17B	108.1	O1—C1—C2	119.23 (13)
C16—N4—C17	110.77 (12)	O2—C1—C2	115.62 (13)
C16—N4—H4B	108.8 (15)	C2—C3—C4	117.93 (14)
C17—N4—H4B	109.6 (15)	C2—C3—H3	121.0
C16—N4—H4A	112.4 (15)	C4—C3—H3	121.0
C17—N4—H4A	110.8 (16)	C10—C11—C12	120.02 (14)
H4B—N4—H4A	104 (2)	C10—C11—H11	120.0
C15—N3—C18	112.15 (12)	C12—C11—H11	120.0
C15—N3—H3B	110.8 (14)	C5—C4—C3	120.28 (14)
C18—N3—H3B	109.0 (14)	C5—C4—H4	119.9
C15—N3—H3A	108.6 (14)	C3—C4—H4	119.9
C18—N3—H3A	108.7 (15)	H9B—O9—H9A	110 (2)
H3B—N3—H3A	107 (2)	H11B—O11—H11A	103 (3)
C8—O5—Co1	114.39 (9)	H12A—O12—H12B	104 (3)
C6—N1—C2	121.59 (13)

N4—C16—C15—N3	56.04 (16)	C8—C9—N2—Co1	−2.77 (16)
N3—C18—C17—N4	−57.15 (17)	C12—C13—N2—C9	−0.7 (2)
C15—C16—N4—C17	−58.43 (16)	C14—C13—N2—C9	179.69 (12)
C18—C17—N4—C16	59.08 (16)	C12—C13—N2—Co1	179.15 (11)
C16—C15—N3—C18	−55.72 (17)	C14—C13—N2—Co1	−0.48 (16)
C17—C18—N3—C15	56.17 (17)	N1—Co1—N2—C9	−12.6 (3)
N2—Co1—O5—C8	−8.50 (11)	O8—Co1—N2—C9	−178.50 (11)
N1—Co1—O5—C8	168.13 (11)	O2—Co1—N2—C9	100.29 (11)
O8—Co1—O5—C8	−17.59 (17)	O4—Co1—N2—C9	−80.74 (11)
O2—Co1—O5—C8	−115.43 (11)	O5—Co1—N2—C9	5.75 (10)
O4—Co1—O5—C8	91.75 (11)	N1—Co1—N2—C13	167.6 (2)
N2—Co1—N1—C6	−59.3 (3)	O8—Co1—N2—C13	1.66 (10)
O8—Co1—N1—C6	105.67 (11)	O2—Co1—N2—C13	−79.55 (11)
O2—Co1—N1—C6	−175.04 (11)	O4—Co1—N2—C13	99.42 (11)
O4—Co1—N1—C6	10.90 (10)	O5—Co1—N2—C13	−174.09 (11)
O5—Co1—N1—C6	−77.18 (11)	Co1—O8—C14—O7	−176.49 (13)
N2—Co1—N1—C2	116.5 (3)	Co1—O8—C14—C13	3.39 (16)
O8—Co1—N1—C2	−78.56 (11)	N2—C13—C14—O7	177.88 (14)
O2—Co1—N1—C2	0.73 (10)	C12—C13—C14—O7	−1.7 (2)
O4—Co1—N1—C2	−173.33 (11)	N2—C13—C14—O8	−2.00 (18)
O5—Co1—N1—C2	98.59 (11)	C12—C13—C14—O8	178.38 (14)
N2—Co1—O4—C7	156.74 (10)	Co1—O5—C8—O6	−171.44 (13)
N1—Co1—O4—C7	−12.98 (10)	Co1—O5—C8—C9	9.52 (16)
O8—Co1—O4—C7	−125.39 (10)	N2—C9—C8—O6	175.91 (13)
O2—Co1—O4—C7	−25.34 (16)	C10—C9—C8—O6	−6.8 (2)
O5—Co1—O4—C7	80.51 (11)	N2—C9—C8—O5	−4.96 (19)
N2—Co1—O2—C1	−176.16 (10)	C10—C9—C8—O5	172.35 (14)
N1—Co1—O2—C1	−6.37 (10)	C6—N1—C2—C3	−0.1 (2)
O8—Co1—O2—C1	109.39 (11)	Co1—N1—C2—C3	−175.70 (10)
O4—Co1—O2—C1	6.00 (17)	C6—N1—C2—C1	179.60 (12)
O5—Co1—O2—C1	−97.55 (11)	Co1—N1—C2—C1	3.96 (15)
N2—Co1—O8—C14	−2.85 (11)	N1—C6—C5—C4	1.1 (2)
N1—Co1—O8—C14	180.00 (10)	C7—C6—C5—C4	−176.42 (13)
O2—Co1—O8—C14	107.02 (11)	N2—C13—C12—C11	0.8 (2)
O4—Co1—O8—C14	−100.60 (11)	C14—C13—C12—C11	−179.66 (13)
O5—Co1—O8—C14	6.25 (17)	N2—C9—C10—C11	1.3 (2)
Co1—O4—C7—O3	−168.85 (12)	C8—C9—C10—C11	−175.84 (14)
Co1—O4—C7—C6	12.83 (16)	Co1—O2—C1—O1	−169.47 (12)
C2—N1—C6—C5	−1.3 (2)	Co1—O2—C1—C2	10.27 (16)
Co1—N1—C6—C5	174.37 (11)	N1—C2—C1—O1	170.25 (13)
C2—N1—C6—C7	176.50 (12)	C3—C2—C1—O1	−10.1 (2)
Co1—N1—C6—C7	−7.81 (15)	N1—C2—C1—O2	−9.50 (18)
O3—C7—C6—N1	177.41 (13)	C3—C2—C1—O2	170.14 (14)
O4—C7—C6—N1	−4.14 (18)	N1—C2—C3—C4	1.6 (2)
O3—C7—C6—C5	−4.9 (2)	C1—C2—C3—C4	−178.01 (13)
O4—C7—C6—C5	173.53 (14)	C9—C10—C11—C12	−1.2 (2)
C10—C9—N2—C13	−0.4 (2)	C13—C12—C11—C10	0.2 (2)
C8—C9—N2—C13	177.06 (12)	C6—C5—C4—C3	0.5 (2)
C10—C9—N2—Co1	179.80 (11)	C2—C3—C4—C5	−1.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12B···O3ⁱ	0.79 (3)	2.06 (3)	2.8428 (18)	174 (3)
O11—H11B···O5	0.83 (3)	2.00 (3)	2.8290 (18)	177 (3)
O11—H11A···O1ⁱⁱ	0.81 (3)	2.02 (3)	2.8173 (19)	170 (3)
O10—H10B···O7	0.79 (3)	2.15 (3)	2.9213 (19)	165 (3)
O10—H10A···O11ⁱⁱⁱ	0.87 (3)	1.99 (3)	2.854 (2)	172 (3)
O9—H9B···O8	0.79 (3)	1.96 (3)	2.7521 (18)	175 (2)
O9—H9A···O12^iv	0.83 (3)	2.01 (3)	2.840 (2)	173 (3)
N4—H4B···O3^v	0.89 (2)	1.92 (2)	2.7973 (18)	165 (2)
N4—H4A···O6ⁱⁱⁱ	0.91 (2)	1.89 (2)	2.7592 (17)	161 (2)
N3—H3B···O9^vi	0.91 (2)	1.86 (2)	2.6958 (18)	152 (2)
N3—H3A···O2	0.91 (2)	2.50 (2)	3.1126 (19)	124.5 (18)
N3—H3A···O1	0.91 (2)	1.88 (2)	2.7957 (18)	176 (2)
C18—H18B···O10^vii	0.97	2.58	3.457 (2)	151
C17—H17B···O7^vii	0.97	2.36	3.127 (2)	135
C16—H16B···O12^iv	0.97	2.52	3.293 (2)	137
C15—H15B···O10^vi	0.97	2.60	3.261 (2)	126
C15—H15A···O2	0.97	2.54	3.140 (2)	120

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

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)[Co(C₇H₃NO₄)₂]·4H₂O
M_r	549.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	7.9537 (16), 13.420 (3), 21.004 (4)
β (°)	90.55 (3)
V (Å³)	2241.8 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.84
Crystal size (mm)	0.5 × 0.4 × 0.15

Data collection
Diffractometer	Stoe IPDS 2T diffractometer
Absorption correction	Numerical shape of crystal determined optically
T_min, T_max	0.670, 0.878
No. of measured, independent and observed [I > 2σ(I)] reflections	15339, 6018, 5226
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.077, 1.07
No. of reflections	6018
No. of parameters	364
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.33

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and enCIFer (Allen et al., 2004).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12B···O3ⁱ	0.79 (3)	2.06 (3)	2.8428 (18)	174 (3)
O11—H11B···O5	0.83 (3)	2.00 (3)	2.8290 (18)	177 (3)
O11—H11A···O1ⁱⁱ	0.81 (3)	2.02 (3)	2.8173 (19)	170 (3)
O10—H10B···O7	0.79 (3)	2.15 (3)	2.9213 (19)	165 (3)
O10—H10A···O11ⁱⁱⁱ	0.87 (3)	1.99 (3)	2.854 (2)	172 (3)
O9—H9B···O8	0.79 (3)	1.96 (3)	2.7521 (18)	175 (2)
O9—H9A···O12^iv	0.83 (3)	2.01 (3)	2.840 (2)	173 (3)
N4—H4B···O3^v	0.89 (2)	1.92 (2)	2.7973 (18)	165 (2)
N4—H4A···O6ⁱⁱⁱ	0.91 (2)	1.89 (2)	2.7592 (17)	161 (2)
N3—H3B···O9^vi	0.91 (2)	1.86 (2)	2.6958 (18)	152 (2)
N3—H3A···O2	0.91 (2)	2.50 (2)	3.1126 (19)	124.5 (18)
N3—H3A···O1	0.91 (2)	1.88 (2)	2.7957 (18)	176 (2)
C18—H18B···O10^vii	0.97	2.58	3.457 (2)	150.8
C17—H17B···O7^vii	0.97	2.36	3.127 (2)	135.1
C16—H16B···O12^iv	0.97	2.52	3.293 (2)	136.8
C15—H15B···O10^vi	0.97	2.60	3.261 (2)	126.0
C15—H15A···O2	0.97	2.54	3.140 (2)	119.9

Acknowledgements

Support of this investigation by the North Tehran Branch, Islamic Azad University, is gratefully acknowledged.

References

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