Bis[μ-4-(methyl­amino)­benzoato]-κ3O,O′:O;κ3O:O,O′-bis­{aqua­[4-(methyl­amino)­benzoato-κ2O,O′](nicotinamide-κN)cadmium(II)}

Hökelek, T.; Sağlam, E.G.; Tercan, B.; Aybirdi, Ö.; Necefoğlu, H.

doi:10.1107/S1600536810046258

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Pages m1559-m1560

https://doi.org/10.1107/S1600536810046258

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Bis[μ-4-(methylamino)benzoato]-κ³O,O′:O;κ³O:O,O′-bis{aqua[4-(methylamino)benzoato-κ²O,O′](nicotinamide-κN)cadmium(II)}

Tuncer Hökelek,^a ^* Ertuğrul Gazi Sağlam,^b Barış Tercan,^c Özgür Aybirdi ^d and Hacali Necefoğlu ^d

^aDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey, ^bDepartment of Chemistry, Ankara University, 06100 Tandoğan, Ankara, Turkey, ^cDepartment of Physics, Karabük University, 78050 Karabük, Turkey, and ^dDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 5 November 2010; accepted 9 November 2010; online 13 November 2010)

In the dinuclear centrosymmetric Cd^II compound, [Cd₂(C₈H₈NO₂)₄(C₆H₆N₂O)₂(H₂O)₂], the metal atom is chelated by two carboxylate groups from 4-(methylamino)benzoate (PMAB) anions, and coordinated by one nicotinamide and one water molecule; a carboxylate O atom from the adjacent PMAB anion bridges to the Cd atom, completing the irregular seven-coordination geometry. In the crystal, intermolecular O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. π–π contacts between the pyridine rings [centroid–centroid distance = 3.965 (1) Å] may further stabilize the structure. A weak C—H⋯π interaction also occurs.

Related literature

For niacin, see: Krishnamachari (1974 ). For N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Greenaway et al. (1984 ); Hökelek & Necefoğlu (1996 ); Hökelek et al. (2009a ,b ,c ,d , 2010 ).

Experimental

Crystal data

[Cd₂(C₈H₈NO₂)₄(C₆H₆N₂O)₂(H₂O)₂]
M_r = 1105.72
Triclinic, $[P \overline 1]$
a = 9.5286 (2) Å
b = 10.1734 (2) Å
c = 13.2876 (3) Å
α = 72.831 (3)°
β = 75.741 (3)°
γ = 67.172 (2)°
V = 1121.51 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 100 K
0.37 × 0.26 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.734, T_max = 0.901
20025 measured reflections
5581 independent reflections
5250 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.061
S = 1.08
5581 reflections
324 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.77 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—N1	2.3265 (15)
Cd1—O1	2.3170 (14)
Cd1—O2	2.3844 (13)
Cd1—O3	2.5099 (15)
Cd1—O4	2.3185 (14)
Cd1—O4ⁱ	2.5625 (13)
Cd1—O6	2.3152 (14)
Symmetry code: (i) -x, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.83 (3)	2.13 (3)	2.921 (2)	160 (2)
N2—H2B⋯O3ⁱⁱ	0.86 (3)	2.05 (3)	2.901 (3)	170 (3)
O6—H61⋯O5ⁱⁱⁱ	0.79 (4)	1.91 (4)	2.692 (2)	167 (3)
O6—H62⋯O2^iv	0.81 (4)	1.94 (4)	2.743 (2)	179 (3)
C11—H11⋯O2ⁱ	0.93	2.39	3.299 (2)	165
C17—H17⋯O1ⁱ	0.93	2.36	3.216 (3)	153
C21—H21⋯O2^iv	0.93	2.45	3.252 (3)	145
C19—H19⋯Cg3^v	0.93	2.74	3.537 (2)	144
Symmetry codes: (i) -x, -y, -z+1; (ii) x, y-1, z; (iii) x, y+1, z; (iv) -x+1, -y, -z+1; (v) x+1, y-1, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046258/xu5083sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046258/xu5083Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigation on transition metal complexes of nicotinamide (NA), one form of niacin (Krishnamachari, 1974), and/or the nicotinic acid derivative N,N-diethylnicotinamide (DENA), an important respiratory stimulant (Bigoli et al., 1972), the title compound was synthesized and its crystal structure is reported herein.

The title compound, (I), consists of dimeric units located around a crystallographic symmetry centre and made up of two Cd cations, four 4-methylaminobenzoate (PMAB) anions, two nicotinamide (NA) ligands and two water molecules (Fig. 1). Each Cd(II) unit is chelated by the carboxylate O atoms of the two PMAB anions, and the two monomeric units are bridged through the two oxygen atoms of the two carboxylate groups about an inversion center. The coordination number of each Cd^II atom is seven. The Cd1···Cd1ⁱ distance is 3.8204 (14) Å and O4-Cd1-O4ⁱ angle is 77.12 (5)° (symmetry code: (i) -x, -y, 1 - z).

The average Cd-O bond length (Table 1) is 2.4013 (14) Å, and the Cd atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/C9/O4) by 0.4159 (1) and 0.4085 (1) Å, respectively. In (I), the O1-Cd1-O2 and O3-Cd1-O4 angles are 55.71 (5) and 117.52 (4) °, respectively. The corresponding O-M-O (where M is a metal) angles are 55.96 (4)° and 53.78 (4)° in [Cd₂(DMAB)₄(NA)₂(H₂O)₂] (Hökelek et al., 2010), 52.91 (4)° and 53.96 (4)° in [Cd(FB)₂(INA)₂(H₂O)].H₂O (Hökelek et al., 2009a), 60.70 (4)° in [Co(DMAB)₂(INA)(H₂O)₂] (Hökelek et al., 2009b), 58.45 (9)° in [Mn(DMAB)₂(INA)(H₂O)₂] (Hökelek et al., 2009c), 60.03 (6)° in [Zn(MAB)₂(INA)₂].H₂O (Hökelek et al., 2009d), 58.3 (3)° in [Zn₂(DENA)₂(HB)₄].2H₂O (Hökelek & Necefoğlu, 1996) [where NA, INA, DENA, HB, FB, MAB and DMAB are nicotinamide, isonicotinamide, N,N-diethylnicotinamide, 4-hydroxybenzoate, 4-formylbenzoate, 4-methylaminobenzoate and 4-dimethylaminobenzoate, respectively] and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) (Greenaway et al., 1984).

The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2-C7) and B (C10-C15) are 9.86 (16) and 11.74 (11) °, respectively, while those between rings A, B, C (N1/C17-C21), D (Cd1/O1/O2/C1) and E (Cd1/O3/O4/C9) are A/B = 88.35 (6), A/C = 62.90 (7), B/C = 73.43 (6) and D/E = 63.44 (5)°.

In the crystal structure, intermolecular O-H···O, N-H···O and C-H···O hydrogen bonds (Table 2) link the molecules into a three-dimensional network, in which they may be effective in the stabilization of the structure. The π–π contact between the pyridine rings, Cg3—Cg3ⁱ [symmetry code: (i) 1 - x, -1 - y, 1 - z, where Cg3 is the centroid of the ring C (N3/C17-C21)] may further stabilize the structure, with centroid-centroid distance of 3.965 (1) Å. There also exists a weak C-H···π interaction (Table 2).

Related literature top

For niacin, see: Krishnamachari (1974). For N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Greenaway et al. (1984); Hökelek & Necefoğlu (1996); Hökelek et al. (2009a,b,c,d, 2010).

Experimental top

The title compound was prepared by the reaction of 3CdSO₄.H₂O (1.08 g, 5 mmol) in H₂O (30 ml) and NA (1.22 g, 10 mmol) in H₂O (20 ml) with sodium 4-(methylamino)benzoate (1.73 g, 10 mmol) in H₂O (150 ml). The mixture was filtered and set aside to crystallize at ambient temperature for one week, giving colorless single crystals.

Structure description top

For niacin, see: Krishnamachari (1974). For N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Greenaway et al. (1984); Hökelek & Necefoğlu (1996); Hökelek et al. (2009a,b,c,d, 2010).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. Primed atoms are generated by the symmetry operators: (') - x, - y, 1 - z.

Bis[µ-4-(methylamino)benzoato]- κ³O,O':O;κ³O:O,O'- bis{aqua[4-(methylamino)benzoato-κ²O,O'](nicotinamide- κN)cadmium(II)} top

Crystal data top

[Cd₂(C₈H₈NO₂)₄(C₆H₆N₂O)₂(H₂O)₂]	Z = 1
M_r = 1105.72	F(000) = 560
Triclinic, P1	D_x = 1.637 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5286 (2) Å	Cell parameters from 9941 reflections
b = 10.1734 (2) Å	θ = 2.4–28.4°
c = 13.2876 (3) Å	µ = 1.02 mm⁻¹
α = 72.831 (3)°	T = 100 K
β = 75.741 (3)°	Block, colorless
γ = 67.172 (2)°	0.37 × 0.26 × 0.10 mm
V = 1121.51 (5) Å³

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5581 independent reflections
Radiation source: fine-focus sealed tube	5250 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 28.4°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −12→12
T_min = 0.734, T_max = 0.901	k = −13→13
20025 measured reflections	l = −17→16

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0294P)² + 0.9733P] where P = (F_o² + 2F_c²)/3
5581 reflections	(Δ/σ)_max < 0.001
324 parameters	Δρ_max = 1.77 e Å⁻³
1 restraint	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Cd₂(C₈H₈NO₂)₄(C₆H₆N₂O)₂(H₂O)₂]	γ = 67.172 (2)°
M_r = 1105.72	V = 1121.51 (5) Å³
Triclinic, P1	Z = 1
a = 9.5286 (2) Å	Mo Kα radiation
b = 10.1734 (2) Å	µ = 1.02 mm⁻¹
c = 13.2876 (3) Å	T = 100 K
α = 72.831 (3)°	0.37 × 0.26 × 0.10 mm
β = 75.741 (3)°

Data collection top

Bruker Kappa APEXII CCD area-detector diffractometer	5581 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5250 reflections with I > 2σ(I)
T_min = 0.734, T_max = 0.901	R_int = 0.023
20025 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	1 restraint
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 1.77 e Å⁻³
5581 reflections	Δρ_min = −0.48 e Å⁻³
324 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Cd1	0.183285 (14)	0.043205 (13)	0.484176 (10)	0.01391 (5)
O1	0.08486 (15)	0.16573 (15)	0.62175 (12)	0.0210 (3)
O2	0.32071 (15)	0.00805 (14)	0.62305 (11)	0.0175 (3)
O3	0.04603 (16)	0.29436 (15)	0.38267 (12)	0.0234 (3)
O4	−0.01778 (15)	0.10432 (14)	0.39110 (11)	0.0175 (3)
O5	0.37181 (18)	−0.60649 (17)	0.33609 (16)	0.0357 (4)
O6	0.37108 (16)	0.12104 (15)	0.36256 (12)	0.0188 (3)
H61	0.357 (3)	0.205 (4)	0.357 (2)	0.039 (8)*
H62	0.462 (4)	0.084 (3)	0.366 (2)	0.042 (8)*
N1	0.32666 (17)	−0.18369 (16)	0.44351 (13)	0.0157 (3)
N2	0.1327 (2)	−0.4634 (2)	0.38591 (18)	0.0281 (4)
H2A	0.071 (3)	−0.385 (3)	0.400 (2)	0.037 (7)*
H2B	0.099 (3)	−0.528 (3)	0.380 (2)	0.039 (8)*
N3	0.1429 (3)	0.0766 (2)	1.10668 (16)	0.0335 (4)
H3A	0.051 (4)	0.113 (4)	1.137 (3)	0.053 (9)*
N4	−0.3405 (3)	0.5412 (3)	−0.00800 (18)	0.0413 (5)
H4A	−0.345 (5)	0.491 (5)	−0.048 (3)	0.100 (17)*
C1	0.2004 (2)	0.09189 (19)	0.66971 (15)	0.0155 (3)
C2	0.1916 (2)	0.0959 (2)	0.78140 (15)	0.0170 (3)
C3	0.0524 (2)	0.1725 (2)	0.83657 (17)	0.0232 (4)
H3	−0.0311	0.2287	0.8004	0.028*
C4	0.0371 (2)	0.1661 (2)	0.94354 (18)	0.0276 (4)
H4	−0.0565	0.2179	0.9785	0.033*
C5	0.1613 (2)	0.0820 (2)	1.00047 (16)	0.0240 (4)
C6	0.3012 (2)	0.0073 (2)	0.94509 (17)	0.0251 (4)
H6	0.3854	−0.0478	0.9808	0.030*
C7	0.3151 (2)	0.0148 (2)	0.83732 (16)	0.0227 (4)
H7	0.4091	−0.0354	0.8017	0.027*
C8	0.2541 (4)	−0.0243 (3)	1.1746 (2)	0.0446 (6)
H8A	0.2118	−0.0199	1.2474	0.067*
H8B	0.3456	0.0014	1.1554	0.067*
H8C	0.2792	−0.1218	1.1661	0.067*
C9	−0.0265 (2)	0.23868 (19)	0.35120 (15)	0.0163 (3)
C10	−0.1183 (2)	0.32451 (19)	0.26270 (15)	0.0171 (3)
C11	−0.2098 (2)	0.2690 (2)	0.23138 (16)	0.0207 (4)
H11	−0.2212	0.1806	0.2710	0.025*
C12	−0.2835 (2)	0.3414 (2)	0.14353 (18)	0.0265 (4)
H12	−0.3439	0.3015	0.1251	0.032*
C13	−0.2687 (2)	0.4745 (2)	0.08146 (18)	0.0288 (5)
C14	−0.1827 (3)	0.5343 (2)	0.1148 (2)	0.0324 (5)
H14	−0.1749	0.6246	0.0769	0.039*
C15	−0.1087 (2)	0.4601 (2)	0.20394 (18)	0.0248 (4)
H15	−0.0520	0.5016	0.2246	0.030*
C16	−0.3123 (3)	0.6668 (3)	−0.0834 (2)	0.0487 (7)
H16A	−0.3610	0.6892	−0.1446	0.073*
H16B	−0.2034	0.6454	−0.1052	0.073*
H16C	−0.3538	0.7491	−0.0506	0.073*
C17	0.2634 (2)	−0.26755 (19)	0.42175 (15)	0.0157 (3)
H17	0.1566	−0.2411	0.4335	0.019*
C18	0.3509 (2)	−0.39229 (19)	0.38237 (15)	0.0164 (3)
C19	0.5101 (2)	−0.4288 (2)	0.36180 (18)	0.0221 (4)
H19	0.5715	−0.5092	0.3328	0.027*
C20	0.5760 (2)	−0.3436 (2)	0.38513 (19)	0.0244 (4)
H20	0.6823	−0.3663	0.3725	0.029*
C21	0.4810 (2)	−0.2241 (2)	0.42749 (17)	0.0193 (4)
H21	0.5258	−0.1694	0.4456	0.023*
C22	0.2834 (2)	−0.4945 (2)	0.36559 (16)	0.0188 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.01123 (7)	0.01258 (7)	0.01849 (7)	−0.00263 (5)	−0.00261 (5)	−0.00593 (5)
O1	0.0179 (6)	0.0192 (6)	0.0262 (7)	−0.0015 (5)	−0.0074 (5)	−0.0088 (6)
O2	0.0140 (6)	0.0195 (6)	0.0188 (6)	−0.0045 (5)	−0.0017 (5)	−0.0063 (5)
O3	0.0197 (7)	0.0205 (7)	0.0329 (8)	−0.0079 (5)	−0.0083 (6)	−0.0050 (6)
O4	0.0160 (6)	0.0144 (6)	0.0197 (7)	−0.0047 (5)	−0.0032 (5)	−0.0003 (5)
O5	0.0222 (7)	0.0254 (8)	0.0654 (12)	−0.0095 (6)	0.0063 (7)	−0.0276 (8)
O6	0.0144 (6)	0.0140 (6)	0.0246 (7)	−0.0028 (5)	−0.0022 (5)	−0.0031 (5)
N1	0.0139 (7)	0.0135 (7)	0.0195 (8)	−0.0047 (6)	−0.0023 (6)	−0.0035 (6)
N2	0.0165 (8)	0.0182 (8)	0.0551 (13)	−0.0045 (7)	−0.0054 (8)	−0.0178 (8)
N3	0.0388 (11)	0.0394 (11)	0.0193 (9)	−0.0110 (9)	0.0017 (8)	−0.0103 (8)
N4	0.0413 (12)	0.0427 (13)	0.0295 (11)	−0.0085 (10)	−0.0138 (9)	0.0059 (10)
C1	0.0152 (8)	0.0129 (7)	0.0199 (9)	−0.0072 (6)	−0.0012 (7)	−0.0037 (7)
C2	0.0170 (8)	0.0171 (8)	0.0187 (9)	−0.0080 (7)	−0.0005 (7)	−0.0054 (7)
C3	0.0185 (9)	0.0243 (9)	0.0265 (10)	−0.0051 (7)	−0.0019 (8)	−0.0092 (8)
C4	0.0214 (10)	0.0338 (11)	0.0274 (11)	−0.0078 (9)	0.0038 (8)	−0.0146 (9)
C5	0.0299 (10)	0.0247 (9)	0.0199 (10)	−0.0138 (8)	0.0017 (8)	−0.0070 (8)
C6	0.0236 (10)	0.0280 (10)	0.0213 (10)	−0.0049 (8)	−0.0052 (8)	−0.0060 (8)
C7	0.0184 (9)	0.0268 (10)	0.0211 (10)	−0.0043 (8)	−0.0016 (7)	−0.0085 (8)
C8	0.0619 (18)	0.0446 (15)	0.0201 (11)	−0.0107 (13)	−0.0055 (11)	−0.0079 (10)
C9	0.0109 (8)	0.0155 (8)	0.0193 (9)	−0.0021 (6)	0.0002 (6)	−0.0045 (7)
C10	0.0143 (8)	0.0138 (8)	0.0188 (9)	−0.0019 (6)	−0.0010 (7)	−0.0024 (7)
C11	0.0209 (9)	0.0163 (8)	0.0233 (10)	−0.0036 (7)	−0.0057 (7)	−0.0037 (7)
C12	0.0258 (10)	0.0246 (10)	0.0279 (11)	−0.0039 (8)	−0.0096 (8)	−0.0061 (8)
C13	0.0226 (10)	0.0263 (10)	0.0242 (10)	0.0016 (8)	−0.0048 (8)	0.0011 (8)
C14	0.0267 (11)	0.0198 (10)	0.0364 (13)	−0.0050 (8)	−0.0034 (9)	0.0093 (9)
C15	0.0200 (9)	0.0173 (9)	0.0328 (11)	−0.0068 (7)	−0.0034 (8)	0.0007 (8)
C16	0.0348 (14)	0.0494 (16)	0.0388 (15)	−0.0064 (12)	−0.0058 (11)	0.0129 (12)
C17	0.0125 (8)	0.0144 (8)	0.0200 (9)	−0.0045 (6)	−0.0021 (6)	−0.0039 (7)
C18	0.0157 (8)	0.0123 (8)	0.0210 (9)	−0.0056 (6)	−0.0021 (7)	−0.0029 (7)
C19	0.0161 (9)	0.0146 (8)	0.0334 (11)	−0.0036 (7)	0.0009 (8)	−0.0081 (8)
C20	0.0118 (8)	0.0186 (9)	0.0414 (12)	−0.0052 (7)	0.0001 (8)	−0.0079 (8)
C21	0.0152 (8)	0.0142 (8)	0.0292 (10)	−0.0061 (7)	−0.0047 (7)	−0.0035 (7)
C22	0.0185 (9)	0.0140 (8)	0.0245 (10)	−0.0058 (7)	−0.0035 (7)	−0.0046 (7)

Geometric parameters (Å, º) top

Cd1—N1	2.3265 (15)	C6—H6	0.9300
Cd1—O1	2.3170 (14)	C7—C6	1.387 (3)
Cd1—O2	2.3844 (13)	C7—H7	0.9300
Cd1—O3	2.5099 (15)	C8—H8A	0.9600
Cd1—O4	2.3185 (14)	C8—H8B	0.9600
Cd1—O4ⁱ	2.5625 (13)	C8—H8C	0.9600
Cd1—O6	2.3152 (14)	C9—C10	1.489 (3)
Cd1—C1	2.7077 (18)	C10—C11	1.397 (3)
O1—C1	1.267 (2)	C10—C15	1.395 (3)
O2—C1	1.276 (2)	C11—C12	1.376 (3)
O3—C9	1.249 (2)	C11—H11	0.9300
O4—C9	1.289 (2)	C12—C13	1.402 (3)
O5—C22	1.232 (2)	C12—H12	0.9300
O6—H61	0.80 (3)	C13—N4	1.381 (3)
O6—H62	0.81 (3)	C13—C14	1.401 (4)
N1—C17	1.344 (2)	C14—H14	0.9300
N1—C21	1.343 (2)	C15—C14	1.393 (3)
N2—C22	1.319 (3)	C15—H15	0.9300
N2—H2A	0.83 (3)	C16—N4	1.444 (3)
N2—H2B	0.86 (3)	C16—H16A	0.9600
N3—C5	1.366 (3)	C16—H16B	0.9600
N3—C8	1.439 (4)	C16—H16C	0.9600
N3—H3A	0.86 (3)	C17—C18	1.391 (2)
N4—H4A	0.86 (4)	C17—H17	0.9300
C2—C1	1.478 (3)	C19—C18	1.390 (3)
C2—C3	1.400 (3)	C19—C20	1.385 (3)
C2—C7	1.390 (3)	C19—H19	0.9300
C3—H3	0.9300	C20—H20	0.9300
C4—C3	1.377 (3)	C21—C20	1.383 (3)
C4—H4	0.9300	C21—H21	0.9300
C5—C4	1.407 (3)	C22—C18	1.507 (2)
C5—C6	1.399 (3)

O1—Cd1—O2	55.71 (5)	C3—C4—H4	119.6
O1—Cd1—O3	80.21 (5)	C5—C4—H4	119.6
O1—Cd1—O4	106.64 (5)	N3—C5—C4	119.6 (2)
O1—Cd1—O4ⁱ	79.05 (5)	N3—C5—C6	122.2 (2)
O1—Cd1—N1	143.81 (5)	C6—C5—C4	118.18 (19)
O1—Cd1—C1	27.83 (5)	C5—C6—H6	119.8
O2—Cd1—O3	121.55 (5)	C7—C6—C5	120.5 (2)
O2—Cd1—O4ⁱ	91.77 (4)	C7—C6—H6	119.8
O2—Cd1—C1	28.12 (5)	C2—C7—H7	119.3
O3—Cd1—O4ⁱ	117.52 (4)	C6—C7—C2	121.35 (18)
O3—Cd1—C1	103.17 (5)	C6—C7—H7	119.3
O4—Cd1—O2	161.16 (5)	N3—C8—H8A	109.5
O4—Cd1—O3	54.22 (4)	N3—C8—H8B	109.5
O4—Cd1—O4ⁱ	77.12 (5)	N3—C8—H8C	109.5
O4—Cd1—N1	98.06 (5)	H8A—C8—H8B	109.5
O4—Cd1—C1	133.53 (5)	H8A—C8—H8C	109.5
O4ⁱ—Cd1—C1	82.17 (5)	H8B—C8—H8C	109.5
O6—Cd1—O1	112.54 (5)	O3—C9—O4	120.79 (17)
O6—Cd1—O2	88.69 (5)	O3—C9—C10	120.31 (17)
O6—Cd1—O3	73.74 (5)	O4—C9—C10	118.82 (16)
O6—Cd1—O4	105.81 (5)	C11—C10—C9	121.45 (17)
O6—Cd1—O4ⁱ	165.88 (5)	C15—C10—C9	120.91 (18)
O6—Cd1—N1	84.67 (5)	C15—C10—C11	117.54 (18)
O6—Cd1—C1	104.26 (5)	C10—C11—H11	119.1
N1—Cd1—O2	95.16 (5)	C12—C11—C10	121.82 (19)
N1—Cd1—O3	135.97 (5)	C12—C11—H11	119.1
N1—Cd1—O4ⁱ	81.23 (5)	C11—C12—C13	120.8 (2)
N1—Cd1—C1	119.34 (6)	C11—C12—H12	119.6
C1—O1—Cd1	93.51 (11)	C13—C12—H12	119.6
C1—O2—Cd1	90.17 (11)	N4—C13—C12	119.0 (2)
C9—O3—Cd1	88.13 (11)	N4—C13—C14	123.2 (2)
Cd1—O4—Cd1ⁱ	102.88 (5)	C14—C13—C12	117.8 (2)
C9—O4—Cd1	95.93 (11)	C13—C14—H14	119.6
C9—O4—Cd1ⁱ	139.46 (11)	C15—C14—C13	120.8 (2)
Cd1—O6—H61	113 (2)	C15—C14—H14	119.6
Cd1—O6—H62	124 (2)	C10—C15—H15	119.5
H61—O6—H62	102 (3)	C14—C15—C10	121.1 (2)
C17—N1—Cd1	123.06 (12)	C14—C15—H15	119.5
C21—N1—Cd1	118.29 (12)	N4—C16—H16A	109.5
C21—N1—C17	118.08 (15)	N4—C16—H16B	109.5
C22—N2—H2A	123 (2)	N4—C16—H16C	109.5
C22—N2—H2B	116.2 (19)	H16A—C16—H16B	109.5
H2A—N2—H2B	120 (3)	H16A—C16—H16C	109.5
C5—N3—C8	123.2 (2)	H16B—C16—H16C	109.5
C5—N3—H3A	117 (2)	N1—C17—C18	122.70 (16)
C8—N3—H3A	117 (2)	N1—C17—H17	118.6
C13—N4—C16	121.7 (2)	C18—C17—H17	118.6
C13—N4—H4A	122 (3)	C17—C18—C22	123.63 (16)
C16—N4—H4A	103 (3)	C19—C18—C17	118.41 (17)
O1—C1—Cd1	58.66 (9)	C19—C18—C22	117.89 (16)
O1—C1—O2	119.58 (17)	C18—C19—H19	120.5
O1—C1—C2	119.89 (16)	C20—C19—C18	119.07 (17)
O2—C1—Cd1	61.71 (10)	C20—C19—H19	120.5
O2—C1—C2	120.41 (17)	C19—C20—H20	120.6
C2—C1—Cd1	167.59 (12)	C21—C20—C19	118.87 (17)
C3—C2—C1	120.01 (17)	C21—C20—H20	120.6
C7—C2—C1	121.66 (17)	N1—C21—C20	122.78 (17)
C7—C2—C3	118.10 (18)	N1—C21—H21	118.6
C2—C3—H3	119.4	C20—C21—H21	118.6
C4—C3—C2	121.1 (2)	O5—C22—N2	122.37 (18)
C4—C3—H3	119.4	O5—C22—C18	118.50 (17)
C3—C4—C5	120.76 (19)	N2—C22—C18	119.10 (16)

O2—Cd1—O1—C1	−5.82 (10)	O6—Cd1—C1—C2	−161.5 (6)
O3—Cd1—O1—C1	−145.30 (11)	N1—Cd1—C1—O1	−156.66 (10)
O4—Cd1—O1—C1	166.82 (10)	N1—Cd1—C1—O2	33.58 (12)
O4ⁱ—Cd1—O1—C1	93.97 (11)	N1—Cd1—C1—C2	−69.7 (6)
O6—Cd1—O1—C1	−77.59 (11)	Cd1—O1—C1—O2	10.37 (17)
N1—Cd1—O1—C1	35.80 (15)	Cd1—O1—C1—C2	−165.67 (14)
O1—Cd1—O2—C1	5.76 (10)	Cd1—O2—C1—O1	−10.05 (16)
O3—Cd1—O2—C1	54.46 (11)	Cd1—O2—C1—C2	165.96 (14)
O4—Cd1—O2—C1	−16.57 (19)	Cd1—O3—C9—O4	9.37 (17)
O4ⁱ—Cd1—O2—C1	−69.69 (10)	Cd1—O3—C9—C10	−167.39 (15)
O6—Cd1—O2—C1	124.42 (10)	Cd1—O4—C9—O3	−10.20 (18)
N1—Cd1—O2—C1	−151.05 (10)	Cd1ⁱ—O4—C9—O3	107.6 (2)
O1—Cd1—O3—C9	−124.35 (11)	Cd1—O4—C9—C10	166.61 (13)
O2—Cd1—O3—C9	−163.39 (10)	Cd1ⁱ—O4—C9—C10	−75.6 (2)
O4—Cd1—O3—C9	−5.50 (10)	Cd1—N1—C17—C18	170.27 (14)
O4ⁱ—Cd1—O3—C9	−52.25 (12)	C21—N1—C17—C18	−0.8 (3)
O6—Cd1—O3—C9	118.55 (11)	Cd1—N1—C21—C20	−168.42 (16)
N1—Cd1—O3—C9	54.71 (13)	C17—N1—C21—C20	3.1 (3)
C1—Cd1—O3—C9	−140.19 (11)	C8—N3—C5—C4	169.5 (2)
O1—Cd1—O4—Cd1ⁱ	−74.23 (6)	C8—N3—C5—C6	−11.1 (4)
O1—Cd1—O4—C9	69.63 (11)	C3—C2—C1—Cd1	−75.0 (6)
O2—Cd1—O4—Cd1ⁱ	−55.11 (15)	C3—C2—C1—O1	4.7 (3)
O2—Cd1—O4—C9	88.75 (17)	C3—C2—C1—O2	−171.30 (17)
O3—Cd1—O4—Cd1ⁱ	−138.50 (7)	C7—C2—C1—Cd1	99.4 (6)
O3—Cd1—O4—C9	5.36 (10)	C7—C2—C1—O1	179.06 (17)
O4ⁱ—Cd1—O4—Cd1ⁱ	0.0	C7—C2—C1—O2	3.1 (3)
O4ⁱ—Cd1—O4—C9	143.86 (12)	C1—C2—C3—C4	173.52 (18)
O6—Cd1—O4—Cd1ⁱ	165.74 (5)	C7—C2—C3—C4	−1.0 (3)
O6—Cd1—O4—C9	−50.40 (11)	C1—C2—C7—C6	−173.35 (18)
N1—Cd1—O4—Cd1ⁱ	79.03 (5)	C3—C2—C7—C6	1.1 (3)
N1—Cd1—O4—C9	−137.11 (11)	C5—C4—C3—C2	0.0 (3)
C1—Cd1—O4—Cd1ⁱ	−65.79 (7)	N3—C5—C4—C3	−179.5 (2)
C1—Cd1—O4—C9	78.07 (12)	C6—C5—C4—C3	1.0 (3)
O1—Cd1—N1—C17	105.36 (15)	N3—C5—C6—C7	179.6 (2)
O1—Cd1—N1—C21	−83.55 (16)	C4—C5—C6—C7	−1.0 (3)
O2—Cd1—N1—C17	138.80 (14)	C2—C7—C6—C5	−0.1 (3)
O2—Cd1—N1—C21	−50.11 (15)	O3—C9—C10—C11	−175.08 (17)
O3—Cd1—N1—C17	−73.07 (16)	O3—C9—C10—C15	8.7 (3)
O3—Cd1—N1—C21	98.02 (15)	O4—C9—C10—C11	8.1 (3)
O4—Cd1—N1—C17	−27.75 (15)	O4—C9—C10—C15	−168.09 (17)
O4ⁱ—Cd1—N1—C17	47.80 (14)	C9—C10—C11—C12	−173.83 (18)
O4—Cd1—N1—C21	143.34 (14)	C15—C10—C11—C12	2.5 (3)
O4ⁱ—Cd1—N1—C21	−141.11 (15)	C9—C10—C15—C14	173.80 (19)
O6—Cd1—N1—C17	−133.01 (15)	C11—C10—C15—C14	−2.5 (3)
O6—Cd1—N1—C21	38.08 (14)	C10—C11—C12—C13	0.3 (3)
C1—Cd1—N1—C17	123.62 (14)	C11—C12—C13—N4	177.9 (2)
C1—Cd1—N1—C21	−65.29 (15)	C11—C12—C13—C14	−3.0 (3)
O1—Cd1—C1—O2	−169.76 (17)	C12—C13—N4—C16	−171.1 (2)
O1—Cd1—C1—C2	87.0 (6)	C14—C13—N4—C16	9.9 (4)
O2—Cd1—C1—O1	169.76 (17)	N4—C13—C14—C15	−178.1 (2)
O2—Cd1—C1—C2	−103.2 (6)	C12—C13—C14—C15	2.9 (3)
O3—Cd1—C1—O1	35.18 (11)	C10—C15—C14—C13	−0.1 (3)
O3—Cd1—C1—O2	−134.59 (10)	N1—C17—C18—C19	−2.0 (3)
O3—Cd1—C1—C2	122.2 (6)	N1—C17—C18—C22	174.98 (18)
O4—Cd1—C1—O1	−17.53 (13)	C20—C19—C18—C17	2.6 (3)
O4ⁱ—Cd1—C1—O1	−81.36 (11)	C20—C19—C18—C22	−174.56 (19)
O4—Cd1—C1—O2	172.70 (9)	C18—C19—C20—C21	−0.5 (3)
O4ⁱ—Cd1—C1—O2	108.88 (10)	N1—C21—C20—C19	−2.5 (3)
O4—Cd1—C1—C2	69.5 (6)	O5—C22—C18—C17	−175.9 (2)
O4ⁱ—Cd1—C1—C2	5.6 (6)	O5—C22—C18—C19	1.1 (3)
O6—Cd1—C1—O1	111.46 (11)	N2—C22—C18—C17	2.1 (3)
O6—Cd1—C1—O2	−58.31 (11)	N2—C22—C18—C19	179.1 (2)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.83 (3)	2.13 (3)	2.921 (2)	160 (2)
N2—H2B···O3ⁱⁱ	0.86 (3)	2.05 (3)	2.901 (3)	170 (3)
O6—H61···O5ⁱⁱⁱ	0.79 (4)	1.91 (4)	2.692 (2)	167 (3)
O6—H62···O2^iv	0.81 (4)	1.94 (4)	2.743 (2)	179 (3)
C11—H11···O2ⁱ	0.93	2.39	3.299 (2)	165
C17—H17···O1ⁱ	0.93	2.36	3.216 (3)	153
C21—H21···O2^iv	0.93	2.45	3.252 (3)	145
C19—H19···Cg3^v	0.93	2.74	3.537 (2)	144

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

Experimental details

Crystal data
Chemical formula	[Cd₂(C₈H₈NO₂)₄(C₆H₆N₂O)₂(H₂O)₂]
M_r	1105.72
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	9.5286 (2), 10.1734 (2), 13.2876 (3)
α, β, γ (°)	72.831 (3), 75.741 (3), 67.172 (2)
V (Å³)	1121.51 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.37 × 0.26 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.734, 0.901
No. of measured, independent and observed [I > 2σ(I)] reflections	20025, 5581, 5250
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.061, 1.08
No. of reflections	5581
No. of parameters	324
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)	1.77, −0.48

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Cd1—N1	2.3265 (15)	Cd1—O4	2.3185 (14)
Cd1—O1	2.3170 (14)	Cd1—O4ⁱ	2.5625 (13)
Cd1—O2	2.3844 (13)	Cd1—O6	2.3152 (14)
Cd1—O3	2.5099 (15)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.83 (3)	2.13 (3)	2.921 (2)	160 (2)
N2—H2B···O3ⁱⁱ	0.86 (3)	2.05 (3)	2.901 (3)	170 (3)
O6—H61···O5ⁱⁱⁱ	0.79 (4)	1.91 (4)	2.692 (2)	167 (3)
O6—H62···O2^iv	0.81 (4)	1.94 (4)	2.743 (2)	179 (3)
C11—H11···O2ⁱ	0.93	2.39	3.299 (2)	165
C17—H17···O1ⁱ	0.93	2.36	3.216 (3)	153
C21—H21···O2^iv	0.93	2.45	3.252 (3)	145
C19—H19···Cg3^v	0.93	2.74	3.537 (2)	144

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

Acknowledgements

The authors are indebted to Anadolu University and the Medicinal Plants and Medicine Research Centre of Anadolu University, Eskişehir, Turkey, for the use of X-ray diffractometer. This work was supported financially by Kafkas University Research Fund (grant No. 2009-FEF-03).

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