Di-μ-nicotinamide-κ2N1:O;κ2O:N1-bis­[aqua­bis­(3-chloro­benzoato-κ2O,O′)cadmium]

Bozkurt, N.; Dilek, N.; Çaylak Delibaş, N.; Necefoğlu, H.; Hökelek, T.

doi:10.1107/S1600536813015948

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 69| Part 7| July 2013| Pages m389-m390

https://doi.org/10.1107/S1600536813015948

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Di-μ-nicotinamide-κ²N¹:O;κ²O:N¹-bis[aquabis(3-chlorobenzoato-κ²O,O′)cadmium]

Nihat Bozkurt,^a Nefise Dilek,^b Nagihan Çaylak Delibaş,^c Hacali Necefoğlu ^a and Tuncer Hökelek ^d ^*

^aDepartment of Chemistry, Kafkas University, 36100 Kars, Turkey, ^bAksaray University, Department of Physics, 68100, Aksaray, Turkey, ^cDepartment of Physics, Sakarya University, 54187 Esentepe, Sakarya, Turkey, and ^dDepartment of Physics, Hacettepe University, 06800 Beytepe, Ankara, Turkey
^*Correspondence e-mail: merzifon@hacettepe.edu.tr

(Received 6 June 2013; accepted 7 June 2013; online 15 June 2013)

In the centrosymmetric dinuclear title compound, [Cd₂(C₇H₄ClO₂)₄(C₆H₆N₂O)₂(H₂O)₂], the Cd^II atom is coordinated by one N atom from one bridging nicotinamide ligand and one O atom from another symmetry-related bridging nicotinamide ligand, four O atoms from two 3-chlorobenzoate ligands and one water molecule in an irregular geometry. The dihedral angles between the carboxylate groups and the adjacent benzene rings are 6.98 (12) and 2.42 (13)°, while the benzene rings are oriented at a dihedral angle of 4.33 (6)°. Intermolecular O—H⋯O, N—H⋯O and weak C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. π–π interactions, indicated by short centroid–centroid distances [3.892 (1) Å between the pyridine rings and 3.683 (1) Å between the benzene rings] further stabilize the structure.

Related literature

For niacin, see: Krishnamachari (1974 ). For the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972 ). For related structures, see: Hökelek et al. (2009a ,b , 2010a ,b ); Necefoğlu et al. (2011a ,b ); Greenaway et al. (1984 ).

Experimental

Crystal data

[Cd₂(C₇H₄ClO₂)₄(C₆H₆N₂O)₂(H₂O)₂]
M_r = 1127.32
Triclinic, $[P \overline 1]$
a = 7.5835 (2) Å
b = 12.3652 (3) Å
c = 12.4893 (3) Å
α = 66.878 (2)°
β = 78.678 (3)°
γ = 83.222 (3)°
V = 1055.02 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.33 mm⁻¹
T = 296 K
0.38 × 0.24 × 0.12 mm

Data collection

Bruker SMART BREEZE CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.689, T_max = 0.853
18369 measured reflections
4310 independent reflections
4106 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.052
S = 1.09
4310 reflections
296 parameters
103 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected bond lengths (Å)

Cd1—O1	2.3234 (14)
Cd1—O2	2.4800 (13)
Cd1—O3	2.5447 (15)
Cd1—O4	2.3110 (16)
Cd1—O5ⁱ	2.3175 (12)
Cd1—O6	2.3019 (14)
Cd1—N1	2.3384 (14)
Symmetry code: (i) -x+1, -y+2, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O3ⁱ	0.83 (3)	2.26 (2)	3.026 (2)	155 (2)
N2—H22⋯O2ⁱⁱ	0.83 (2)	2.09 (2)	2.913 (2)	170 (2)
O6—H61⋯O1ⁱⁱⁱ	0.85 (4)	2.15 (4)	2.897 (2)	146 (3)
O6—H62⋯O3ⁱⁱⁱ	0.81 (3)	1.94 (3)	2.710 (2)	158 (3)
C8—H8⋯O5ⁱ	0.93	2.43	3.158 (2)	135
C10—H10⋯O2ⁱⁱ	0.93	2.54	3.403 (3)	154
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x, -y+2, -z+1; (iii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); 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 ); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813015948/bq2387sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813015948/bq2387Isup2.hkl

checkCIF report

Comment top

As a part of our ongoing investigations of 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 center and made up of two Cd cations, four 3-chlorobenzoate (CB) anions, which act in bidentate modes, two nicotinamide (NA) ligands and two water molecules (Fig. 1). Both of the Cd^II centres are seven-coordinated, and the two monomeric units are bridged through the two nicotinamide (NA) ligands about an inversion center. The Cd1···Cd1a [symmetry code: (a) 1 - x, - y, 1 - z] distance is 7.1647 (3)Å. In the molecule, two Cd—O bond distances [2.4800 (13)Å and 2.5447 (15)Å] are significantly longer than the other four, and the average Cd—O bond length is 2.3798 (14)Å (Table 1). The Cd atom is displaced out of the least-squares planes of the carboxylate groups (O1/C1/O2) and (O3/C14/O4) by -0.2003 (1)Å and -0.3909 (1)Å, respectively.

The dihedral angles between the planar carboxylate groups and the adjacent benzene rings A (C2—C7) and C (C15—C20) are 6.98 (12)° and 2.42 (13)°, respectively, while those between rings A, B (N1/C8—C12) and C are A/B = 80.48 (7)°, A/C = 4.33 (6)°, B/C = 81.80 (7)°.

In (I), the O1-Cd1-O2 and O3-Cd1-O4 angles are 54.22 (4)° and 53.32 (5) °, respectively. The corresponding O—M—O (where M is a metal) angles are 57.75 (2)° in [Cu(C₇H₅O₂F)(C₇H₄O₂F)₂(C₆H₆N₂O)₂], (II) (Necefoğlu et al., 2011a), 60.32 (4)° in [Co(C₈H₇O₃)₂(C₆H₆N₂O)(H₂O)₂], (III) (Hökelek et al., 2010a), 59.02 (8)° in [Zn(C₈H₈NO₂)₂(C₆H₆N₂O)₂].H₂O, (IV) (Hökelek et al., 2009a), 60.03 (6)° in [Zn(C₉H₁₀NO₂)₂(C₆H₆N₂O)₂(H₂O)₂], (V) (Hökelek et al., 2009b), 57.53 (5)°, 56.19 (5)° and 59.04 (4)° in [Zn(C₈H₇O₃)₂(C₆H₆N₂O)₂], (VI) (Hökelek et al., 2010b), 57.61 (8)° in [Mn₂(C₇H₄O₂Br)₄(C₆H₆N₂O)₂(H₂O)₂], (VII) (Necefoğlu et al., 2011b) and 55.2 (1)° in [Cu(Asp)₂(py)₂] (where Asp is acetylsalicylate and py is pyridine) [(VIII); Greenaway et al., 1984].

In the crystal structure, intermolecular O—H···O, N—H···O and C—H···O hydrogen bonds link the molecules into a three dimensional network (Table 2), in which they may be effective in the stabilization of the structure. The π···π contacts between the pyridine rings and between the benzene rings, Cg2—Cg2ⁱ and Cg1—Cg3ⁱⁱ [symmetry codes: (i) 2 - x, - y, - z; (ii) 1 - x, 1 - y, 1 - z, where Cg1, Cg2 and Cg3 are the centroids of the rings A (C2—C7), B (N1/C8—C12) and C (C15—C20), respectively] may further stabilize the structure, with centroid-centroid distances of 3.892 (1)Å and 3.683 (1)Å, respectively.

Related literature top

For niacin, see: Krishnamachari (1974). For the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (2009a,b); Hökelek et al. (2010a,b); Necefoğlu et al. (2011a,b); Greenaway et al. (1984).

Experimental top

The title compound was prepared by the reaction of 3CdSO₄.8H₂O (1.283 g, 5 mmol) in H₂O (50 ml) and nicotinamide (1.220 g, 10 mmol) in H₂O (50 ml) with sodium 3-chlorobenzoate (1.790 g, 10 mmol) in H₂O (100 ml) at room temperature. The mixture was filtered and set aside to crystallize at ambient temperature for two weeks, giving colorless single crystals.

Structure description top

For niacin, see: Krishnamachari (1974). For the nicotinic acid derivative N,N-diethylnicotinamide, see: Bigoli et al. (1972). For related structures, see: Hökelek et al. (2009a,b); Hökelek et al. (2010a,b); Necefoğlu et al. (2011a,b); Greenaway et al. (1984).

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); 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); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (a) 1 - x, - y, 1 - z].

Di-µ-nicotinamide-κ²N¹:O;κ²O:N¹-bis[aquabis(3-chlorobenzoato-κ²O,O')cadmium] top

Crystal data top

[Cd₂(C₇H₄ClO₂)₄(C₆H₆N₂O)₂(H₂O)₂]	Z = 1
M_r = 1127.32	F(000) = 560
Triclinic, P1	D_x = 1.774 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5835 (2) Å	Cell parameters from 9868 reflections
b = 12.3652 (3) Å	θ = 2.7–28.4°
c = 12.4893 (3) Å	µ = 1.33 mm⁻¹
α = 66.878 (2)°	T = 296 K
β = 78.678 (3)°	Block, colorless
γ = 83.222 (3)°	0.38 × 0.24 × 0.12 mm
V = 1055.02 (5) Å³

Data collection top

Bruker SMART BREEZE CCD diffractometer	4310 independent reflections
Radiation source: fine-focus sealed tube	4106 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 26.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −9→9
T_min = 0.689, T_max = 0.853	k = −15→15
18369 measured reflections	l = −15→13

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.052	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0281P)² + 0.3773P] where P = (F_o² + 2F_c²)/3
4310 reflections	(Δ/σ)_max = 0.002
296 parameters	Δρ_max = 0.50 e Å⁻³
103 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Cd₂(C₇H₄ClO₂)₄(C₆H₆N₂O)₂(H₂O)₂]	γ = 83.222 (3)°
M_r = 1127.32	V = 1055.02 (5) Å³
Triclinic, P1	Z = 1
a = 7.5835 (2) Å	Mo Kα radiation
b = 12.3652 (3) Å	µ = 1.33 mm⁻¹
c = 12.4893 (3) Å	T = 296 K
α = 66.878 (2)°	0.38 × 0.24 × 0.12 mm
β = 78.678 (3)°

Data collection top

Bruker SMART BREEZE CCD diffractometer	4310 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	4106 reflections with I > 2σ(I)
T_min = 0.689, T_max = 0.853	R_int = 0.020
18369 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	103 restraints
wR(F²) = 0.052	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Δρ_max = 0.50 e Å⁻³
4310 reflections	Δρ_min = −0.31 e Å⁻³
296 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	0.460563 (15)	0.713174 (9)	0.502386 (11)	0.02850 (5)
Cl1	0.20058 (11)	1.03333 (7)	−0.11806 (6)	0.0761 (2)
Cl2	0.76396 (11)	0.40476 (8)	1.09335 (6)	0.0821 (2)
O1	0.53731 (18)	0.68689 (12)	0.32444 (12)	0.0428 (3)
O2	0.31326 (17)	0.81613 (13)	0.32598 (12)	0.0409 (3)
O3	0.7424 (2)	0.58157 (12)	0.54856 (12)	0.0454 (3)
O4	0.5701 (2)	0.64166 (16)	0.67878 (14)	0.0635 (5)
O5	0.35989 (16)	1.12711 (11)	0.55996 (14)	0.0421 (3)
O6	0.2965 (2)	0.54660 (13)	0.57771 (15)	0.0428 (3)
H61	0.340 (4)	0.488 (3)	0.631 (3)	0.086 (11)*
H62	0.266 (4)	0.523 (2)	0.532 (2)	0.059 (8)*
N1	0.22851 (19)	0.80844 (12)	0.59063 (13)	0.0305 (3)
N2	0.0768 (2)	1.19067 (14)	0.60728 (15)	0.0359 (3)
H21	0.110 (3)	1.259 (2)	0.5826 (19)	0.040 (6)*
H22	−0.033 (3)	1.1805 (19)	0.6266 (19)	0.040 (6)*
C1	0.4252 (2)	0.76332 (15)	0.27256 (16)	0.0322 (4)
C2	0.4302 (2)	0.79357 (16)	0.14374 (16)	0.0342 (4)
C3	0.3235 (3)	0.88734 (17)	0.08028 (17)	0.0386 (4)
H3	0.2453	0.9300	0.1181	0.046*
C4	0.3347 (3)	0.91633 (19)	−0.03919 (18)	0.0476 (5)
C5	0.4493 (4)	0.8553 (3)	−0.0977 (2)	0.0640 (7)
H5	0.4561	0.8766	−0.1785	0.077*
C6	0.5542 (4)	0.7616 (3)	−0.0341 (2)	0.0681 (7)
H6	0.6318	0.7192	−0.0725	0.082*
C7	0.5445 (3)	0.7307 (2)	0.0856 (2)	0.0497 (5)
H7	0.6152	0.6672	0.1275	0.060*
C8	0.2617 (2)	0.91606 (15)	0.57989 (16)	0.0312 (4)
H8	0.3762	0.9434	0.5445	0.037*
C9	0.1366 (2)	0.98948 (14)	0.61809 (15)	0.0271 (3)
C10	−0.0336 (2)	0.94833 (16)	0.67092 (17)	0.0354 (4)
H10	−0.1225	0.9951	0.6971	0.042*
C11	−0.0685 (3)	0.83632 (17)	0.68393 (18)	0.0415 (4)
H11	−0.1813	0.8063	0.7200	0.050*
C12	0.0650 (2)	0.76927 (15)	0.64305 (17)	0.0351 (4)
H12	0.0398	0.6939	0.6524	0.042*
C13	0.1971 (2)	1.10895 (15)	0.59403 (15)	0.0297 (3)
C14	0.6964 (3)	0.57773 (16)	0.65218 (17)	0.0386 (4)
C15	0.7945 (2)	0.49355 (16)	0.74759 (17)	0.0346 (4)
C16	0.7431 (3)	0.48946 (19)	0.86197 (18)	0.0429 (4)
H16	0.6506	0.5397	0.8790	0.051*
C17	0.8306 (3)	0.4102 (2)	0.94991 (19)	0.0494 (5)
C18	0.9655 (3)	0.3336 (2)	0.9270 (2)	0.0538 (5)
H18	1.0216	0.2793	0.9876	0.065*
C19	1.0164 (3)	0.3383 (2)	0.8131 (2)	0.0527 (5)
H19	1.1086	0.2877	0.7965	0.063*
C20	0.9308 (3)	0.41792 (17)	0.72359 (18)	0.0404 (4)
H20	0.9652	0.4205	0.6470	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02751 (7)	0.02414 (7)	0.03423 (8)	0.00202 (5)	−0.00289 (5)	−0.01339 (5)
Cl1	0.0897 (5)	0.0728 (4)	0.0522 (4)	0.0005 (4)	−0.0339 (3)	−0.0001 (3)
Cl2	0.0835 (5)	0.1212 (6)	0.0423 (3)	0.0194 (4)	−0.0211 (3)	−0.0333 (4)
O1	0.0440 (7)	0.0409 (7)	0.0385 (7)	0.0112 (6)	−0.0088 (6)	−0.0123 (6)
O2	0.0344 (7)	0.0516 (8)	0.0382 (7)	0.0078 (6)	−0.0040 (5)	−0.0224 (6)
O3	0.0644 (9)	0.0350 (7)	0.0377 (8)	−0.0055 (6)	−0.0119 (6)	−0.0122 (6)
O4	0.0594 (10)	0.0753 (11)	0.0474 (9)	0.0313 (9)	−0.0172 (8)	−0.0197 (8)
O5	0.0267 (6)	0.0326 (7)	0.0697 (10)	−0.0027 (5)	0.0032 (6)	−0.0273 (7)
O6	0.0511 (8)	0.0310 (7)	0.0461 (9)	−0.0080 (6)	0.0020 (7)	−0.0172 (7)
N1	0.0301 (7)	0.0272 (7)	0.0351 (8)	0.0009 (5)	−0.0029 (6)	−0.0146 (6)
N2	0.0293 (8)	0.0296 (8)	0.0502 (10)	0.0022 (6)	−0.0013 (7)	−0.0201 (7)
C1	0.0283 (8)	0.0334 (9)	0.0335 (9)	−0.0042 (7)	−0.0019 (7)	−0.0117 (7)
C2	0.0309 (8)	0.0385 (9)	0.0321 (9)	−0.0056 (7)	−0.0004 (7)	−0.0133 (7)
C3	0.0379 (9)	0.0408 (10)	0.0366 (10)	−0.0029 (8)	−0.0055 (8)	−0.0140 (8)
C4	0.0524 (12)	0.0499 (11)	0.0354 (11)	−0.0120 (9)	−0.0107 (9)	−0.0065 (9)
C5	0.0791 (17)	0.0805 (17)	0.0312 (11)	−0.0132 (14)	−0.0016 (11)	−0.0206 (11)
C6	0.0763 (18)	0.0812 (18)	0.0502 (14)	0.0032 (14)	0.0068 (12)	−0.0384 (14)
C7	0.0484 (12)	0.0561 (13)	0.0443 (12)	0.0056 (10)	−0.0013 (9)	−0.0240 (10)
C8	0.0249 (8)	0.0310 (8)	0.0389 (10)	−0.0014 (6)	0.0020 (7)	−0.0176 (7)
C9	0.0259 (8)	0.0270 (8)	0.0295 (8)	0.0012 (6)	−0.0030 (6)	−0.0134 (7)
C10	0.0284 (8)	0.0366 (9)	0.0406 (10)	−0.0002 (7)	0.0045 (7)	−0.0191 (8)
C11	0.0306 (9)	0.0411 (10)	0.0489 (12)	−0.0095 (7)	0.0088 (8)	−0.0178 (9)
C12	0.0357 (9)	0.0282 (8)	0.0403 (10)	−0.0048 (7)	−0.0020 (7)	−0.0127 (7)
C13	0.0273 (8)	0.0300 (8)	0.0342 (9)	0.0005 (6)	−0.0021 (7)	−0.0167 (7)
C14	0.0415 (10)	0.0341 (9)	0.0385 (10)	−0.0038 (8)	−0.0101 (8)	−0.0098 (8)
C15	0.0317 (9)	0.0337 (9)	0.0380 (10)	−0.0029 (7)	−0.0055 (7)	−0.0127 (8)
C16	0.0375 (10)	0.0509 (11)	0.0425 (11)	0.0084 (8)	−0.0089 (8)	−0.0220 (9)
C17	0.0425 (11)	0.0649 (14)	0.0395 (11)	0.0019 (10)	−0.0117 (9)	−0.0173 (10)
C18	0.0424 (11)	0.0559 (13)	0.0525 (13)	0.0086 (9)	−0.0170 (10)	−0.0078 (10)
C19	0.0398 (11)	0.0489 (12)	0.0624 (14)	0.0113 (9)	−0.0064 (10)	−0.0184 (11)
C20	0.0382 (10)	0.0390 (10)	0.0414 (11)	−0.0016 (8)	0.0000 (8)	−0.0155 (8)

Geometric parameters (Å, º) top

Cd1—O1	2.3234 (14)	C3—H3	0.9300
Cd1—O2	2.4800 (13)	C4—C5	1.373 (4)
Cd1—O3	2.5447 (15)	C5—C6	1.383 (4)
Cd1—O4	2.3110 (16)	C5—H5	0.9300
Cd1—O5ⁱ	2.3175 (12)	C6—H6	0.9300
Cd1—O6	2.3019 (14)	C7—C6	1.379 (3)
Cd1—N1	2.3384 (14)	C7—H7	0.9300
Cd1—C1	2.7496 (18)	C8—H8	0.9300
Cl1—C4	1.739 (2)	C9—C8	1.383 (2)
Cl2—C17	1.740 (2)	C9—C10	1.385 (2)
O1—C1	1.257 (2)	C9—C13	1.497 (2)
O2—C1	1.257 (2)	C10—C11	1.381 (3)
O3—C14	1.256 (2)	C10—H10	0.9300
O4—C14	1.247 (3)	C11—H11	0.9300
O5—Cd1ⁱ	2.3175 (12)	C12—C11	1.380 (3)
O5—C13	1.241 (2)	C12—H12	0.9300
O6—H61	0.85 (3)	C15—C14	1.499 (3)
O6—H62	0.82 (3)	C15—C16	1.387 (3)
N1—C8	1.333 (2)	C15—C20	1.380 (3)
N1—C12	1.332 (2)	C16—C17	1.377 (3)
N2—C13	1.317 (2)	C16—H16	0.9300
N2—H21	0.83 (2)	C17—C18	1.376 (3)
N2—H22	0.83 (2)	C18—H18	0.9300
C1—C2	1.496 (3)	C19—C18	1.378 (3)
C2—C7	1.386 (3)	C19—H19	0.9300
C3—C2	1.392 (3)	C20—C19	1.382 (3)
C3—C4	1.378 (3)	C20—H20	0.9300

O1—Cd1—O2	54.22 (4)	C4—C3—H3	120.3
O1—Cd1—O3	82.45 (4)	C3—C4—Cl1	119.17 (18)
O1—Cd1—N1	137.15 (5)	C5—C4—Cl1	119.11 (18)
O1—Cd1—C1	27.07 (5)	C5—C4—C3	121.7 (2)
O2—Cd1—O3	136.12 (4)	C4—C5—C6	118.8 (2)
O2—Cd1—C1	27.20 (5)	C4—C5—H5	120.6
O3—Cd1—C1	109.10 (5)	C6—C5—H5	120.6
O4—Cd1—O1	135.63 (5)	C5—C6—H6	119.7
O4—Cd1—O2	169.88 (5)	C7—C6—C5	120.5 (2)
O4—Cd1—O3	53.32 (5)	C7—C6—H6	119.7
O4—Cd1—O5ⁱ	88.27 (6)	C2—C7—H7	119.8
O4—Cd1—N1	87.04 (5)	C6—C7—C2	120.4 (2)
O4—Cd1—C1	162.39 (6)	C6—C7—H7	119.8
O5ⁱ—Cd1—O1	93.65 (5)	N1—C8—C9	124.08 (15)
O5ⁱ—Cd1—O2	88.64 (5)	N1—C8—H8	118.0
O5ⁱ—Cd1—O3	87.51 (4)	C9—C8—H8	118.0
O5ⁱ—Cd1—N1	90.96 (5)	C8—C9—C10	117.80 (15)
O5ⁱ—Cd1—C1	90.09 (5)	C8—C9—C13	116.21 (15)
O6—Cd1—O1	89.05 (5)	C10—C9—C13	125.95 (15)
O6—Cd1—O2	96.40 (6)	C9—C10—H10	120.7
O6—Cd1—O3	88.63 (5)	C11—C10—C9	118.53 (16)
O6—Cd1—O4	86.82 (7)	C11—C10—H10	120.7
O6—Cd1—O5ⁱ	174.96 (6)	C10—C11—H11	120.2
O6—Cd1—N1	89.95 (5)	C12—C11—C10	119.61 (16)
O6—Cd1—C1	94.24 (6)	C12—C11—H11	120.2
N1—Cd1—O2	83.38 (5)	N1—C12—C11	122.44 (16)
N1—Cd1—O3	140.36 (5)	N1—C12—H12	118.8
N1—Cd1—C1	110.52 (5)	C11—C12—H12	118.8
C1—O1—Cd1	95.71 (11)	O5—C13—N2	122.76 (16)
C1—O2—Cd1	88.42 (11)	O5—C13—C9	117.92 (15)
C14—O3—Cd1	86.39 (12)	N2—C13—C9	119.30 (15)
C14—O4—Cd1	97.51 (13)	O3—C14—C15	119.50 (18)
C13—O5—Cd1ⁱ	136.29 (11)	O4—C14—O3	121.95 (18)
Cd1—O6—H62	118.6 (19)	O4—C14—C15	118.55 (18)
Cd1—O6—H61	115 (2)	C16—C15—C14	119.32 (17)
H62—O6—H61	108 (3)	C20—C15—C14	120.79 (18)
C8—N1—Cd1	115.65 (11)	C20—C15—C16	119.86 (18)
C12—N1—Cd1	126.66 (11)	C15—C16—H16	120.4
C12—N1—C8	117.53 (15)	C17—C16—C15	119.19 (19)
C13—N2—H21	117.5 (16)	C17—C16—H16	120.4
C13—N2—H22	123.5 (15)	C16—C17—Cl2	118.88 (17)
H21—N2—H22	118 (2)	C18—C17—C16	121.3 (2)
O1—C1—O2	121.43 (17)	C18—C17—Cl2	119.75 (17)
O1—C1—C2	118.66 (16)	C17—C18—C19	119.2 (2)
O1—C1—Cd1	57.23 (10)	C17—C18—H18	120.4
O2—C1—Cd1	64.37 (10)	C19—C18—H18	120.4
O2—C1—C2	119.89 (16)	C18—C19—C20	120.2 (2)
C2—C1—Cd1	172.93 (12)	C18—C19—H19	119.9
C3—C2—C1	120.25 (17)	C20—C19—H19	119.9
C7—C2—C1	120.45 (17)	C15—C20—C19	120.2 (2)
C7—C2—C3	119.28 (18)	C15—C20—H20	119.9
C2—C3—H3	120.3	C19—C20—H20	119.9
C4—C3—C2	119.33 (19)

O2—Cd1—O1—C1	2.65 (10)	Cd1—O1—C1—O2	−4.98 (18)
O3—Cd1—O1—C1	−170.02 (11)	Cd1—O1—C1—C2	173.31 (13)
O4—Cd1—O1—C1	−174.29 (11)	Cd1—O2—C1—O1	4.64 (17)
O5ⁱ—Cd1—O1—C1	−83.03 (11)	Cd1—O2—C1—C2	−173.62 (14)
O6—Cd1—O1—C1	101.24 (11)	Cd1—O3—C14—O4	−8.9 (2)
N1—Cd1—O1—C1	12.33 (14)	Cd1—O3—C14—C15	170.72 (15)
O1—Cd1—O2—C1	−2.64 (10)	Cd1—O4—C14—O3	9.8 (2)
O3—Cd1—O2—C1	7.87 (13)	Cd1—O4—C14—C15	−169.75 (14)
O4—Cd1—O2—C1	165.1 (3)	Cd1ⁱ—O5—C13—N2	−3.1 (3)
O5ⁱ—Cd1—O2—C1	92.85 (11)	Cd1ⁱ—O5—C13—C9	175.50 (12)
O6—Cd1—O2—C1	−86.82 (11)	C12—N1—C8—C9	−1.0 (3)
N1—Cd1—O2—C1	−176.03 (11)	Cd1—N1—C12—C11	−174.35 (15)
O1—Cd1—O3—C14	−171.24 (11)	C8—N1—C12—C11	1.0 (3)
O2—Cd1—O3—C14	−179.82 (10)	O1—C1—C2—C3	−172.19 (17)
O4—Cd1—O3—C14	5.05 (11)	O1—C1—C2—C7	6.0 (3)
O5ⁱ—Cd1—O3—C14	94.75 (11)	O2—C1—C2—C3	6.1 (3)
O6—Cd1—O3—C14	−82.01 (11)	O2—C1—C2—C7	−175.64 (18)
N1—Cd1—O3—C14	6.26 (14)	C1—C2—C7—C6	−177.4 (2)
C1—Cd1—O3—C14	−176.02 (10)	C3—C2—C7—C6	0.8 (3)
O1—Cd1—O4—C14	0.16 (19)	C4—C3—C2—C1	177.72 (17)
O2—Cd1—O4—C14	−165.6 (3)	C4—C3—C2—C7	−0.5 (3)
O3—Cd1—O4—C14	−5.11 (12)	C2—C3—C4—Cl1	179.81 (15)
O5ⁱ—Cd1—O4—C14	−93.29 (14)	C2—C3—C4—C5	−0.2 (3)
O6—Cd1—O4—C14	85.54 (14)	Cl1—C4—C5—C6	−179.3 (2)
N1—Cd1—O4—C14	175.66 (14)	C3—C4—C5—C6	0.7 (4)
C1—Cd1—O4—C14	−8.5 (3)	C2—C7—C6—C5	−0.4 (4)
O1—Cd1—N1—C8	−95.81 (14)	C4—C5—C6—C7	−0.4 (4)
O1—Cd1—N1—C12	79.59 (17)	C10—C9—C8—N1	0.1 (3)
O2—Cd1—N1—C8	−87.92 (13)	C13—C9—C8—N1	−177.73 (16)
O2—Cd1—N1—C12	87.48 (15)	C8—C9—C10—C11	0.8 (3)
O3—Cd1—N1—C8	87.85 (14)	C13—C9—C10—C11	178.40 (18)
O3—Cd1—N1—C12	−96.76 (16)	C8—C9—C13—O5	−11.4 (2)
O4—Cd1—N1—C8	88.82 (13)	C8—C9—C13—N2	167.21 (17)
O4—Cd1—N1—C12	−95.78 (16)	C10—C9—C13—O5	170.94 (18)
O5ⁱ—Cd1—N1—C8	0.60 (13)	C10—C9—C13—N2	−10.4 (3)
O5ⁱ—Cd1—N1—C12	176.00 (15)	C9—C10—C11—C12	−0.8 (3)
O6—Cd1—N1—C8	175.64 (13)	N1—C12—C11—C10	−0.1 (3)
O6—Cd1—N1—C12	−8.96 (15)	C16—C15—C14—O3	−179.91 (18)
C1—Cd1—N1—C8	−89.86 (13)	C16—C15—C14—O4	−0.3 (3)
C1—Cd1—N1—C12	85.54 (15)	C20—C15—C14—O3	−2.0 (3)
O1—Cd1—C1—O2	175.29 (18)	C20—C15—C14—O4	177.61 (19)
O2—Cd1—C1—O1	−175.29 (18)	C14—C15—C16—C17	178.51 (19)
O3—Cd1—C1—O1	10.47 (12)	C20—C15—C16—C17	0.6 (3)
O3—Cd1—C1—O2	−174.24 (10)	C14—C15—C20—C19	−178.02 (18)
O4—Cd1—C1—O1	13.3 (3)	C16—C15—C20—C19	−0.1 (3)
O4—Cd1—C1—O2	−171.40 (18)	C15—C16—C17—Cl2	−179.44 (16)
O5ⁱ—Cd1—C1—O1	97.86 (11)	C15—C16—C17—C18	−1.2 (3)
O5ⁱ—Cd1—C1—O2	−86.85 (11)	Cl2—C17—C18—C19	179.63 (18)
O6—Cd1—C1—O1	−79.54 (11)	C16—C17—C18—C19	1.4 (4)
O6—Cd1—C1—O2	95.75 (11)	C20—C19—C18—C17	−1.0 (4)
N1—Cd1—C1—O1	−171.08 (10)	C15—C20—C19—C18	0.3 (3)
N1—Cd1—C1—O2	4.21 (12)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3ⁱ	0.83 (3)	2.26 (2)	3.026 (2)	155 (2)
N2—H22···O2ⁱⁱ	0.83 (2)	2.09 (2)	2.913 (2)	170 (2)
O6—H61···O1ⁱⁱⁱ	0.85 (4)	2.15 (4)	2.897 (2)	146 (3)
O6—H62···O3ⁱⁱⁱ	0.81 (3)	1.94 (3)	2.710 (2)	158 (3)
C8—H8···O5ⁱ	0.93	2.43	3.158 (2)	135
C10—H10···O2ⁱⁱ	0.93	2.54	3.403 (3)	154

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cd₂(C₇H₄ClO₂)₄(C₆H₆N₂O)₂(H₂O)₂]
M_r	1127.32
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.5835 (2), 12.3652 (3), 12.4893 (3)
α, β, γ (°)	66.878 (2), 78.678 (3), 83.222 (3)
V (Å³)	1055.02 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.33
Crystal size (mm)	0.38 × 0.24 × 0.12

Data collection
Diffractometer	Bruker SMART BREEZE CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012)
T_min, T_max	0.689, 0.853
No. of measured, independent and observed [I > 2σ(I)] reflections	18369, 4310, 4106
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.052, 1.09
No. of reflections	4310
No. of parameters	296
No. of restraints	103
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.31

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

Selected bond lengths (Å) top

Cd1—O1	2.3234 (14)	Cd1—O5ⁱ	2.3175 (12)
Cd1—O2	2.4800 (13)	Cd1—O6	2.3019 (14)
Cd1—O3	2.5447 (15)	Cd1—N1	2.3384 (14)
Cd1—O4	2.3110 (16)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H21···O3ⁱ	0.83 (3)	2.26 (2)	3.026 (2)	155 (2)
N2—H22···O2ⁱⁱ	0.83 (2)	2.09 (2)	2.913 (2)	170 (2)
O6—H61···O1ⁱⁱⁱ	0.85 (4)	2.15 (4)	2.897 (2)	146 (3)
O6—H62···O3ⁱⁱⁱ	0.81 (3)	1.94 (3)	2.710 (2)	158 (3)
C8—H8···O5ⁱ	0.93	2.43	3.158 (2)	135
C10—H10···O2ⁱⁱ	0.93	2.54	3.403 (3)	154

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.

Acknowledgements

The authors acknowledge the Aksaray University Science and Technology Application and Research Center, Aksaray, Turkey, for use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State of Planning Organization).

References

Bigoli, F., Braibanti, A., Pellinghelli, M. A. & Tiripicchio, A. (1972). Acta Cryst. B28, 962–966. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Bruker (2012). 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
Greenaway, F. T., Pazeshk, A., Cordes, A. W., Noble, M. C. & Sorenson, J. R. J. (1984). Inorg. Chim. Acta, 93, 67–71. CSD CrossRef CAS Web of Science Google Scholar
Hökelek, T., Dal, H., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009a). Acta Cryst. E65, m1365–m1366. Web of Science CrossRef IUCr Journals Google Scholar
Hökelek, T., Dal, H., Tercan, B., Aybirdi, Ö. & Necefoğlu, H. (2009b). Acta Cryst. E65, m651–m652. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Saka, G., Tercan, B., Tenlik, E. & Necefoğlu, H. (2010b). Acta Cryst. E66, m1135–m1136. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hökelek, T., Süzen, Y., Tercan, B., Tenlik, E. & Necefoğlu, H. (2010a). Acta Cryst. E66, m784–m785. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krishnamachari, K. A. V. R. (1974). Am. J. Clin. Nutr. 27, 108–111. CAS PubMed Web of Science Google Scholar
Necefoğlu, H., Özbek, F. E., Öztürk, V., Adıgüzel, V. & Hökelek, T. (2011b). Acta Cryst. E67, m1128–m1129. Web of Science CSD CrossRef IUCr Journals Google Scholar
Necefoğlu, H., Özbek, F. E., Öztürk, V., Tercan, B. & Hökelek, T. (2011a). Acta Cryst. E67, m887–m888. Web of Science CSD CrossRef IUCr Journals 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

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