catena-Poly[[aqua­bis­(4-formyl­benzoato-κ2O1,O1′)cadmium]-μ-pyrazine-κ2N:N′]

Çelik, F.; Dilek, N.; Çaylak Delibaş, N.; Necefoğlu, H.; Hökelek, T.

doi:10.1107/S1600536813035010

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Pages m37-m38

doi:10.1107/S1600536813035010

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catena-Poly[[aquabis(4-formylbenzoato-κ²O¹,O^1′)cadmium]-μ-pyrazine-κ²N:N′]

Fatih Çelik,^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 26 December 2013; accepted 31 December 2013; online 11 January 2014)

The polymeric title compound, [Cd(C₈H₅O₃)₂(C₄H₄N₂)(H₂O)]_n, contains two 4-formylbenzoate (FB) anions, one pyrazine molecule and one coordinating water molecule; the FB anions act as bidentate ligands. The O atom, the aldehyde H atom and the benzene ring of one of the FB anions are disordered over two positions. The O atoms were freely refined [refined occupancy ratio 0.79 (2):0.21 (2)], while the aldehyde H atoms and the benzene ring atoms were refined with fixed occupancy ratios of 0.8:0.2 and 0.5:0.5, respectively. In the ordered FB anion, the carboxylate group is twisted away from the attached benzene ring (A) by 22.7 (8)°. In the disordered FB anion, the corresponding angles are 15.6 (10) and 11.4 (11)° for rings B and B′, respectively. Benzene rings A and B are oriented at a dihedral angle of 24.2 (7), A and B′ at 43.0 (8)°. The pyrazine ring makes dihedral angles of 67.5 (4), 89.6 (7) and 86.2 (7)°, respectively, with benzene rings A, B and B′. The pyrazine ligands bridge the Cd^II cations, forming polymeric chains running along the b-axis direction. In the crystal, O—H_water ⋯ O_carboxylate hydrogen bonds link adjacent chains into layers parallel to the bc plane. These layers are linked via C—H_pyrazine ⋯ O_formyl hydrogen bonds, forming a three-dimensional network. π–π interactions [centroid–centroid distances = 3.870 (11)–3.951 (5) Å] further stabilize the crystal structure. There is also a weak C—H⋯π interaction present.

CCDC reference: 979254

Related literature

For structural functions and coordination relationships of the arylcarboxylate ion in transition metal complexes of benzoic acid derivatives, see: Nadzhafov et al. (1981 ); Shnulin et al. (1981 ). For applications of transition metal complexes with biochemical molecules in biological systems, see: Antolini et al. (1982 ). Some benzoic acid derivatives such as 4-aminobenzoic acid have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes, see: Chen & Chen (2002 ); Amiraslanov et al. (1979 ); Hauptmann et al. (2000 ). For related structures, see: Hökelek et al. (2009 ); Sertçelik et al. (2013 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Cd(C₈H₅O₃)₂(C₄H₄N₂)(H₂O)]
M_r = 508.76
Monoclinic, P 2₁ /c
a = 22.6016 (5) Å
b = 7.4947 (2) Å
c = 11.9196 (3) Å
β = 99.673 (4)°
V = 1990.38 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.14 mm⁻¹
T = 294 K
0.45 × 0.35 × 0.15 mm

Data collection

Bruker SMART BREEZE CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2012 ) T_min = 0.625, T_max = 0.842
40178 measured reflections
3587 independent reflections
3497 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.144
S = 1.35
3587 reflections
287 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.77 e Å⁻³
Δρ_min = −1.85 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the pyrazine ring N1/N2/C17—C20.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H72⋯O5ⁱ	0.82 (2)	2.10 (6)	2.727 (7)	133 (7)
C18—H18⋯O6Aⁱⁱ	0.93	2.52	3.394 (14)	157
C19—H19⋯O3ⁱⁱⁱ	0.93	2.43	3.085 (10)	127
C8—H8⋯Cg1^iv	0.93	2.93	3.691 (10)	147
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 publication routines (Farrugia, 2012) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 979254

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813035010/su2679sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813035010/su2679Isup2.hkl

checkCIF report

Comment top

The structural functions and coordination relationships of the arylcarboxylate ion in transition metal complexes of benzoic acid derivatives change depending on the nature and position of the substituent groups on the benzene ring, the nature of the additional ligand molecule or solvent, and the medium of the synthesis (Nadzhafov et al., 1981; Shnulin et al., 1981). Transition metal complexes with biochemically active ligands frequently show interesting physical and/or chemical properties, as a result they may find applications in biological systems (Antolini et al., 1982). Some benzoic acid derivatives, such as 4-aminobenzoic acid, have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes (Chen & Chen, 2002; Amiraslanov et al., 1979; Hauptmann et al., 2000). The title compound was synthesized and its crystal structure is reported on herein.

The asymmetric unit of the title polymeric compound contains one Cd^II ion, two 4-formylbenzoate (FB) anions, one pyrazine molecule and one coordinated water molecule; the FB anions act as bidentate ligands (Fig. 1). The pyrazine ligands bridge the adjacent Cd^II ions forming polymeric chains running along the b-axis direction (Fig. 2). The distances between the symmetry related Cd^II ions [Cd1 ···Cd1ⁱ; symmetry code (i) = x, y + 1, z] is 7.495 (3) Å.

The O1—Cd1—O2 and O4—Cd1—O5 angles are 53.89 (17)° and 53.88 (18) °, respectively. The corresponding O—M—O (M = metal) angles are 52.91 (4)° and 53.96 (4)° in [Cd(C₈H₅O₃)₂(C₆H₆N₂O)₂(H₂O)].H₂O (Hökelek et al., 2009) and 53.50 (14)° in [Cu₂(C₈H₅O₃)₄(C₆H₆N₂O)₄] (Sertçelik et al., 2013).

The near equality of the C1—O1 [1.262 (9) Å], C1—O2 [1.234 (9) Å] and C9—O4 [1.242 (9) Å], C9—O5 [1.247 (9) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The average Cd—O and Cd—N distances are 2.373 (5) and 2.307 (6) Å, respectively, close to standard values (Allen et al., 1987). The Cd atom lies 0.0175 (5) Å and 0.0153 (4) Å below of the carboxylate groups [(O1/O2/C1) and (O4/O5/C9)], respectively. The dihedral angles between the planar carboxylate groups [(O1/O2/C1) and (O4/O5/C9)] and the adjacent benzene rings [A (C2—C7), B (C10/C11A,C12A,C13/C14A/C15A) and B' (C10/C11B/C12B/C13/C14B/C15B)] are 22.7 (8) and 15.6 (10) and 11.4 (11) °, respectively, while the benzene rings, A to B and A to B', are oriented at dihedral angles of 24.2 (7) and 43.0 (8) °, respectively. On the other hand, the pyrazine ring C (N1/N2/C17—C20) is oriented with respect to benzene rings A, B and B' at dihedral angles of 67.5 (4), 89.6 (7) and 86.2 (7) °, respectively.

In the crystal, O–H_water ··· O_carboxylate hydrogen bonds (Table 1) link adjacent chains into layers parallel to the bc plane. The layers are linked via C–H_pyrazine ··· O_formyl hydrogen bonds (Table 1), forming a three-dimensional network.

There is a slipped parallel π-π contact between inversion related benzene rings, A···Aⁱ, with a centroid-centroid distance of 3.951 (5) Å [normal distance 3.581 (4) Å, slippage 1.668 Å; symmetry code: (i) - x +1, - y, - z +1], and π-π interactions between the disordered benzene rings, B···Bⁱⁱ and B'···B'ⁱⁱ with centroid-centroid distances of 3.870 (11) and 3.873 (12) Å, respectively [symmetry code: (ii) -x, y+1/2, -z+1/2] . There is also a weak C—H···π interaction present (Table 1).

Related literature top

For structural functions and coordination relationships of the arylcarboxylate ion in transition metal complexes of benzoic acid derivatives, see: Nadzhafov et al. (1981); Shnulin et al. (1981). For applications of transition metal complexes with biochemical molecules in biological systems, see: Antolini et al. (1982). Some benzoic acid derivatives such as 4-aminobenzoic acid have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes, see: Chen & Chen (2002); Amiraslanov et al. (1979); Hauptmann et al. (2000). For related structures, see: Hökelek et al. (2009); Sertçelik et al. (2013). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by the reaction of CdSO₄.8/3H₂O (1.28 g, 5 mmol) in H₂O (50 ml) and pyrazine (0.80 g, 10 mmol) in H₂O (30 ml) with sodium 4-formylbenzoate (1.72 g, 10 mmol) in H₂O (50 ml). The mixture was filtered and set aside to crystallize at ambient temperature for several days, giving plate-like colourless single crystals.

Structure description top

For structural functions and coordination relationships of the arylcarboxylate ion in transition metal complexes of benzoic acid derivatives, see: Nadzhafov et al. (1981); Shnulin et al. (1981). For applications of transition metal complexes with biochemical molecules in biological systems, see: Antolini et al. (1982). Some benzoic acid derivatives such as 4-aminobenzoic acid have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes, see: Chen & Chen (2002); Amiraslanov et al. (1979); Hauptmann et al. (2000). For related structures, see: Hökelek et al. (2009); Sertçelik et al. (2013). For bond-length data, see: Allen et al. (1987).

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 publication routines (Farrugia, 2012) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The asymmetric unit of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Part of the polymeric chain of the title compound. Only the water H atoms and the major components of the disordered aldehyde and benzene ring are shown.

catena-Poly[[aquabis(4-formylbenzoato-κ²O¹,O^1')cadmium]-µ-pyrazine-κ²N:N'] top

Crystal data top

[Cd(C₈H₅O₃)₂(C₄H₄N₂)(H₂O)]	F(000) = 1016
M_r = 508.76	D_x = 1.684 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9816 reflections
a = 22.6016 (5) Å	θ = 2.7–28.4°
b = 7.4947 (2) Å	µ = 1.14 mm⁻¹
c = 11.9196 (3) Å	T = 294 K
β = 99.673 (4)°	Plate, colourless
V = 1990.38 (9) Å³	0.45 × 0.35 × 0.15 mm
Z = 4

Data collection top

Bruker SMART BREEZE CCD diffractometer	3587 independent reflections
Radiation source: fine-focus sealed tube	3497 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
φ and ω scans	θ_max = 25.3°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −27→27
T_min = 0.625, T_max = 0.842	k = −8→8
40178 measured reflections	l = −14→14

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.35	w = 1/[σ²(F_o²) + (0.0316P)² + 14.8406P] where P = (F_o² + 2F_c²)/3
3587 reflections	(Δ/σ)_max < 0.001
287 parameters	Δρ_max = 1.77 e Å⁻³
3 restraints	Δρ_min = −1.85 e Å⁻³

Crystal data top

[Cd(C₈H₅O₃)₂(C₄H₄N₂)(H₂O)]	V = 1990.38 (9) Å³
M_r = 508.76	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 22.6016 (5) Å	µ = 1.14 mm⁻¹
b = 7.4947 (2) Å	T = 294 K
c = 11.9196 (3) Å	0.45 × 0.35 × 0.15 mm
β = 99.673 (4)°

Data collection top

Bruker SMART BREEZE CCD diffractometer	3587 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2012)	3497 reflections with I > 2σ(I)
T_min = 0.625, T_max = 0.842	R_int = 0.048
40178 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	3 restraints
wR(F²) = 0.144	H atoms treated by a mixture of independent and constrained refinement
S = 1.35	w = 1/[σ²(F_o²) + (0.0316P)² + 14.8406P] where P = (F_o² + 2F_c²)/3
3587 reflections	Δρ_max = 1.77 e Å⁻³
287 parameters	Δρ_min = −1.85 e Å⁻³

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	Occ. (<1)
Cd1	0.25229 (2)	0.17641 (6)	0.12918 (4)	0.02711 (18)
O1	0.3237 (2)	0.1914 (8)	0.2983 (4)	0.0451 (13)
O2	0.3601 (2)	0.1504 (9)	0.1430 (5)	0.0567 (16)
O3	0.6257 (4)	0.2685 (15)	0.5777 (8)	0.105 (3)
O4	0.1447 (2)	0.1687 (9)	0.0798 (5)	0.0551 (16)
O5	0.1829 (2)	0.1597 (8)	0.2594 (5)	0.0503 (15)
O6A	−0.1449 (4)	0.134 (2)	0.2280 (11)	0.124 (6)	0.79 (2)
O6B	−0.111 (2)	0.139 (9)	0.378 (6)	0.16 (3)	0.21 (2)
O7	0.2521 (2)	0.1713 (7)	−0.0625 (4)	0.0362 (11)
H71	0.263 (3)	0.278 (4)	−0.054 (7)	0.056*
H72	0.221 (2)	0.168 (9)	−0.109 (6)	0.056*
N1	0.2519 (2)	0.4797 (9)	0.1242 (4)	0.0299 (13)
N2	0.2503 (2)	0.8645 (6)	0.1216 (5)	0.0263 (11)
C1	0.3678 (3)	0.1700 (9)	0.2472 (6)	0.0330 (15)
C2	0.4297 (3)	0.1712 (9)	0.3143 (6)	0.0304 (14)
C3	0.4421 (3)	0.2522 (11)	0.4201 (6)	0.0406 (17)
H3	0.4112	0.3025	0.4521	0.049*
C4	0.5005 (4)	0.2584 (12)	0.4780 (6)	0.047 (2)
H4	0.5089	0.3158	0.5480	0.056*
C5	0.5460 (3)	0.1806 (12)	0.4330 (7)	0.047 (2)
C6	0.5336 (4)	0.0950 (14)	0.3294 (8)	0.059 (2)
H6	0.5645	0.0402	0.2996	0.071*
C7	0.4760 (3)	0.0897 (12)	0.2694 (7)	0.0452 (19)
H7	0.4681	0.0321	0.1993	0.054*
C8	0.6082 (4)	0.1889 (19)	0.4960 (10)	0.082 (4)
H8	0.6366	0.1221	0.4662	0.099*
C9	0.1387 (3)	0.1613 (9)	0.1813 (6)	0.0335 (15)
C10	0.0767 (3)	0.1475 (10)	0.2111 (6)	0.0351 (16)
C13	−0.0386 (4)	0.1296 (14)	0.2620 (8)	0.054 (2)
C11A	0.0653 (14)	0.171 (3)	0.320 (3)	0.050 (4)	0.50
H11A	0.0972	0.1880	0.3797	0.060*	0.50
C12A	0.0074 (12)	0.170 (3)	0.342 (2)	0.050 (4)	0.50
H12A	0.0005	0.1985	0.4151	0.060*	0.50
C14A	−0.0278 (12)	0.089 (3)	0.153 (2)	0.050 (4)	0.50
H14A	−0.0592	0.0529	0.0966	0.060*	0.50
C15A	0.0301 (13)	0.104 (3)	0.128 (3)	0.050 (4)	0.50
H15A	0.0369	0.0829	0.0548	0.060*	0.50
C11B	0.0702 (14)	0.106 (4)	0.319 (3)	0.057 (5)	0.50
H11B	0.1038	0.0856	0.3747	0.068*	0.50
C12B	0.0126 (12)	0.093 (3)	0.348 (2)	0.057 (5)	0.50
H12B	0.0076	0.0606	0.4208	0.068*	0.50
C14B	−0.0305 (12)	0.171 (3)	0.153 (2)	0.057 (5)	0.50
H14B	−0.0635	0.1966	0.0976	0.068*	0.50
C15B	0.0255 (13)	0.174 (3)	0.126 (3)	0.057 (5)	0.50
H15B	0.0303	0.1945	0.0515	0.068*	0.50
C16	−0.0996 (5)	0.1259 (19)	0.2908 (12)	0.081 (3)
H16A	−0.1021	0.1161	0.3677	0.097*	0.80
H16B	−0.1313	0.1104	0.2310	0.097*	0.20
C17	0.2264 (3)	0.5861 (11)	0.0310 (7)	0.0441 (18)
H17	0.2087	0.5283	−0.0352	0.053*
C18	0.2260 (3)	0.7705 (9)	0.0313 (6)	0.0391 (17)
H18	0.2080	0.8306	−0.0339	0.047*
C19	0.2755 (3)	0.7728 (10)	0.2113 (6)	0.0381 (17)
H19	0.2933	0.8340	0.2762	0.046*
C20	0.2764 (3)	0.5877 (9)	0.2121 (6)	0.0375 (16)
H20	0.2954	0.5323	0.2783	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.0334 (3)	0.0204 (3)	0.0268 (3)	−0.00118 (19)	0.00312 (19)	−0.00010 (18)
O1	0.031 (3)	0.060 (4)	0.045 (3)	0.007 (2)	0.007 (2)	−0.010 (3)
O2	0.042 (3)	0.092 (5)	0.035 (3)	−0.008 (3)	0.002 (2)	−0.001 (3)
O3	0.068 (5)	0.147 (9)	0.084 (6)	−0.017 (5)	−0.030 (4)	0.003 (6)
O4	0.036 (3)	0.087 (5)	0.043 (3)	0.002 (3)	0.008 (2)	0.009 (3)
O5	0.034 (3)	0.071 (4)	0.045 (3)	−0.006 (3)	0.001 (2)	−0.021 (3)
O6A	0.036 (6)	0.233 (17)	0.102 (10)	0.008 (7)	0.013 (5)	0.026 (10)
O6B	0.10 (4)	0.21 (7)	0.20 (7)	0.00 (4)	0.10 (4)	0.04 (5)
O7	0.044 (3)	0.037 (3)	0.027 (2)	0.000 (2)	0.004 (2)	0.002 (2)
N1	0.010 (2)	0.068 (4)	0.011 (2)	0.000 (2)	−0.0008 (17)	−0.005 (3)
N2	0.035 (3)	0.006 (2)	0.038 (3)	0.002 (2)	0.003 (2)	−0.001 (2)
C1	0.035 (4)	0.023 (4)	0.041 (4)	−0.001 (3)	0.004 (3)	0.002 (3)
C2	0.035 (3)	0.024 (3)	0.033 (3)	−0.003 (3)	0.007 (3)	0.004 (3)
C3	0.039 (4)	0.048 (5)	0.037 (4)	0.003 (3)	0.012 (3)	−0.008 (3)
C4	0.047 (4)	0.060 (6)	0.031 (4)	−0.007 (4)	0.000 (3)	−0.006 (4)
C5	0.034 (4)	0.057 (5)	0.050 (5)	−0.001 (4)	0.001 (3)	0.010 (4)
C6	0.038 (4)	0.078 (7)	0.064 (6)	0.008 (4)	0.014 (4)	−0.006 (5)
C7	0.040 (4)	0.054 (5)	0.043 (4)	0.003 (4)	0.012 (3)	−0.008 (4)
C8	0.042 (5)	0.123 (11)	0.075 (7)	−0.004 (6)	−0.011 (5)	0.002 (7)
C9	0.037 (4)	0.021 (3)	0.042 (4)	0.001 (3)	0.006 (3)	−0.004 (3)
C10	0.034 (4)	0.035 (4)	0.034 (4)	−0.002 (3)	0.002 (3)	−0.003 (3)
C13	0.041 (4)	0.068 (6)	0.057 (5)	0.002 (4)	0.013 (4)	−0.006 (5)
C11A	0.039 (6)	0.070 (11)	0.042 (6)	0.009 (8)	0.006 (4)	0.002 (8)
C12A	0.039 (6)	0.070 (11)	0.042 (6)	0.009 (8)	0.006 (4)	0.002 (8)
C14A	0.039 (6)	0.070 (11)	0.042 (6)	0.009 (8)	0.006 (4)	0.002 (8)
C15A	0.039 (6)	0.070 (11)	0.042 (6)	0.009 (8)	0.006 (4)	0.002 (8)
C11B	0.039 (6)	0.089 (14)	0.040 (6)	0.012 (10)	0.002 (4)	0.004 (10)
C12B	0.039 (6)	0.089 (14)	0.040 (6)	0.012 (10)	0.002 (4)	0.004 (10)
C14B	0.039 (6)	0.089 (14)	0.040 (6)	0.012 (10)	0.002 (4)	0.004 (10)
C15B	0.039 (6)	0.089 (14)	0.040 (6)	0.012 (10)	0.002 (4)	0.004 (10)
C16	0.055 (7)	0.117 (10)	0.075 (7)	−0.005 (6)	0.023 (6)	0.002 (7)
C17	0.045 (4)	0.036 (4)	0.047 (4)	−0.004 (3)	−0.003 (3)	−0.013 (3)
C18	0.049 (4)	0.022 (4)	0.041 (4)	−0.005 (3)	−0.007 (3)	0.005 (3)
C19	0.056 (5)	0.026 (4)	0.030 (4)	−0.011 (3)	−0.002 (3)	0.002 (3)
C20	0.051 (4)	0.023 (4)	0.037 (4)	−0.001 (3)	0.004 (3)	0.006 (3)

Geometric parameters (Å, º) top

Cd1—N1	2.274 (6)	C6—H6	0.9300
Cd1—O7	2.284 (5)	C7—H7	0.9300
Cd1—N2ⁱ	2.340 (5)	C8—H8	0.9300
Cd1—O1	2.364 (5)	C9—C10	1.505 (10)
Cd1—O5	2.388 (5)	C10—C15A	1.36 (3)
Cd1—O4	2.405 (5)	C10—C11B	1.36 (3)
Cd1—O2	2.423 (6)	C10—C11A	1.38 (3)
Cd1—C9	2.744 (7)	C10—C15B	1.42 (3)
Cd1—C1	2.750 (7)	C13—C12A	1.33 (3)
O1—C1	1.262 (9)	C13—C14B	1.38 (3)
O2—C1	1.234 (9)	C13—C14A	1.40 (3)
O3—C8	1.154 (14)	C13—C12B	1.44 (3)
O4—C9	1.242 (9)	C13—C16	1.475 (13)
O5—C9	1.247 (9)	C11A—C12A	1.38 (3)
O6A—C16	1.165 (15)	C11A—H11A	0.9300
O6A—H16B	0.3504	C12A—H12A	0.9300
O6B—C16	1.12 (6)	C14A—C15A	1.39 (3)
O7—H71	0.83 (2)	C14A—H14A	0.9300
O7—H72	0.82 (2)	C15A—H15A	0.9300
N1—C20	1.365 (9)	C11B—C12B	1.40 (3)
N1—C17	1.410 (10)	C11B—H11B	0.9300
N2—C19	1.318 (9)	C12B—H12B	0.9300
N2—C18	1.326 (9)	C14B—C15B	1.36 (3)
N2—Cd1ⁱⁱ	2.340 (5)	C14B—H14B	0.9300
C1—C2	1.491 (9)	C15B—H15B	0.9300
C2—C3	1.385 (10)	C16—H16A	0.9300
C2—C7	1.394 (10)	C16—H16B	0.9300
C3—C4	1.383 (11)	C17—C18	1.382 (11)
C3—H3	0.9300	C17—H17	0.9300
C4—C5	1.368 (12)	C18—H18	0.9300
C4—H4	0.9300	C19—C20	1.387 (10)
C5—C6	1.378 (12)	C19—H19	0.9300
C5—C8	1.479 (12)	C20—H20	0.9300
C6—C7	1.376 (11)

N1—Cd1—O7	89.51 (17)	C6—C7—H7	120.2
N1—Cd1—N2ⁱ	176.30 (17)	C2—C7—H7	120.2
O7—Cd1—N2ⁱ	87.02 (18)	O3—C8—C5	127.7 (12)
N1—Cd1—O1	88.49 (18)	O3—C8—H8	116.1
O7—Cd1—O1	137.71 (18)	C5—C8—H8	116.1
N2ⁱ—Cd1—O1	94.94 (19)	O4—C9—O5	121.6 (7)
N1—Cd1—O5	93.98 (19)	O4—C9—C10	119.4 (6)
O7—Cd1—O5	139.32 (18)	O5—C9—C10	119.0 (6)
N2ⁱ—Cd1—O5	87.8 (2)	O4—C9—Cd1	61.2 (4)
O1—Cd1—O5	82.94 (17)	O5—C9—Cd1	60.4 (4)
N1—Cd1—O4	91.1 (2)	C10—C9—Cd1	178.3 (5)
O7—Cd1—O4	85.57 (18)	C15A—C10—C11B	116 (2)
N2ⁱ—Cd1—O4	87.4 (2)	C15A—C10—C11A	118.0 (17)
O1—Cd1—O4	136.69 (18)	C11B—C10—C15B	120.2 (17)
O5—Cd1—O4	53.88 (18)	C11A—C10—C15B	113.1 (19)
N1—Cd1—O2	94.7 (2)	C15A—C10—C9	119.1 (14)
O7—Cd1—O2	84.23 (18)	C11B—C10—C9	119.6 (14)
N2ⁱ—Cd1—O2	86.3 (2)	C11A—C10—C9	122.9 (15)
O1—Cd1—O2	53.89 (17)	C15B—C10—C9	120.3 (14)
O5—Cd1—O2	135.59 (18)	C12A—C13—C14B	114.6 (19)
O4—Cd1—O2	168.3 (2)	C12A—C13—C14A	119.0 (16)
N1—Cd1—C9	92.74 (18)	C14B—C13—C12B	119.6 (15)
O7—Cd1—C9	112.4 (2)	C14A—C13—C12B	112.0 (17)
N2ⁱ—Cd1—C9	87.41 (19)	C12A—C13—C16	119.1 (14)
O1—Cd1—C9	109.87 (19)	C14B—C13—C16	120.2 (14)
O5—Cd1—C9	26.99 (19)	C14A—C13—C16	122.0 (14)
O4—Cd1—C9	26.9 (2)	C12B—C13—C16	120.2 (14)
O2—Cd1—C9	161.8 (2)	C12A—C11A—C10	121 (2)
N1—Cd1—C1	91.69 (18)	C12A—C11A—H11A	119.5
O7—Cd1—C1	110.7 (2)	C10—C11A—H11A	119.5
N2ⁱ—Cd1—C1	90.73 (19)	C13—C12A—C11A	121.2 (19)
O1—Cd1—C1	27.25 (19)	C13—C12A—H12A	119.4
O5—Cd1—C1	109.70 (19)	C11A—C12A—H12A	119.4
O4—Cd1—C1	163.5 (2)	C15A—C14A—C13	119.6 (18)
O2—Cd1—C1	26.64 (19)	C15A—C14A—H14A	120.2
C9—Cd1—C1	136.7 (2)	C13—C14A—H14A	120.2
C1—O1—Cd1	93.7 (4)	C10—C15A—C14A	121 (2)
C1—O2—Cd1	91.7 (4)	C10—C15A—H15A	119.6
C9—O4—Cd1	91.9 (4)	C14A—C15A—H15A	119.6
C9—O5—Cd1	92.6 (4)	C10—C11B—C12B	120 (2)
Cd1—O7—H71	85 (6)	C10—C11B—H11B	120.1
Cd1—O7—H72	123 (6)	C12B—C11B—H11B	120.1
H71—O7—H72	108 (3)	C11B—C12B—C13	119.2 (19)
C20—N1—C17	109.2 (6)	C11B—C12B—H12B	120.4
C20—N1—Cd1	125.0 (4)	C13—C12B—H12B	120.4
C17—N1—Cd1	125.8 (4)	C15B—C14B—C13	120.3 (18)
C19—N2—C18	116.5 (5)	C15B—C14B—H14B	119.9
C19—N2—Cd1ⁱⁱ	119.1 (4)	C13—C14B—H14B	119.9
C18—N2—Cd1ⁱⁱ	124.4 (4)	C14B—C15B—C10	121 (2)
O2—C1—O1	120.8 (7)	C14B—C15B—H15B	119.5
O2—C1—C2	120.1 (6)	C10—C15B—H15B	119.5
O1—C1—C2	119.1 (6)	O6B—C16—O6A	106 (3)
O2—C1—Cd1	61.7 (4)	O6B—C16—C13	126 (3)
O1—C1—Cd1	59.1 (4)	O6A—C16—C13	127.2 (13)
C2—C1—Cd1	177.9 (5)	O6A—C16—H16A	116.4
C3—C2—C7	119.5 (7)	C13—C16—H16A	116.4
C3—C2—C1	121.2 (6)	O6B—C16—H16B	117.0
C7—C2—C1	119.3 (6)	C13—C16—H16B	117.0
C4—C3—C2	119.9 (7)	H16A—C16—H16B	125.4
C4—C3—H3	120.0	C18—C17—N1	124.4 (7)
C2—C3—H3	120.0	C18—C17—H17	117.8
C5—C4—C3	120.5 (7)	N1—C17—H17	117.8
C5—C4—H4	119.8	N2—C18—C17	122.0 (7)
C3—C4—H4	119.8	N2—C18—H18	119.0
C4—C5—C6	119.7 (7)	C17—C18—H18	119.0
C4—C5—C8	119.7 (9)	N2—C19—C20	122.1 (7)
C6—C5—C8	120.5 (9)	N2—C19—H19	119.0
C7—C6—C5	120.8 (8)	C20—C19—H19	119.0
C7—C6—H6	119.6	N1—C20—C19	125.7 (7)
C5—C6—H6	119.6	N1—C20—H20	117.1
C6—C7—C2	119.5 (7)	C19—C20—H20	117.1

N1—Cd1—O1—C1	−96.7 (4)	Cd1—O5—C9—O4	0.4 (7)
O7—Cd1—O1—C1	−9.0 (6)	Cd1—O5—C9—C10	178.2 (5)
N2ⁱ—Cd1—O1—C1	82.0 (4)	N1—Cd1—C9—O4	87.0 (5)
O5—Cd1—O1—C1	169.1 (5)	O7—Cd1—C9—O4	−3.6 (5)
O4—Cd1—O1—C1	173.4 (4)	N2ⁱ—Cd1—C9—O4	−89.3 (5)
O2—Cd1—O1—C1	0.2 (4)	O1—Cd1—C9—O4	176.3 (4)
C9—Cd1—O1—C1	171.0 (4)	O5—Cd1—C9—O4	−179.6 (7)
N1—Cd1—O2—C1	84.5 (5)	O2—Cd1—C9—O4	−159.0 (7)
O7—Cd1—O2—C1	173.5 (5)	C1—Cd1—C9—O4	−177.7 (4)
N2ⁱ—Cd1—O2—C1	−99.1 (5)	N1—Cd1—C9—O5	−93.4 (4)
O1—Cd1—O2—C1	−0.2 (4)	O7—Cd1—C9—O5	176.0 (4)
O5—Cd1—O2—C1	−16.1 (6)	N2ⁱ—Cd1—C9—O5	90.3 (4)
O4—Cd1—O2—C1	−156.6 (9)	O1—Cd1—C9—O5	−4.0 (5)
C9—Cd1—O2—C1	−29.3 (10)	O4—Cd1—C9—O5	179.6 (7)
N1—Cd1—O4—C9	−94.0 (5)	O2—Cd1—C9—O5	20.6 (9)
O7—Cd1—O4—C9	176.6 (5)	C1—Cd1—C9—O5	2.0 (6)
N2ⁱ—Cd1—O4—C9	89.4 (5)	O4—C9—C10—C15A	14.6 (15)
O1—Cd1—O4—C9	−5.0 (6)	O5—C9—C10—C15A	−163.3 (13)
O5—Cd1—O4—C9	0.2 (4)	O4—C9—C10—C11B	167.6 (15)
O2—Cd1—O4—C9	146.8 (9)	O5—C9—C10—C11B	−10.3 (16)
C1—Cd1—O4—C9	5.7 (10)	O4—C9—C10—C11A	−167.9 (13)
N1—Cd1—O5—C9	88.2 (4)	O5—C9—C10—C11A	14.2 (15)
O7—Cd1—O5—C9	−5.7 (6)	O4—C9—C10—C15B	−11.1 (16)
N2ⁱ—Cd1—O5—C9	−88.6 (4)	O5—C9—C10—C15B	171.0 (13)
O1—Cd1—O5—C9	176.2 (5)	C15A—C10—C11A—C12A	−7 (2)
O4—Cd1—O5—C9	−0.2 (4)	C11B—C10—C11A—C12A	−97 (8)
O2—Cd1—O5—C9	−171.0 (4)	C15B—C10—C11A—C12A	17 (3)
C1—Cd1—O5—C9	−178.6 (4)	C9—C10—C11A—C12A	175.2 (14)
O7—Cd1—N1—C20	−150.7 (5)	C14B—C13—C12A—C11A	−29 (2)
O1—Cd1—N1—C20	−13.0 (5)	C14A—C13—C12A—C11A	−1 (3)
O5—Cd1—N1—C20	69.8 (5)	C12B—C13—C12A—C11A	79 (5)
O4—Cd1—N1—C20	123.7 (5)	C16—C13—C12A—C11A	178.4 (16)
O2—Cd1—N1—C20	−66.6 (5)	C10—C11A—C12A—C13	7 (3)
C9—Cd1—N1—C20	96.9 (5)	C12A—C13—C14A—C15A	−4 (2)
C1—Cd1—N1—C20	−40.0 (5)	C14B—C13—C14A—C15A	83 (5)
O7—Cd1—N1—C17	29.5 (5)	C12B—C13—C14A—C15A	−30 (2)
O1—Cd1—N1—C17	167.3 (5)	C16—C13—C14A—C15A	176.7 (15)
O5—Cd1—N1—C17	−109.9 (5)	C11B—C10—C15A—C14A	26 (3)
O4—Cd1—N1—C17	−56.0 (5)	C11A—C10—C15A—C14A	2 (2)
O2—Cd1—N1—C17	113.7 (5)	C15B—C10—C15A—C14A	−81 (6)
C9—Cd1—N1—C17	−82.9 (5)	C9—C10—C15A—C14A	179.9 (14)
C1—Cd1—N1—C17	140.2 (5)	C13—C14A—C15A—C10	3 (3)
Cd1—O2—C1—O1	0.4 (7)	C15A—C10—C11B—C12B	−26 (3)
Cd1—O2—C1—C2	−178.8 (5)	C11A—C10—C11B—C12B	75 (7)
Cd1—O1—C1—O2	−0.4 (8)	C15B—C10—C11B—C12B	−1 (3)
Cd1—O1—C1—C2	178.8 (5)	C9—C10—C11B—C12B	180.0 (16)
N1—Cd1—C1—O2	−97.0 (5)	C10—C11B—C12B—C13	−2 (3)
O7—Cd1—C1—O2	−6.9 (5)	C12A—C13—C12B—C11B	−83 (5)
N2ⁱ—Cd1—C1—O2	80.2 (5)	C14B—C13—C12B—C11B	2 (3)
O1—Cd1—C1—O2	179.6 (7)	C14A—C13—C12B—C11B	29 (3)
O5—Cd1—C1—O2	168.1 (5)	C16—C13—C12B—C11B	−176.9 (17)
O4—Cd1—C1—O2	163.5 (7)	C12A—C13—C14B—C15B	28 (3)
C9—Cd1—C1—O2	167.2 (4)	C14A—C13—C14B—C15B	−78 (5)
N1—Cd1—C1—O1	83.4 (4)	C12B—C13—C14B—C15B	1 (3)
O7—Cd1—C1—O1	173.5 (4)	C16—C13—C14B—C15B	−180.0 (17)
N2ⁱ—Cd1—C1—O1	−99.4 (4)	C13—C14B—C15B—C10	−4 (3)
O5—Cd1—C1—O1	−11.5 (5)	C15A—C10—C15B—C14B	90 (7)
O4—Cd1—C1—O1	−16.1 (10)	C11B—C10—C15B—C14B	5 (3)
O2—Cd1—C1—O1	−179.6 (7)	C11A—C10—C15B—C14B	−18 (3)
C9—Cd1—C1—O1	−12.4 (6)	C9—C10—C15B—C14B	−176.8 (16)
O2—C1—C2—C3	157.1 (7)	C12A—C13—C16—O6B	−8 (5)
O1—C1—C2—C3	−22.1 (10)	C14B—C13—C16—O6B	−159 (5)
O2—C1—C2—C7	−22.7 (10)	C14A—C13—C16—O6B	171 (5)
O1—C1—C2—C7	158.2 (7)	C12B—C13—C16—O6B	21 (5)
C7—C2—C3—C4	2.7 (11)	C12A—C13—C16—O6A	160.9 (19)
C1—C2—C3—C4	−177.0 (7)	C14B—C13—C16—O6A	10 (3)
C2—C3—C4—C5	−1.8 (13)	C14A—C13—C16—O6A	−20 (3)
C3—C4—C5—C6	−0.2 (14)	C12B—C13—C16—O6A	−171 (2)
C3—C4—C5—C8	179.8 (9)	C20—N1—C17—C18	−1.0 (10)
C4—C5—C6—C7	1.2 (15)	Cd1—N1—C17—C18	178.8 (6)
C8—C5—C6—C7	−178.8 (10)	C19—N2—C18—C17	0.5 (11)
C5—C6—C7—C2	−0.3 (14)	Cd1ⁱⁱ—N2—C18—C17	179.5 (6)
C3—C2—C7—C6	−1.7 (12)	N1—C17—C18—N2	0.2 (13)
C1—C2—C7—C6	178.0 (8)	C18—N2—C19—C20	−0.3 (11)
C4—C5—C8—O3	−7.4 (19)	Cd1ⁱⁱ—N2—C19—C20	−179.4 (6)
C6—C5—C8—O3	172.6 (13)	C17—N1—C20—C19	1.2 (10)
Cd1—O4—C9—O5	−0.4 (7)	Cd1—N1—C20—C19	−178.6 (6)
Cd1—O4—C9—C10	−178.2 (6)	N2—C19—C20—N1	−0.6 (13)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the pyrazine ring N1/N2/C17—C20.

D—H···A	D—H	H···A	D···A	D—H···A
O7—H72···O5ⁱⁱⁱ	0.82 (2)	2.10 (6)	2.727 (7)	133 (7)
C18—H18···O6A^iv	0.93	2.52	3.394 (14)	157
C19—H19···O3^v	0.93	2.43	3.085 (10)	127
C8—H8···Cg1^vi	0.93	2.93	3.691 (10)	147

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the pyrazine ring N1/N2/C17—C20.

D—H···A	D—H	H···A	D···A	D—H···A
O7—H72···O5ⁱ	0.82 (2)	2.10 (6)	2.727 (7)	133 (7)
C18—H18···O6Aⁱⁱ	0.93	2.52	3.394 (14)	157
C19—H19···O3ⁱⁱⁱ	0.93	2.43	3.085 (10)	127
C8—H8···Cg1^iv	0.93	2.93	3.691 (10)	147

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

Acknowledgements

The authors acknowledge the Aksaray University, Science and Technology Application and Research Center, Aksaray, Turkey, for the use of the Bruker SMART BREEZE CCD diffractometer (purchased under grant No. 2010K120480 of the State of Planning Organization). This work was supported financially by Kafkas University Research Fund (grant No. 2012-FEF-12).

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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Pages m37-m38

doi:10.1107/S1600536813035010

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