metal-organic compounds
catena-Poly[[aquabis(4-formylbenzoato-κ2O1,O1′)cadmium]-μ-pyrazine-κ2N:N′]
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
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 CdII cations, forming polymeric chains running along the b-axis direction. In the crystal, O—Hwater ⋯ Ocarboxylate hydrogen bonds link adjacent chains into layers parallel to the bc plane. These layers are linked via C—Hpyrazine ⋯ Oformyl hydrogen bonds, forming a three-dimensional network. π–π interactions [centroid–centroid distances = 3.870 (11)–3.951 (5) Å] further stabilize the 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
|
Data collection: APEX2 (Bruker, 2012); cell 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
10.1107/S1600536813035010/su2679sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813035010/su2679Isup2.hkl
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.
Atoms H71 and H72 (for H2O) were located in a difference and refined with a distance restraint: 0-H = 0.82 (2) Å and H···H = 1.35 (2) Å with Uiso(H) = 1.5Ueq(O). The C-bound H-atoms were positioned geometrically and constrained to ride on their parent atom: C—H = 0.93 Å with Uiso(H) = 1.2Ueq(C). In one of the two FB anions, the O atom, O6, the aldehyde H atom, H16, and the benzene ring B (C10—C15) are disordered over two positions. The O atoms (O6A and O6B) were freely refined [ratio 0.79 (2):0.21 (2)]. The aldehyde H atoms (H16A and H16B) were refined with a fixed occupancy ratio of 0.8:0.2. The benzene ring atoms [(C11A, H11A, C12A, H12A, C14A, H14A, C15A, H15A) and (C11B, H11B, C12B, H12B, C14B, H14B, C15B, H15B)] were refined with a fixed occupancy ratio of 0.5:0.5.
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
is reported on herein.The
of the title polymeric compound contains one CdII 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 CdII ions forming polymeric chains running along the b-axis direction (Fig. 2). The distances between the symmetry related CdII 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–Hwater ··· Ocarboxylate hydrogen bonds (Table 1) link adjacent chains into layers parallel to the bc plane. The layers are linked via C–Hpyrazine ··· Oformyl 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).
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).
Data collection: APEX2 (Bruker, 2012); cell
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).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. |
[Cd(C8H5O3)2(C4H4N2)(H2O)] | F(000) = 1016 |
Mr = 508.76 | Dx = 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 |
Bruker SMART BREEZE CCD diffractometer | 3587 independent reflections |
Radiation source: fine-focus sealed tube | 3497 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
φ and ω scans | θmax = 25.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | h = −27→27 |
Tmin = 0.625, Tmax = 0.842 | k = −8→8 |
40178 measured reflections | l = −14→14 |
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(Fo2) + (0.0316P)2 + 14.8406P] where P = (Fo2 + 2Fc2)/3 |
3587 reflections | (Δ/σ)max < 0.001 |
287 parameters | Δρmax = 1.77 e Å−3 |
3 restraints | Δρmin = −1.85 e Å−3 |
[Cd(C8H5O3)2(C4H4N2)(H2O)] | V = 1990.38 (9) Å3 |
Mr = 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)° |
Bruker SMART BREEZE CCD diffractometer | 3587 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2012) | 3497 reflections with I > 2σ(I) |
Tmin = 0.625, Tmax = 0.842 | Rint = 0.048 |
40178 measured reflections |
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(Fo2) + (0.0316P)2 + 14.8406P] where P = (Fo2 + 2Fc2)/3 |
3587 reflections | Δρmax = 1.77 e Å−3 |
287 parameters | Δρmin = −1.85 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | 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* |
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) |
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. |
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···O6Aiv | 0.93 | 2.52 | 3.394 (14) | 157 |
C19—H19···O3v | 0.93 | 2.43 | 3.085 (10) | 127 |
C8—H8···Cg1vi | 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. |
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···Cg1iv | 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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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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 CdII 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 CdII ions forming polymeric chains running along the b-axis direction (Fig. 2). The distances between the symmetry related CdII 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–Hwater ··· Ocarboxylate hydrogen bonds (Table 1) link adjacent chains into layers parallel to the bc plane. The layers are linked via C–Hpyrazine ··· Oformyl 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).