Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810046258/xu5083sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536810046258/xu5083Isup2.hkl |
CCDC reference: 802982
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.003 Å
- R factor = 0.024
- wR factor = 0.061
- Data-to-parameter ratio = 17.2
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Cd1 -- O3 .. 10.70 su
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 3.70 PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.14 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Uiso(max)/Uso(min) ... 5.26 Ratio PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cd1 -- O1 .. 9.66 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cd1 -- O4 .. 8.38 su PLAT420_ALERT_2_C D-H Without Acceptor N3 - H3A ... ? PLAT420_ALERT_2_C D-H Without Acceptor N4 - H4A ... ? PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 13 PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density 1.74 eA-3 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 50
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1 PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cd1 ....... 1.99
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 10 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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.
Atoms H3A, H4A (for NH), H2A, H2B (for NH2) and H61, H62 (for H2O) were located in a difference Fourier map and refined isotropically. The remaining H atoms were positioned geometrically with C—H = 0.93 and 0.96 Å for aromatic and methyl H atoms and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for aromatic H atoms.
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 CdII 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).
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).
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).
[Cd2(C8H8NO2)4(C6H6N2O)2(H2O)2] | Z = 1 |
Mr = 1105.72 | F(000) = 560 |
Triclinic, P1 | Dx = 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 |
Bruker Kappa APEXII CCD area-detector diffractometer | 5581 independent reflections |
Radiation source: fine-focus sealed tube | 5250 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
φ and ω scans | θmax = 28.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −12→12 |
Tmin = 0.734, Tmax = 0.901 | k = −13→13 |
20025 measured reflections | l = −17→16 |
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(Fo2) + (0.0294P)2 + 0.9733P] where P = (Fo2 + 2Fc2)/3 |
5581 reflections | (Δ/σ)max < 0.001 |
324 parameters | Δρmax = 1.77 e Å−3 |
1 restraint | Δρmin = −0.48 e Å−3 |
[Cd2(C8H8NO2)4(C6H6N2O)2(H2O)2] | γ = 67.172 (2)° |
Mr = 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)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 5581 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 5250 reflections with I > 2σ(I) |
Tmin = 0.734, Tmax = 0.901 | Rint = 0.023 |
20025 measured reflections |
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 | Δρmax = 1.77 e Å−3 |
5581 reflections | Δρmin = −0.48 e Å−3 |
324 parameters |
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 | ||
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) |
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) |
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. |
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···O2iv | 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···O2iv | 0.93 | 2.45 | 3.252 (3) | 145 |
C19—H19···Cg3v | 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] |
Mr | 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) |
Tmin, Tmax | 0.734, 0.901 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20025, 5581, 5250 |
Rint | 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 |
Δρmax, Δρmin (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).
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. |
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···O2iv | 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···O2iv | 0.93 | 2.45 | 3.252 (3) | 145 |
C19—H19···Cg3v | 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. |
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 CdII 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).