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Acta Cryst. (2007). E63, m2323    [ doi:10.1107/S160053680703927X ]

Tetraaquabis(nicotinamide-[kappa]N)cadmium(II) bis(4-formylbenzoate)

Z.-P. Deng, S. Gao and S. W. Ng

Abstract top

The CdII ion in the title compound, [Cd(C6H6N2O)2(H2O)4](C8H5O3)2, lies on a crystallographic inversion centre in a slightly distorted octahedral environment. In the crystal structure, cations and anions interact through intermolecular hydrogen bonds to form a three-dimensional network. The amide group of the cation and the formyl group of the anion are each disordered over two sites, the approximate ratio of occupancies being 0.59:0.41 for both groups.

Comment top

Cadmium bis(4-formylbenzoate) forms a hydrated 1:2 adduct with imidazole; in the crystal structure, two molecules are linked by two Cd—Ocarboxyl interactions into a dinuclear species. The formylbenzoate anion functions in a chelating mode (Deng et al., 2006a). With the larger benzimidazole ligand, a 1:1 aqua adduct is formed, and one carboxylate anion is bidentate whereas the other is monodentate in the seven-coordinate structure (Deng et al., 2006b). Replacing the N-heterocycle by nicotinamide furnishes the title compound as a salt whose cation has two nicotinamide ligands binding to the tetraaquacadmium group; the carboxylate group is displaced from the coordination sphere and it exists as a free anion (Fig. 1). Hydrogen bonds link the cation and anion into a three-dimensional network.

Related literature top

For literature on metal 4-formylbenzoates, see, for example: Deng et al. (2006a,b).

Experimental top

Cadmium diacetate dihydrate (0.133 g, 0.5 mmol) was added to an aqueous solution of 4-formylbenzoic acid (0.15 g, 1 mmol) and nicotinamide (0.122 g, 1 mmol). The pH value of the mixture was about 5. The solution was set aside for the growth of colorless prismatic crystals. CH&N elemental analysis. Calc. for C28H30N4O12Cd: C 46.26, H 4.16, N 7.71%. Found: C 46.24, H 4.11, N 7.76%.

Refinement top

The amido and formyl parts are disordered over two positions; the occupancies refined to a 0.59 (1):0.41 ratio for both groups. The C6—O1 and C6—O1' bond distances were restrained to within 0.01 Å of each other, as were the C6—N1 and C6—N1' distances. The carbon- and nitrogen bound H atoms were generated geometrically (C—H 0.93, N—H 0.86 Å) and were included in the refinement in the riding-model approximation, with U(H) set to 1.2Ueq(C,N). The water H atoms were located in a difference Fourier map, and were refined with a distance restraint of O—H 0.85 (1) Å; their Uiso(H) values were freely refined. The final difference Fourier map had a large peak at about 1 Å from O3, but was otherwise diffuse.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plot of the formula unit of the salt, [(C6H6N2O)2(H2O)4Cd]2+ 2[C8H5O3]−; only the major disorder components is shown. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are drawn as spheres of arbitrary radius. Symmetry code: i = 1 – x, 1 – y, 1 – z.
Tetraaquabis(nicotinamide-κN)cadmium(II) bis(4-formylbenzoate) top
Crystal data top
[Cd(C6H6N2O)2(H2O)4](C8H5O3)2F000 = 740
Mr = 726.96Dx = 1.657 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 10447 reflections
a = 14.922 (1) Åθ = 3.1–27.5º
b = 7.0382 (4) ŵ = 0.82 mm−1
c = 14.030 (1) ÅT = 295 (2) K
β = 98.634 (2)ºPrism, colourless
V = 1456.8 (2) Å30.35 × 0.24 × 0.18 mm
Z = 2
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		3332 independent reflections
Radiation source: fine-focus sealed tube2816 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.035
T = 295(2) Kθmax = 27.5º
ω scansθmin = 3.1º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −19→19
Tmin = 0.680, Tmax = 0.866k = −9→8
13559 measured reflectionsl = −17→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.151  w = 1/[σ2(Fo2) + (0.0584P)2 + 5.994P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.001
3332 reflectionsΔρmax = 1.08 e Å−3
249 parametersΔρmin = −0.46 e Å−3
6 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cd(C6H6N2O)2(H2O)4](C8H5O3)2V = 1456.8 (2) Å3
Mr = 726.96Z = 2
Monoclinic, P21/cMo Kα
a = 14.922 (1) ŵ = 0.82 mm−1
b = 7.0382 (4) ÅT = 295 (2) K
c = 14.030 (1) Å0.35 × 0.24 × 0.18 mm
β = 98.634 (2)º
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		3332 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2816 reflections with I > 2σ(I)
Tmin = 0.680, Tmax = 0.866Rint = 0.035
13559 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0486 restraints
wR(F2) = 0.151H atoms treated by a mixture of
independent and constrained refinement
S = 1.14Δρmax = 1.08 e Å−3
3332 reflectionsΔρmin = −0.46 e Å−3
249 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cd10.50000.50000.50000.03018 (17)
O1W0.4608 (3)0.7588 (6)0.4012 (3)0.0380 (8)
H1W10.415 (2)0.739 (9)0.359 (3)0.042 (16)*
H1W20.498 (3)0.835 (7)0.381 (4)0.046 (18)*
O2W0.5403 (3)0.6836 (6)0.6390 (3)0.0429 (9)
H2W10.550 (4)0.626 (8)0.693 (2)0.047 (17)*
H2W20.503 (3)0.771 (7)0.649 (5)0.053 (19)*
O10.9598 (11)0.607 (3)0.579 (2)0.059 (5)0.589 (12)
N10.8621 (11)0.553 (2)0.6850 (11)0.047 (3)0.589 (12)
H1N10.90560.54240.73250.056*0.589 (12)
H1N20.80680.54080.69450.056*0.589 (12)
O1'0.8628 (13)0.638 (2)0.6856 (12)0.045 (4)0.411 (12)
N1'0.9589 (15)0.547 (5)0.587 (3)0.048 (7)0.411 (12)
H1N31.00320.55480.63380.057*0.411 (12)
H1N40.96870.51330.53070.057*0.411 (12)
O20.3258 (3)0.6507 (8)0.2597 (3)0.0641 (14)
O30.4294 (3)0.5203 (6)0.1818 (3)0.0447 (9)
O40.0030 (5)0.6015 (14)−0.1545 (5)0.061 (3)0.589 (12)
O4'0.1012 (6)0.5493 (16)−0.2424 (6)0.044 (3)0.411 (12)
N20.6443 (3)0.5390 (6)0.4632 (3)0.0329 (9)
C10.6592 (3)0.5775 (7)0.3732 (4)0.0348 (10)
H10.61040.57210.32350.042*
C20.7431 (4)0.6246 (8)0.3510 (3)0.0376 (11)
H20.75040.65530.28810.045*
C30.8166 (3)0.6255 (8)0.4242 (4)0.0352 (10)
H30.87430.65390.41080.042*
C40.8033 (3)0.5835 (7)0.5178 (3)0.0303 (9)
C50.7159 (3)0.5422 (7)0.5338 (3)0.0320 (10)
H50.70650.51540.59640.038*
C60.8796 (3)0.5866 (8)0.6012 (4)0.0388 (11)
C70.3503 (4)0.5841 (8)0.1864 (3)0.0361 (11)
C80.2813 (3)0.5820 (7)0.0956 (3)0.0314 (9)
C90.3067 (4)0.5421 (7)0.0065 (4)0.0361 (11)
H90.36670.51240.00250.043*
C100.2440 (4)0.5460 (8)−0.0759 (4)0.0400 (12)
H100.26250.5257−0.13550.048*
C110.1527 (3)0.5804 (8)−0.0705 (4)0.0360 (10)
C120.1262 (4)0.6195 (8)0.0193 (4)0.0414 (12)
H120.06560.64290.02400.050*
C130.1909 (3)0.6228 (8)0.1008 (4)0.0375 (11)
H130.17370.65270.16010.045*
C140.0842 (4)0.5798 (9)−0.1583 (4)0.0465 (13)
H140.10300.5625−0.21790.056*0.589 (12)
H14'0.02430.6036−0.15100.056*0.411 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0234 (2)0.0379 (3)0.0283 (2)−0.0023 (2)0.00111 (16)0.0026 (2)
O1W0.039 (2)0.040 (2)0.0349 (18)0.0032 (17)0.0037 (15)0.0051 (16)
O2W0.046 (2)0.041 (2)0.039 (2)0.0073 (18)−0.0027 (17)−0.0019 (17)
O10.029 (5)0.090 (15)0.061 (7)−0.017 (6)0.009 (5)−0.013 (10)
N10.030 (4)0.066 (9)0.039 (5)−0.013 (7)−0.009 (4)0.006 (6)
O1'0.041 (6)0.058 (10)0.034 (6)−0.011 (8)0.003 (4)0.006 (7)
N1'0.026 (8)0.058 (16)0.053 (12)0.000 (8)−0.013 (7)−0.008 (11)
O20.058 (3)0.100 (4)0.0311 (19)0.025 (3)−0.0045 (18)−0.005 (2)
O30.045 (2)0.044 (2)0.044 (2)0.0017 (17)−0.0005 (16)−0.0002 (17)
O40.034 (4)0.107 (7)0.039 (4)−0.010 (4)−0.010 (3)−0.007 (4)
O4'0.028 (4)0.075 (7)0.027 (4)0.010 (4)0.000 (3)0.000 (4)
N20.0265 (19)0.037 (2)0.035 (2)−0.0021 (16)0.0027 (16)0.0034 (17)
C10.035 (2)0.035 (2)0.033 (2)0.003 (2)0.0001 (19)−0.002 (2)
C20.043 (3)0.043 (3)0.029 (2)0.007 (2)0.011 (2)−0.001 (2)
C30.030 (2)0.039 (3)0.039 (3)0.000 (2)0.0111 (19)0.001 (2)
C40.025 (2)0.032 (2)0.033 (2)0.0003 (19)0.0017 (17)−0.0002 (19)
C50.029 (2)0.037 (3)0.030 (2)0.0011 (19)0.0039 (18)0.0063 (19)
C60.028 (2)0.043 (3)0.043 (3)−0.003 (2)0.001 (2)0.000 (2)
C70.040 (3)0.040 (3)0.028 (2)−0.002 (2)0.005 (2)0.005 (2)
C80.036 (2)0.027 (2)0.031 (2)−0.004 (2)0.0028 (19)0.0007 (19)
C90.035 (2)0.040 (3)0.034 (2)−0.002 (2)0.009 (2)0.003 (2)
C100.044 (3)0.043 (3)0.033 (2)0.000 (2)0.009 (2)−0.002 (2)
C110.035 (2)0.032 (2)0.040 (3)−0.005 (2)0.003 (2)0.001 (2)
C120.033 (2)0.046 (3)0.045 (3)0.001 (2)0.003 (2)−0.007 (2)
C130.040 (3)0.038 (3)0.035 (2)0.001 (2)0.010 (2)−0.002 (2)
C140.043 (3)0.050 (3)0.045 (3)−0.005 (3)−0.001 (2)−0.003 (3)
Geometric parameters (Å, °) top
Cd1—N22.305 (4)C1—C21.376 (7)
Cd1—N2i2.305 (4)C1—H10.9300
Cd1—O1wi2.311 (4)C2—C31.385 (7)
Cd1—O1w2.311 (4)C2—H20.9300
Cd1—O2w2.342 (4)C3—C41.389 (7)
Cd1—O2wi2.342 (4)C3—H30.9300
O1W—H1W10.85 (1)C4—C51.387 (6)
O1W—H1W20.85 (1)C4—C61.505 (7)
O2W—H2W10.85 (1)C5—H50.9300
O2W—H2W20.85 (1)C7—C81.512 (7)
O1—C61.289 (15)C8—C91.388 (7)
N1—C61.264 (16)C8—C131.392 (7)
N1—H1N10.8600C9—C101.373 (8)
N1—H1N20.8600C9—H90.9300
O1'—C61.299 (15)C10—C111.397 (7)
N1'—C61.259 (19)C10—H100.9300
N1'—H1N30.8600C11—C121.404 (7)
N1'—H1N40.8600C11—C141.477 (7)
O2—C71.235 (6)C12—C131.381 (7)
O3—C71.274 (7)C12—H120.9300
O4—C141.231 (9)C13—H130.9300
O4'—C141.263 (10)C14—H140.9300
N2—C11.342 (6)C14—H14'0.9300
N2—C51.344 (6)
N2—Cd1—N2i180.00 (5)C5—C4—C6119.8 (4)
N2—Cd1—O1Wi93.85 (14)C3—C4—C6122.2 (4)
N2i—Cd1—O1Wi86.15 (14)N2—C5—C4123.2 (4)
N2—Cd1—O1W86.15 (14)N2—C5—H5118.4
N2i—Cd1—O1W93.85 (14)C4—C5—H5118.4
O1Wi—Cd1—O1W180.00 (15)N1'—C6—N1116 (2)
N2—Cd1—O2W89.39 (15)N1—C6—O1125.1 (15)
N2i—Cd1—O2W90.61 (15)N1'—C6—O1'121 (2)
O1Wi—Cd1—O2W85.69 (14)O1—C6—O1'120.1 (15)
O1W—Cd1—O2W94.31 (14)N1'—C6—C4120 (2)
N2—Cd1—O2Wi90.61 (15)N1—C6—C4118.9 (8)
N2i—Cd1—O2Wi89.39 (15)O1—C6—C4115.7 (13)
O1Wi—Cd1—O2Wi94.31 (14)O1'—C6—C4119.0 (9)
O1W—Cd1—O2Wi85.69 (14)O2—C7—O3124.6 (5)
O2W—Cd1—O2Wi180.0O2—C7—C8117.1 (5)
Cd1—O1W—H1W1113 (4)O3—C7—C8118.3 (4)
Cd1—O1W—H1W2126 (4)C9—C8—C13119.0 (5)
H1W1—O1W—H1W2111 (6)C9—C8—C7121.1 (4)
Cd1—O2W—H2W1118 (5)C13—C8—C7119.8 (4)
Cd1—O2W—H2W2116 (5)C10—C9—C8120.7 (5)
H2W1—O2W—H2W2103 (6)C10—C9—H9119.6
C6—N1—H1N1120.0C8—C9—H9119.6
C6—N1—H1N2120.0C9—C10—C11120.3 (5)
H1N1—N1—H1N2120.0C9—C10—H10119.8
C6—N1'—H1N3120.0C11—C10—H10119.8
C6—N1'—H1N4120.0C10—C11—C12119.4 (5)
H1N3—N1'—H1N4120.0C10—C11—C14120.9 (5)
C1—N2—C5117.7 (4)C12—C11—C14119.7 (5)
C1—N2—Cd1121.8 (3)C13—C12—C11119.3 (5)
C5—N2—Cd1120.2 (3)C13—C12—H12120.3
N2—C1—C2123.1 (5)C11—C12—H12120.3
N2—C1—H1118.4C12—C13—C8121.1 (5)
C2—C1—H1118.4C12—C13—H13119.5
C1—C2—C3118.7 (5)C8—C13—H13119.5
C1—C2—H2120.7O4—C14—C11121.8 (6)
C3—C2—H2120.7O4'—C14—C11124.6 (6)
C2—C3—C4119.3 (4)O4—C14—H14119.1
C2—C3—H3120.3C11—C14—H14119.1
C4—C3—H3120.3O4'—C14—H14'117.7
C5—C4—C3118.0 (4)C11—C14—H14'117.7
O1Wi—Cd1—N2—C1137.5 (4)C5—C4—C6—O1173.3 (11)
O1W—Cd1—N2—C1−42.5 (4)C3—C4—C6—O1−8.3 (13)
O2W—Cd1—N2—C1−136.8 (4)C5—C4—C6—O1'−31.8 (11)
O2Wi—Cd1—N2—C143.2 (4)C3—C4—C6—O1'146.6 (9)
O1Wi—Cd1—N2—C5−49.1 (4)O2—C7—C8—C9168.4 (5)
O1W—Cd1—N2—C5130.9 (4)O3—C7—C8—C9−10.6 (7)
O2W—Cd1—N2—C536.6 (4)O2—C7—C8—C13−10.9 (8)
O2Wi—Cd1—N2—C5−143.4 (4)O3—C7—C8—C13170.1 (5)
C5—N2—C1—C2−1.8 (8)C13—C8—C9—C101.2 (8)
Cd1—N2—C1—C2171.7 (4)C7—C8—C9—C10−178.1 (5)
N2—C1—C2—C32.5 (8)C8—C9—C10—C11−3.4 (8)
C1—C2—C3—C4−1.5 (8)C9—C10—C11—C122.9 (8)
C2—C3—C4—C50.0 (8)C9—C10—C11—C14−178.3 (5)
C2—C3—C4—C6−178.5 (5)C10—C11—C12—C13−0.1 (8)
C1—N2—C5—C40.1 (7)C14—C11—C12—C13−179.0 (5)
Cd1—N2—C5—C4−173.5 (4)C11—C12—C13—C8−2.1 (8)
C3—C4—C5—N20.7 (8)C9—C8—C13—C121.6 (8)
C6—C4—C5—N2179.2 (5)C7—C8—C13—C12−179.1 (5)
C5—C4—C6—N1'151.4 (18)C10—C11—C14—O4176.8 (8)
C3—C4—C6—N1'−30.1 (19)C12—C11—C14—O4−4.4 (11)
C5—C4—C6—N1−0.7 (11)C10—C11—C14—O4'0.1 (11)
C3—C4—C6—N1177.7 (9)C12—C11—C14—O4'178.9 (8)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O20.85 (1)1.88 (2)2.715 (6)168 (6)
O1W—H1W2···O3ii0.85 (1)1.98 (1)2.828 (6)172 (6)
O2W—H2W1···O3i0.85 (1)2.02 (1)2.871 (6)178 (7)
O2W—H2W2···O3iii0.85 (1)1.93 (1)2.782 (6)174 (7)
N1—H1N1···O4iv0.862.032.86 (2)163
N1'—H1N3···O4'iv0.862.102.95 (4)173
Symmetry codes: (ii) −x+1, y+1/2, −z+1/2; (i) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z+1/2; (iv) x+1, y, z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W1···O20.85 (1)1.88 (2)2.715 (6)168 (6)
O1W—H1W2···O3i0.85 (1)1.98 (1)2.828 (6)172 (6)
O2W—H2W1···O3ii0.85 (1)2.02 (1)2.871 (6)178 (7)
O2W—H2W2···O3iii0.85 (1)1.93 (1)2.782 (6)174 (7)
N1—H1N1···O4iv0.862.032.86 (2)163
N1'—H1N3···O4'iv0.862.102.95 (4)173
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z+1/2; (iv) x+1, y, z+1.
Acknowledgements top

The authors thank the Heilongjiang Province Natural Science Foundation (grant No. B200501), the Scientific Fund for Remarkable Teachers of Heilongjiang Province (grant No. 1054 G036) and the University of Malaya for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Deng, Z.-P., Gao, S. & Ng, S. W. (2006a). Acta Cryst. E62, m3249–m3250.

Deng, Z.-P., Gao, S. & Ng, S. W. (2006b). Acta Cryst. E62, m3251–m3253.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.

Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Westrip, S. P. (2007). publCIF. In preparation.