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Acta Cryst. (2007). E63, m1813-m1814    [ doi:10.1107/S1600536807026013 ]

Bis([mu]-3-amino-5-carboxybenzoato-[kappa]2O:O')bis[(5-aminoisophthalato)triaquasodium(I)]

R.-H. Zeng, Z.-Q. Fang, F. Sun, L.-S. Jiang and Y.-W. Tang

Abstract top

In the title dinuclear complex, [Na2(C8H6NO4)2(C8H7NO4)2(H2O)6], which is located on a crystallographic inversion centre, each Na+ cation is coordinated by three carboxylate O atoms from three isophthalate ligands and by three water molecules, displaying a distorted octahedral geometry. The separation in the centrosymmetric dinuclear complex is 10.251 (3) Å. Intra- and intermolecular N-H...O and O-H...O hydrogen bonds and [pi]-[pi] interactions (interplanar distance of about 3.43 Å) produce a supramolecular network.

Comment top

Molecular self-assembly of supramolecular architectures has received much attention during recent decades (Kim et al., 2003; Iglesias et al., 2003; Moulton & Zaworotko, 2001). The structures and properties of such systems depend on the coordination and geometric preferences of both the central metals ions and bridging building blocks as well as the influence of weaker non-covalent interactions, such as hydrogen bonds and π-π stacking interactions.

As illustrated in Fig. 1, in the dinuclear centrosymmetric structure of (I) each NaI centre is coordinated by three carboxyl O atoms from three 5-aminoisophthalato ligands, and three water molecules. In the distorted octahedral geometry each of the water molecules is located trans to a carboxyl O atom (Table 1). The Na···Na separation within the centrosymmetric dinuclear complex is 10.251 (3) Å, and the the two central 5-aminoisophthalato ligands are parallel to each other at a plane to plane distance of about 3.43 Å, thus indicating a π stacking interaction (Fig 1). The structure is further extended to a supramolecular network through intra and intermolecular N—H···O and O—H···O hydrogen bonding interactions (Fig 2., Table 2).

Related literature top

For related literature, see: Iglesias et al. (2003); Kim et al. (2003); Moulton & Zaworotko (2001).

Experimental top

The title complex was prepared by the addition of 5-aminoisophthalic acid to a hot aqueous solution. The pH was then adjusted to 7.0 to 8.0 with NaOH (0.1 mol/L). The resulting solution was filtered, and colourless crystals were obtained at room temperature on slow evaporation of the solvent over several days.

Refinement top

Carbon-bound H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 Å, N—H = 0.96 Å and with Uiso(H) = 1.2 Ueq(C) and 1.5 Ueq(N). Water H atoms were tentatively located in difference Fourier maps and were refined with distance restraints of O–H = 0.82 Å and H···H = 1.29 Å, each within a standard deviation of 0.01 Å, and Uiso(H) = 1.5 Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to the labelled atoms by the symmetry operator (−x, −y, 2 − z). Intramolecular hydrogen bonds are shown as blue dashed lines and the π-stacking interaction between the central 5-aminoisophthalato ligands is indicated as a dashed green line, connecting the centroid of the atoms C1 through C6 and O1 and O2 with that of their counterparts created by the inversion center.
[Figure 2] Fig. 2. View of the supramolecular network via intra and intermolecular hydrogen bonds. The hydrogen bonds are indicated as dashed lines.
Bis(µ-3-amino-5-carboxybenzoato-κ2O:O')bis[(5- aminoisophthalato)triaquasodium(I)] top
Crystal data top
[Na2(C8H6NO4)2(C8H7NO4)2(H2O)6]Z = 1
Mr = 876.64F000 = 456
Triclinic, P1Dx = 1.618 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 8.1889 (3) ÅCell parameters from 3500 reflections
b = 8.8821 (3) Åθ = 1.7–26.0º
c = 12.6381 (5) ŵ = 0.16 mm−1
α = 95.251 (2)ºT = 293 (2) K
β = 98.649 (2)ºBlock, colourless
γ = 95.200 (2)º0.19 × 0.16 × 0.15 mm
V = 899.86 (6) Å3
Data collection top
Bruker APEXII area-detector
diffractometer		2714 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
Monochromator: graphiteθmax = 26.0º
T = 293(2) Kθmin = 1.6º
φ and ω scansh = −10→10
Absorption correction: nonek = −10→10
11809 measured reflectionsl = −15→14
3506 independent reflections
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)] = 0.038H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.110  w = 1/[σ2(Fo2) + (0.0543P)2 + 0.2242P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
3506 reflectionsΔρmax = 0.24 e Å−3
292 parametersΔρmin = −0.22 e Å−3
9 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Na2(C8H6NO4)2(C8H7NO4)2(H2O)6]γ = 95.200 (2)º
Mr = 876.64V = 899.86 (6) Å3
Triclinic, P1Z = 1
a = 8.1889 (3) ÅMo Kα
b = 8.8821 (3) ŵ = 0.16 mm−1
c = 12.6381 (5) ÅT = 293 (2) K
α = 95.251 (2)º0.19 × 0.16 × 0.15 mm
β = 98.649 (2)º
Data collection top
Bruker APEXII area-detector
diffractometer		3506 independent reflections
Absorption correction: none2714 reflections with I > 2σ(I)
11809 measured reflectionsRint = 0.029
Refinement top
R[F2 > 2σ(F2)] = 0.0389 restraints
wR(F2) = 0.110H atoms treated by a mixture of
independent and constrained refinement
S = 1.06Δρmax = 0.24 e Å−3
3506 reflectionsΔρmin = −0.22 e Å−3
292 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
xyzUiso*/Ueq
C10.1175 (2)0.2786 (2)1.00350 (14)0.0251 (4)
C20.0923 (2)0.16994 (19)1.08453 (14)0.0233 (4)
C30.2264 (2)0.0955 (2)1.12436 (14)0.0253 (4)
H30.32920.11681.10310.030*
C40.2060 (2)−0.01048 (19)1.19577 (14)0.0241 (4)
C50.0531 (2)−0.04674 (19)1.22571 (14)0.0242 (4)
H50.0403−0.12141.27170.029*
C6−0.0814 (2)0.02815 (19)1.18715 (14)0.0230 (4)
C7−0.0614 (2)0.13772 (19)1.11621 (14)0.0237 (4)
H7−0.15070.18901.09020.028*
C8−0.2484 (2)−0.0130 (2)1.22114 (14)0.0247 (4)
C9−0.0748 (2)0.5059 (2)0.74424 (15)0.0288 (4)
C10−0.0515 (2)0.60556 (19)0.65623 (14)0.0237 (4)
C11−0.1875 (2)0.6705 (2)0.60714 (14)0.0252 (4)
H11−0.29090.65130.62790.030*
C12−0.1679 (2)0.76336 (19)0.52771 (14)0.0228 (4)
C13−0.0155 (2)0.79463 (19)0.49608 (14)0.0242 (4)
H13−0.00420.85850.44270.029*
C140.12133 (19)0.72997 (19)0.54466 (14)0.0234 (4)
C150.1019 (2)0.63570 (19)0.62487 (14)0.0246 (4)
H150.19300.59240.65780.030*
C160.2881 (2)0.7633 (2)0.50918 (15)0.0258 (4)
N10.34825 (17)−0.08917 (17)1.23537 (13)0.0293 (4)
H1A0.3487−0.17411.19220.044*
H1B0.3411−0.11241.30170.044*
H1C0.4417−0.02911.23640.044*
N2−0.31119 (17)0.83326 (16)0.47749 (12)0.0264 (3)
H2A−0.40440.78230.48920.040*
H2B−0.31060.83050.40700.040*
H2C−0.30560.92940.50580.040*
Na10.32524 (8)0.39379 (8)0.81767 (6)0.0301 (2)
O10.25624 (15)0.31616 (16)0.98325 (11)0.0368 (4)
O2−0.01689 (14)0.32523 (15)0.95567 (11)0.0339 (3)
H20.00440.37130.90520.051*
O3−0.26498 (14)−0.13253 (14)1.26574 (11)0.0322 (3)
O4−0.36025 (15)0.07342 (15)1.20278 (12)0.0395 (4)
O50.05126 (15)0.45954 (16)0.79542 (11)0.0371 (4)
O6−0.21793 (16)0.4762 (2)0.76354 (14)0.0593 (5)
O70.40436 (15)0.69099 (17)0.54356 (12)0.0427 (4)
O80.30116 (15)0.86535 (14)0.44630 (11)0.0314 (3)
O1W0.41376 (17)0.65365 (16)0.88767 (13)0.0410 (4)
O2W0.44720 (16)0.44095 (16)0.66516 (12)0.0386 (4)
O3W0.60029 (16)0.34300 (16)0.89387 (12)0.0373 (4)
H1W0.394 (2)0.7293 (17)0.8580 (17)0.045*
H4W0.5484 (12)0.447 (2)0.6801 (17)0.045*
H6W0.618 (2)0.342 (2)0.9601 (8)0.045*
H3W0.430 (2)0.5095 (19)0.6268 (16)0.045*
H2W0.5147 (12)0.662 (2)0.9063 (17)0.045*
H5W0.678 (2)0.402 (2)0.8828 (15)0.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0227 (9)0.0293 (9)0.0253 (10)0.0025 (7)0.0064 (7)0.0093 (8)
C20.0221 (8)0.0267 (9)0.0227 (9)0.0019 (7)0.0060 (7)0.0081 (7)
C30.0188 (8)0.0320 (10)0.0272 (10)0.0012 (7)0.0080 (7)0.0094 (8)
C40.0196 (8)0.0292 (9)0.0256 (10)0.0062 (7)0.0046 (7)0.0088 (7)
C50.0244 (9)0.0277 (9)0.0232 (10)0.0035 (7)0.0064 (7)0.0110 (7)
C60.0202 (8)0.0265 (9)0.0234 (10)0.0012 (7)0.0062 (7)0.0064 (7)
C70.0198 (8)0.0289 (9)0.0250 (10)0.0045 (7)0.0057 (7)0.0100 (7)
C80.0197 (8)0.0336 (10)0.0225 (10)0.0017 (7)0.0059 (7)0.0096 (8)
C90.0228 (9)0.0380 (11)0.0288 (10)0.0034 (7)0.0068 (7)0.0164 (8)
C100.0209 (8)0.0285 (9)0.0235 (10)0.0023 (7)0.0045 (7)0.0114 (7)
C110.0165 (8)0.0320 (9)0.0298 (10)0.0020 (7)0.0081 (7)0.0114 (8)
C120.0179 (8)0.0266 (9)0.0252 (10)0.0052 (6)0.0034 (7)0.0080 (7)
C130.0226 (8)0.0281 (9)0.0251 (10)0.0041 (7)0.0071 (7)0.0126 (7)
C140.0191 (8)0.0293 (9)0.0243 (10)0.0037 (7)0.0073 (7)0.0093 (7)
C150.0188 (8)0.0305 (9)0.0270 (10)0.0061 (7)0.0040 (7)0.0121 (8)
C160.0192 (8)0.0327 (10)0.0287 (10)0.0041 (7)0.0087 (7)0.0104 (8)
N10.0208 (7)0.0370 (9)0.0346 (9)0.0085 (6)0.0090 (6)0.0155 (7)
N20.0203 (7)0.0315 (8)0.0309 (9)0.0071 (6)0.0074 (6)0.0131 (7)
Na10.0243 (4)0.0364 (4)0.0333 (4)0.0055 (3)0.0091 (3)0.0139 (3)
O10.0230 (7)0.0520 (9)0.0403 (9)0.0012 (6)0.0096 (6)0.0268 (7)
O20.0253 (7)0.0444 (8)0.0382 (9)0.0081 (6)0.0090 (6)0.0269 (6)
O30.0261 (7)0.0376 (8)0.0378 (8)0.0032 (5)0.0111 (6)0.0204 (6)
O40.0219 (7)0.0433 (8)0.0612 (10)0.0099 (6)0.0156 (6)0.0261 (7)
O50.0241 (7)0.0519 (9)0.0415 (9)0.0095 (6)0.0062 (6)0.0312 (7)
O60.0203 (7)0.1007 (14)0.0673 (11)0.0035 (7)0.0110 (7)0.0613 (10)
O70.0201 (7)0.0584 (9)0.0607 (10)0.0144 (6)0.0170 (6)0.0377 (8)
O80.0275 (7)0.0370 (7)0.0362 (8)0.0061 (5)0.0150 (6)0.0191 (6)
O1W0.0332 (7)0.0402 (8)0.0507 (10)0.0047 (6)0.0033 (7)0.0152 (7)
O2W0.0291 (7)0.0446 (9)0.0455 (9)0.0031 (6)0.0092 (6)0.0189 (7)
O3W0.0290 (7)0.0459 (9)0.0384 (9)0.0006 (6)0.0062 (6)0.0148 (7)
Geometric parameters (Å, °) top
C1—O11.225 (2)C13—H130.9300
C1—O21.295 (2)C14—C151.391 (2)
C1—C21.494 (2)C14—C161.513 (2)
C2—C31.387 (2)C15—H150.9300
C2—C71.391 (2)C16—O71.243 (2)
C3—C41.378 (2)C16—O81.267 (2)
C3—H30.9300N1—H1A0.8900
C4—C51.381 (2)N1—H1B0.8900
C4—N11.460 (2)N1—H1C0.8900
C5—C61.387 (2)N2—H2A0.8900
C5—H50.9300N2—H2B0.8900
C6—C71.397 (2)N2—H2C0.8900
C6—C81.518 (2)Na1—O52.3520 (14)
C7—H70.9300Na1—O2W2.3535 (16)
C8—O31.253 (2)Na1—O12.3922 (14)
C8—O41.256 (2)Na1—O1W2.4011 (16)
C9—O61.242 (2)Na1—O3W2.4115 (15)
C9—O51.257 (2)Na1—O3i2.4347 (15)
C9—C101.507 (2)O2—H20.8200
C10—C151.384 (2)O3—Na1i2.4347 (15)
C10—C111.390 (2)O1W—H1W0.816 (9)
C11—C121.374 (2)O1W—H2W0.819 (9)
C11—H110.9300O2W—H4W0.818 (9)
C12—C131.379 (2)O2W—H3W0.822 (9)
C12—N21.465 (2)O3W—H6W0.829 (9)
C13—C141.391 (2)O3W—H5W0.824 (9)
O1—C1—O2123.59 (16)C14—C15—H15119.6
O1—C1—C2121.24 (15)O7—C16—O8123.72 (15)
O2—C1—C2115.14 (14)O7—C16—C14118.79 (15)
C3—C2—C7120.26 (15)O8—C16—C14117.48 (15)
C3—C2—C1117.75 (15)C4—N1—H1A109.5
C7—C2—C1121.93 (15)C4—N1—H1B109.5
C4—C3—C2119.41 (15)H1A—N1—H1B109.5
C4—C3—H3120.3C4—N1—H1C109.5
C2—C3—H3120.3H1A—N1—H1C109.5
C3—C4—C5121.02 (15)H1B—N1—H1C109.5
C3—C4—N1118.45 (14)C12—N2—H2A109.5
C5—C4—N1120.47 (15)C12—N2—H2B109.5
C4—C5—C6119.98 (15)H2A—N2—H2B109.5
C4—C5—H5120.0C12—N2—H2C109.5
C6—C5—H5120.0H2A—N2—H2C109.5
C5—C6—C7119.47 (15)H2B—N2—H2C109.5
C5—C6—C8119.25 (15)O5—Na1—O2W110.25 (5)
C7—C6—C8121.27 (15)O5—Na1—O182.66 (5)
C2—C7—C6119.81 (16)O2W—Na1—O1166.86 (6)
C2—C7—H7120.1O5—Na1—O1W87.51 (5)
C6—C7—H7120.1O2W—Na1—O1W87.97 (6)
O3—C8—O4124.40 (16)O1—Na1—O1W95.25 (6)
O3—C8—C6117.05 (15)O5—Na1—O3W163.62 (6)
O4—C8—C6118.55 (15)O2W—Na1—O3W84.43 (5)
O6—C9—O5123.50 (16)O1—Na1—O3W83.12 (5)
O6—C9—C10118.04 (15)O1W—Na1—O3W85.74 (5)
O5—C9—C10118.45 (15)O5—Na1—O3i97.80 (5)
C15—C10—C11119.60 (15)O2W—Na1—O3i85.57 (5)
C15—C10—C9121.63 (15)O1—Na1—O3i90.33 (5)
C11—C10—C9118.76 (15)O1W—Na1—O3i172.76 (6)
C12—C11—C10119.53 (15)O3W—Na1—O3i90.36 (5)
C12—C11—H11120.2C1—O1—Na1127.35 (12)
C10—C11—H11120.2C1—O2—H2109.5
C11—C12—C13121.37 (15)C8—O3—Na1i128.48 (12)
C11—C12—N2119.21 (14)C9—O5—Na1154.20 (12)
C13—C12—N2119.40 (15)Na1—O1W—H1W127.1 (16)
C12—C13—C14119.52 (15)Na1—O1W—H2W108.1 (14)
C12—C13—H13120.2H1W—O1W—H2W105.5 (13)
C14—C13—H13120.2Na1—O2W—H4W110.2 (15)
C15—C14—C13119.26 (15)Na1—O2W—H3W126.7 (15)
C15—C14—C16121.28 (15)H4W—O2W—H3W104.3 (13)
C13—C14—C16119.45 (15)Na1—O3W—H6W115.8 (15)
C10—C15—C14120.72 (15)Na1—O3W—H5W116.8 (15)
C10—C15—H15119.6H6W—O3W—H5W102.8 (13)
Symmetry codes: (i) −x, −y, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3Wii0.891.892.763 (2)168
N1—H1B···O8iii0.891.932.810 (2)170
N1—H1C···O4iv0.891.912.7808 (19)165
N2—H2A···O7v0.891.942.8221 (18)169
N2—H2A···O8v0.892.583.1815 (18)126
N2—H2B···O3vi0.891.932.7981 (19)165
N2—H2C···O8vii0.891.862.750 (2)175
O2—H2···O50.821.732.5491 (17)177
O1W—H1W···O4viii0.816 (9)2.002 (10)2.8150 (19)175 (2)
O2W—H4W···O6iv0.818 (9)2.024 (11)2.8128 (19)162 (2)
O3W—H6W···O1Wix0.829 (9)1.977 (10)2.778 (2)162 (2)
O2W—H3W···O70.822 (9)2.013 (10)2.8322 (19)174 (2)
Symmetry codes: (ii) −x+1, −y, −z+2; (iii) x, y−1, z+1; (iv) x+1, y, z; (v) x−1, y, z; (vi) x, y+1, z−1; (vii) −x, −y+2, −z+1; (viii) −x, −y+1, −z+2; (ix) −x+1, −y+1, −z+2.
Table 1
Selected geometric parameters (Å, °) top
Na1—O52.3520 (14)Na1—O1W2.4011 (16)
Na1—O2W2.3535 (16)Na1—O3W2.4115 (15)
Na1—O12.3922 (14)Na1—O3i2.4347 (15)
O5—Na1—O2W110.25 (5)O1—Na1—O3W83.12 (5)
O5—Na1—O182.66 (5)O1W—Na1—O3W85.74 (5)
O2W—Na1—O1166.86 (6)O5—Na1—O3i97.80 (5)
O5—Na1—O1W87.51 (5)O2W—Na1—O3i85.57 (5)
O2W—Na1—O1W87.97 (6)O1—Na1—O3i90.33 (5)
O1—Na1—O1W95.25 (6)O1W—Na1—O3i172.76 (6)
O5—Na1—O3W163.62 (6)O3W—Na1—O3i90.36 (5)
O2W—Na1—O3W84.43 (5)
Symmetry codes: (i) −x, −y, −z+2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3Wii0.891.892.763 (2)168
N1—H1B···O8iii0.891.932.810 (2)170
N1—H1C···O4iv0.891.912.7808 (19)165
N2—H2A···O7v0.891.942.8221 (18)169
N2—H2A···O8v0.892.583.1815 (18)126
N2—H2B···O3vi0.891.932.7981 (19)165
N2—H2C···O8vii0.891.862.750 (2)175
O2—H2···O50.821.732.5491 (17)177
O1W—H1W···O4viii0.816 (9)2.002 (10)2.8150 (19)175 (2)
O2W—H4W···O6iv0.818 (9)2.024 (11)2.8128 (19)162 (2)
O3W—H6W···O1Wix0.829 (9)1.977 (10)2.778 (2)162 (2)
O2W—H3W···O70.822 (9)2.013 (10)2.8322 (19)174 (2)
Symmetry codes: (ii) −x+1, −y, −z+2; (iii) x, y−1, z+1; (iv) x+1, y, z; (v) x−1, y, z; (vi) x, y+1, z−1; (vii) −x, −y+2, −z+1; (viii) −x, −y+1, −z+2; (ix) −x+1, −y+1, −z+2.
Acknowledgements top

The authors thank South China Normal University for supporting this study.

references
References top

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