Acta Cryst. (2007). E63, m1687 [ doi:10.1107/S1600536807023409 ]
The title compound, Na+·C6H3N2O5-·H2O, was obtained by the reaction of sodium hydroxide with 2,4-dinitrophenol in water. The crystal packing shows a laminated structure with intercalated coordinated 2,4-dinitrophenolate spacers, where Na+ cations and water molecules lie on twofold rotation axes. The laminated structure consists of NaO6 chains linked by 2,4-dinitrophenolate ligands. Each Na+ cation exhibits a distorted octahedral geometry. One cation is surrounded by four water molecules and two O atoms from two 4-nitro groups. The other is surrounded by two O atoms from two 2-nitro groups and four phenolate O atoms.
Compound (I) was obtained as the product of the reaction of sodium hydroxide (0.20 g, 5 mmol) with 2,4-dinitrophenol (0.70 g, 3.8 mmol) in water (10 ml) (yield 0.66 g).
H atoms on water molecules were located in a difference map and refined isotropically. The other H atoms were positioned geometrically and refined as riding, with C—H = 0.94 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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, 2001); software used to prepare material for publication: SHELXTL and local programs.
![[Figure 1]](./hy2061fig1thm.gif)
| Fig. 1. The asymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. |
![[Figure 2]](./hy2061fig2thm.gif)
| Fig. 2. The crystal packing of (I). Dashed lines denote hydrogen bonds. |
| Na+.C6H3NO5−.H2O | F(000) = 456 |
| Mr = 224.11 | Dx = 1.851 Mg m−3 |
| Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: C 2y | Cell parameters from 3132 reflections |
| a = 19.962 (3) Å | θ = 3.2–27.0° |
| b = 11.4615 (17) Å | µ = 0.21 mm−1 |
| c = 3.5291 (5) Å | T = 203 K |
| β = 95.136 (12)° | Needle, yellow |
| V = 804.2 (2) Å3 | 0.20 × 0.10 × 0.10 mm |
| Z = 4 |
| Bruker SMART 1K CCD area-detector diffractometer | 971 independent reflections |
| Radiation source: fine-focus sealed tube | 716 reflections with I > 2σ(I) |
| graphite | Rint = 0.066 |
| Detector resolution: 8.192 pixels mm-1 | θmax = 27.5°, θmin = 3.6° |
| φ and ω scan | h = −25→25 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
| Tmin = 0.959, Tmax = 0.979 | l = −4→4 |
| 5696 measured reflections |
| 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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| S = 0.90 | w = 1/[σ2(Fo2) + (0.0097P)2] where P = (Fo2 + 2Fc2)/3 |
| 971 reflections | (Δ/σ)max < 0.001 |
| 145 parameters | Δρmax = 0.19 e Å−3 |
| 1 restraint | Δρmin = −0.22 e Å−3 |
| Na+.C6H3NO5−.H2O | V = 804.2 (2) Å3 |
| Mr = 224.11 | Z = 4 |
| Monoclinic, C2 | Mo Kα radiation |
| a = 19.962 (3) Å | µ = 0.21 mm−1 |
| b = 11.4615 (17) Å | T = 203 K |
| c = 3.5291 (5) Å | 0.20 × 0.10 × 0.10 mm |
| β = 95.136 (12)° |
| Bruker SMART 1K CCD area-detector diffractometer | 971 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 716 reflections with I > 2σ(I) |
| Tmin = 0.959, Tmax = 0.979 | Rint = 0.066 |
| 5696 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.040 | Δρmax = 0.19 e Å−3 |
| S = 0.90 | Δρmin = −0.22 e Å−3 |
| 971 reflections | Absolute structure: ? |
| 145 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| Na1 | −0.5000 | −0.10008 (15) | 0.0000 | 0.0181 (4) | |
| Na2 | 0.0000 | −0.00873 (14) | 0.0000 | 0.0166 (5) | |
| O5 | −0.07595 (10) | 0.03588 (16) | 0.4527 (6) | 0.0149 (5) | |
| N1 | −0.34206 (13) | −0.1025 (2) | 0.1758 (7) | 0.0173 (7) | |
| O1 | −0.06035 (10) | −0.18077 (16) | 0.7752 (6) | 0.0187 (6) | |
| O4 | −0.38225 (10) | −0.03559 (17) | −0.0055 (6) | 0.0200 (6) | |
| O3 | −0.12530 (9) | −0.3073 (2) | 0.4714 (5) | 0.0207 (5) | |
| N2 | −0.11202 (13) | −0.2052 (2) | 0.5748 (7) | 0.0152 (6) | |
| O2 | −0.35961 (10) | −0.19710 (18) | 0.3024 (6) | 0.0210 (6) | |
| C1 | −0.25320 (16) | 0.0447 (3) | 0.1392 (8) | 0.0139 (8) | |
| H1A | −0.2852 | 0.0976 | 0.0281 | 0.017* | |
| C2 | −0.13592 (15) | 0.0009 (3) | 0.3809 (8) | 0.0120 (7) | |
| C3 | −0.18714 (15) | 0.0772 (3) | 0.2110 (9) | 0.0132 (7) | |
| H3A | −0.1748 | 0.1533 | 0.1457 | 0.016* | |
| C4 | −0.22575 (15) | −0.1487 (3) | 0.3777 (8) | 0.0122 (8) | |
| H4A | −0.2387 | −0.2256 | 0.4282 | 0.015* | |
| C5 | −0.15992 (15) | −0.1149 (3) | 0.4466 (8) | 0.0123 (7) | |
| C6 | −0.27234 (15) | −0.0690 (3) | 0.2343 (9) | 0.0117 (7) | |
| O7 | −0.5000 | −0.2456 (3) | −0.5000 | 0.0178 (8) | |
| O8 | −0.5000 | 0.0418 (3) | −0.5000 | 0.0181 (8) | |
| H2 | −0.5300 (14) | 0.088 (3) | −0.511 (10) | 0.022 (10)* | |
| H1 | −0.4654 (15) | −0.298 (3) | −0.498 (9) | 0.051 (11)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Na1 | 0.0162 (11) | 0.0180 (10) | 0.0203 (11) | 0.000 | 0.0020 (8) | 0.000 |
| Na2 | 0.0116 (10) | 0.0212 (11) | 0.0167 (11) | 0.000 | 0.0002 (8) | 0.000 |
| O5 | 0.0122 (13) | 0.0141 (12) | 0.0178 (13) | −0.0009 (10) | −0.0013 (10) | −0.0014 (10) |
| N1 | 0.0212 (18) | 0.0185 (16) | 0.0129 (16) | 0.0039 (15) | 0.0055 (13) | −0.0065 (14) |
| O1 | 0.0119 (13) | 0.0183 (14) | 0.0236 (13) | −0.0022 (11) | −0.0113 (11) | −0.0010 (10) |
| O4 | 0.0094 (13) | 0.0237 (14) | 0.0258 (15) | 0.0054 (10) | −0.0052 (11) | 0.0030 (11) |
| O3 | 0.0187 (12) | 0.0143 (12) | 0.0288 (14) | 0.0007 (12) | −0.0004 (10) | −0.0036 (13) |
| N2 | 0.0171 (17) | 0.0168 (16) | 0.0128 (15) | 0.0001 (13) | 0.0073 (13) | −0.0014 (13) |
| O2 | 0.0166 (13) | 0.0165 (14) | 0.0298 (14) | −0.0059 (11) | 0.0012 (11) | 0.0006 (11) |
| C1 | 0.0128 (19) | 0.0193 (19) | 0.010 (2) | 0.0038 (15) | 0.0013 (15) | 0.0007 (15) |
| C2 | 0.0126 (19) | 0.0153 (18) | 0.0087 (18) | 0.0033 (16) | 0.0046 (15) | −0.0018 (14) |
| C3 | 0.0162 (19) | 0.0113 (18) | 0.0127 (18) | −0.0015 (15) | 0.0054 (15) | 0.0026 (14) |
| C4 | 0.0145 (19) | 0.0124 (17) | 0.0098 (18) | 0.0024 (14) | 0.0013 (14) | −0.0006 (13) |
| C5 | 0.0108 (18) | 0.0160 (18) | 0.0096 (18) | 0.0045 (16) | −0.0012 (13) | 0.0002 (15) |
| C6 | 0.0077 (19) | 0.017 (2) | 0.0101 (17) | −0.0032 (13) | −0.0011 (13) | −0.0018 (14) |
| O7 | 0.016 (2) | 0.0138 (19) | 0.024 (2) | 0.000 | 0.0046 (17) | 0.000 |
| O8 | 0.012 (2) | 0.013 (2) | 0.029 (2) | 0.000 | −0.0019 (18) | 0.000 |
| Na1—O8i | 2.400 (3) | N1—O4 | 1.245 (3) |
| Na1—O8 | 2.400 (3) | N1—C6 | 1.441 (4) |
| Na1—O7 | 2.428 (2) | O1—N2 | 1.230 (3) |
| Na1—O7i | 2.428 (2) | O3—N2 | 1.247 (3) |
| Na1—O4 | 2.466 (2) | N2—C5 | 1.454 (4) |
| Na1—O4ii | 2.466 (2) | C1—C3 | 1.372 (4) |
| Na1—Na1i | 3.5291 (5) | C1—C6 | 1.407 (4) |
| Na2—O5iii | 2.355 (2) | C1—H1A | 0.9400 |
| Na2—O5 | 2.355 (2) | C2—C5 | 1.436 (4) |
| Na2—O5iv | 2.401 (2) | C2—C3 | 1.435 (4) |
| Na2—O5v | 2.401 (2) | C3—H3A | 0.9400 |
| Na2—O1v | 2.408 (2) | C4—C5 | 1.371 (4) |
| Na2—O1iv | 2.408 (2) | C4—C6 | 1.368 (4) |
| Na2—Na2i | 3.5291 (5) | C4—H4A | 0.9400 |
| O5—C2 | 1.267 (3) | O7—H1 | 0.92 (3) |
| N1—O2 | 1.235 (3) | O8—H2 | 0.80 (3) |
| O8i—Na1—O8 | 94.67 (14) | O5v—Na2—Na2i | 138.40 (5) |
| O8i—Na1—O7 | 179.28 (11) | O1v—Na2—Na2i | 106.54 (5) |
| O8—Na1—O7 | 86.05 (7) | O1iv—Na2—Na2i | 73.46 (5) |
| O8i—Na1—O7i | 86.05 (7) | O5iii—Na2—Na2v | 42.60 (5) |
| O8—Na1—O7i | 179.28 (11) | O5—Na2—Na2v | 137.40 (5) |
| O7—Na1—O7i | 93.23 (12) | O5iv—Na2—Na2v | 138.40 (5) |
| O8i—Na1—O4 | 82.26 (6) | O5v—Na2—Na2v | 41.60 (5) |
| O8—Na1—O4 | 74.23 (6) | O1v—Na2—Na2v | 73.46 (5) |
| O7—Na1—O4 | 97.94 (5) | O1iv—Na2—Na2v | 106.54 (5) |
| O7i—Na1—O4 | 105.88 (5) | Na2i—Na2—Na2v | 180.00 (5) |
| O8i—Na1—O4ii | 74.23 (6) | C2—O5—Na2 | 116.73 (18) |
| O8—Na1—O4ii | 82.26 (6) | C2—O5—Na2i | 127.66 (19) |
| O7—Na1—O4ii | 105.88 (5) | Na2—O5—Na2i | 95.80 (7) |
| O7i—Na1—O4ii | 97.94 (5) | O2—N1—O4 | 122.4 (3) |
| O4—Na1—O4ii | 145.11 (12) | O2—N1—C6 | 118.9 (3) |
| O8i—Na1—Na1i | 42.67 (7) | O4—N1—C6 | 118.6 (3) |
| O8—Na1—Na1i | 137.33 (7) | N2—O1—Na2i | 138.17 (18) |
| O7—Na1—Na1i | 136.61 (6) | N1—O4—Na1 | 112.46 (18) |
| O7i—Na1—Na1i | 43.39 (6) | O1—N2—O3 | 121.8 (2) |
| O4—Na1—Na1i | 95.35 (5) | O1—N2—C5 | 120.8 (3) |
| O4ii—Na1—Na1i | 84.65 (5) | O3—N2—C5 | 117.4 (2) |
| O8i—Na1—Na1v | 137.33 (7) | C3—C1—C6 | 119.0 (3) |
| O8—Na1—Na1v | 42.67 (7) | C3—C1—H1A | 120.5 |
| O7—Na1—Na1v | 43.39 (6) | C6—C1—H1A | 120.5 |
| O7i—Na1—Na1v | 136.61 (6) | O5—C2—C5 | 125.7 (3) |
| O4—Na1—Na1v | 84.65 (5) | O5—C2—C3 | 121.0 (3) |
| O4ii—Na1—Na1v | 95.35 (5) | C5—C2—C3 | 113.3 (3) |
| Na1i—Na1—Na1v | 180.00 (6) | C1—C3—C2 | 123.3 (3) |
| O5iii—Na2—O5 | 154.92 (12) | C1—C3—H3A | 118.4 |
| O5iii—Na2—O5iv | 95.80 (7) | C2—C3—H3A | 118.4 |
| O5—Na2—O5iv | 78.85 (8) | C5—C4—C6 | 119.1 (3) |
| O5iii—Na2—O5v | 78.85 (8) | C5—C4—H4A | 120.4 |
| O5—Na2—O5v | 95.80 (7) | C6—C4—H4A | 120.4 |
| O5iv—Na2—O5v | 155.41 (11) | C4—C5—C2 | 124.1 (3) |
| O5iii—Na2—O1v | 106.72 (7) | C4—C5—N2 | 116.6 (3) |
| O5—Na2—O1v | 93.89 (8) | C2—C5—N2 | 119.2 (3) |
| O5iv—Na2—O1v | 134.48 (8) | C4—C6—C1 | 121.1 (3) |
| O5v—Na2—O1v | 69.40 (7) | C4—C6—N1 | 119.4 (3) |
| O5iii—Na2—O1iv | 93.89 (8) | C1—C6—N1 | 119.5 (3) |
| O5—Na2—O1iv | 106.72 (7) | Na1—O7—Na1v | 93.23 (12) |
| O5iv—Na2—O1iv | 69.40 (7) | Na1—O7—H1 | 120 (2) |
| O5v—Na2—O1iv | 134.48 (8) | Na1v—O7—H1 | 114 (2) |
| O1v—Na2—O1iv | 70.04 (10) | Na1v—O8—Na1 | 94.67 (14) |
| O5iii—Na2—Na2i | 137.40 (5) | Na1v—O8—H2 | 118 (2) |
| O5—Na2—Na2i | 42.60 (5) | Na1—O8—H2 | 116 (2) |
| O5iv—Na2—Na2i | 41.60 (5) |
| Symmetry codes: (i) x, y, z+1; (ii) −x−1, y, −z; (iii) −x, y, −z; (iv) −x, y, −z+1; (v) x, y, z−1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O8—H2···O3vi | 0.80 (3) | 2.25 (3) | 3.035 (3) | 171 (3) |
| O7—H1···O5vii | 0.92 (3) | 2.07 (3) | 2.925 (3) | 154 (3) |
| Symmetry codes: (vi) x−1/2, y+1/2, z−1; (vii) −x−1/2, y−1/2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O8—H2···O3i | 0.80 (3) | 2.25 (3) | 3.035 (3) | 171 (3) |
| O7—H1···O5ii | 0.92 (3) | 2.07 (3) | 2.925 (3) | 154 (3) |
| Symmetry codes: (i) x−1/2, y+1/2, z−1; (ii) −x−1/2, y−1/2, −z. |
We are grateful to the Deutsche Forschungsgemeinschaft (SFB 558 Metall-Substratwechselwirkungen in der heterogenen Katalyse) for financial support.
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Prondzinski, N. von, Babai, A., Mudring, A. V. & Merz, K. (2007). Z. Anorg. Allg. Chem. In the press.
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Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
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2,4-Dinitrophenolate is a versatile ligand for crystal engineering, which is able to coordinate with phenoxy or nitro groups to metal centers, yielding different metal complexes (Prondzinski et al., 2007; Zaderenko et al., 1997). It is known that nitrophenols not only form various π-stacking complexes with other aromatic molecules but also form salts through specific electrostatic or hydrogen-bonding interactions (In et al., 1997). The bonding of electron-donor-acceptor complexes depends strongly on the substitution pattern of nitro and hydroxy groups on the benzene ring.
The asymmetric unit of (I) is shown in Fig. 1, where Na atoms and water molecules each lies on a twofold rotation axis. The crystal packing of (I) shows a laminated structure with intercalated coordinated 2,4-dinitrophenolate spacer (Fig. 2). The laminated structure consists of NaO6 chains linked by 2,4-dinitrophenolate ligands. Each Na atom exhibits a distorted octahedral geometry. The Na1 atom is surrounded by four water molecules and two O atoms from two para-nitro groups. The Na2 atom is surrounded by two O atoms from two ortho-nitro groups and four phenolate O atoms.