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In mol­ecules of 3-nitro­phthalic acid, C8H5NO6, the 2-carboxyl group, which is the central of the three substituents, is almost orthogonal to the arene ring, while the other two substituents are effectively coplanar with the ring. The mol­ecules are linked by two O-H...O hydrogen bonds [H...O = 1.86 and 1.89 Å, O...O = 2.6983 (13) and 2.6809 (12) Å, and O-H...O = 172 and 155°] into sheets containing alternating R_2^2(8) and R_6^6(36) rings; these sheets are linked into a three-dimensional framework by a single C-H...O hydrogen bond [H...O = 2.41 Å, C...O = 3.2663 (15) Å and C-H...O = 150°].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103002555/sk1616sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103002555/sk1616Isup2.hkl
Contains datablock I

CCDC reference: 208025

Comment top

The O—H···O hydrogen bonds in simple carboxylic acids exhibit two main patterns, namely formation of R22(8) (Bernstein et al., 1995) rings, often centrosymmetric, as exemplified by benzoic acid (Sim et al., 1955; Feld et al., 1981; Wilson et al., 1996), and formation of C(4) chains, as exemplified by acetic acid (Jones & Templeton, 1958; Nahringbauer, 1970; Jönsson, 1971). We report here the molecular and supramolecular structure of 3-nitrophthalic acid, (I), in which the two independent carboxyl groups are involved in different supramolecular synthons, one forming an R22(8) ring and the other a C(4) chain.

The molecular conformation of (I) (Fig. 1 and Table 1) is dominated by the avoidance of steric clashing between adjacent substituents; thus, while the nitro group and the carboxyl group containing atom C11 are both nearly coplanar with the aryl ring, the carboxyl group containing C21, which lies between the other two substituents, is almost orthogonal to the ring. While there are no significant differences between corresponding C—O distances in the two carboxyl substituents, the C2—C21 bond is somewhat longer than C1—C11, suggesting a reduction in conjugation. Accordingly, the internal C—C—C angle at C2 has a value more typical of an electron-source substituent rather than an electron-sink substituent (Domenicano & Murray-Rust, 1979).

Molecules of (I) are linked into a single three-dimensional framework by a combination of two O—H···O hydrogen bonds and one C—H···O hydrogen bond (Table 2), and the formation of the framework is readily analysed using the substructure approach (Gregson et al., 2000). Carboxyl atom O22 in the molecule at (x, y, z) acts as hydrogen-bond donor to carboxyl atom O21 in the molecule at (0.5 − x, −0.5 + y, 0.5 − z), while O22 at (0.5 − x, −0.5 + y, 0.5 − z), in turn, acts as donor to O21 at (x, −1 + y, z); this hydrogen bond thus produces a C(4) chain running parallel to the [010] direction and generated by the 21 screw axis along (1/4, y, 1/4). A second, antiparallel, chain, related to the first by inversion, runs through the cell around the 21 screw axis along (3/4, −y, 3/4).

There is a short non-bonded contact between the negatively polarized carbonyl atom O21 in the molecule at (x, y, z) and the positively polarized atom N31 in the molecule at (0.5 − x, 0.5 + y, 0.5 − z). The geometry of this interaction (Fig. 2) resembles that of the perpendicular interaction between pairs of carbonyl groups (Allen et al., 1998). The O···N distance is 2.807 (2) Å, well below the sum of the van der Waals radii for N and O of 3.05 Å (Bondi, 1964), and hence this interaction must be regarded as attractive, and as reinforcing the formation of the chain along [010].

The carboxyl atom O12 in the molecule at acts as hydrogen-bond donor to O11 in the molecule at (1 − x, −y, 1 − z), so generating a centrosymmetric R22(8) motif. The molecules at (x, y, z) and (1 − x, −y, 1 − z) lie in the spiral chains along (1/4, y, 1/4) and (3/4, −y, 3/4), respectively. Hence the combination of the C(4) and R22(8) motifs generates a sheet, parallel to (101), containing R22(8) and R66(36) rings, alternating in a checkerboard fashion (Fig. 2). Just one sheet of this type passes through each unit cell.

Finally, atom C4 in the molecule at (x, y, z), which lies in the (101) sheet passing through (1/4, y, 1/4), acts as hydrogen-bond donor to nitro atom O31 in the molecule at (-x, 2 − y, 1 − z), which lies in the sheet passing through (−0.75, y, 1/4). Propagation of this interaction, via the R22(10) motif (Fig. 3) thus links together all of the (101) sheets to form a single framework.

Of the six possible isomeric nitrophthalic acids, only the structure of 5-nitroisophthalic acid, (II), has been reported (Domenicano et al., 1990) prior to the present report on (I). However, that report (Domenicano et al., 1990) was concerned solely with the intramolecular dimensions, in particular the internal angles of the arene ring, and gave no discussion whatsoever of the supramolecular structure. We have now analysed the supramolecular structure of (II) using coordinates retrieved from the Cambridge Structural Database (CSD; Allen, 2002) for (II) (CSD refcode COFDUW10). Compound (II) was refined in space group A2/c (cf. C2/c) with Z' = 2, but with a disconnected asymmetric unit. The supramolecular structure is determined by four distinct O—H···O hydrogen bonds, which link the molecules into a chain of R22(8) rings running parallel to the [011] direction (Fig. 4). However, the C(4) motif apparent in (I) is absent from (II).

Experimental top

A sample of 3-nitrophthalic acid (Aldrich) was crystallized by slow evaporation of a solution in ethanol.

Refinement top

Compound (I) is monoclinic, and the space group P21/n was uniquely assigned from the systematic absences. All H atoms were treated as riding atoms, with C—H distances of 0.95 Å and O—H distances of 0.84 Å.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Stereoview of part of the crystal structure of (I), showing the formation of a (101) sheet of R2(8) and R66(36) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the R22(10) motif which links the (101) sheets. For the sake of clarity, the unit-cell box has been omitted. Atoms marked with an asterisk (*) are at the symmetry position (-x, 2 − y, 1 − z).
[Figure 4] Fig. 4. Part of the crystal structure of COFDUW10 (Domenicano et al., 1990), showing formation of a chain of R22(8) rings along [011]. For the sake of clarity, the unit-cell box has been omitted; the atom labels and symmetry positions are those used in the original report (Domenicano et al., 1990). Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions (0.5 + x, −y, z), (0.5 + x, −0.5 − y, 0.5 + z) and (x, 0.5 + y, −0.5 + z), respectively.
3-Nitrophthalic acid top
Crystal data top
C8H5NO6F(000) = 432
Mr = 211.13Dx = 1.740 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1827 reflections
a = 9.4972 (2) Åθ = 3.4–27.5°
b = 6.9014 (2) ŵ = 0.15 mm1
c = 12.3077 (3) ÅT = 120 K
β = 92.0599 (11)°Block, brown
V = 806.17 (3) Å30.35 × 0.30 × 0.18 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer
1827 independent reflections
Radiation source: rotating anode1641 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
ϕ scans, and ω scans with κ offsetsθmax = 27.5°, θmin = 3.4°
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
h = 1212
Tmin = 0.945, Tmax = 0.972k = 88
9456 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0344P)2 + 0.4307P]
where P = (Fo2 + 2Fc2)/3
1827 reflections(Δ/σ)max = 0.001
138 parametersΔρmax = 0.32 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C8H5NO6V = 806.17 (3) Å3
Mr = 211.13Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.4972 (2) ŵ = 0.15 mm1
b = 6.9014 (2) ÅT = 120 K
c = 12.3077 (3) Å0.35 × 0.30 × 0.18 mm
β = 92.0599 (11)°
Data collection top
Nonius KappaCCD
diffractometer
1827 independent reflections
Absorption correction: multi-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
1641 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.972Rint = 0.051
9456 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.087H-atom parameters constrained
S = 1.07Δρmax = 0.32 e Å3
1827 reflectionsΔρmin = 0.33 e Å3
138 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.31621 (12)0.42340 (17)0.52082 (10)0.0125 (3)
C20.21751 (12)0.46514 (16)0.43625 (9)0.0105 (2)
C30.13797 (12)0.63375 (17)0.44588 (9)0.0110 (2)
C40.15784 (13)0.76347 (17)0.53133 (10)0.0143 (3)
C50.25745 (13)0.72129 (19)0.61288 (10)0.0165 (3)
C60.33469 (13)0.55049 (19)0.60876 (10)0.0155 (3)
C110.40129 (13)0.24112 (18)0.51580 (10)0.0139 (3)
O110.39628 (10)0.13587 (13)0.43643 (7)0.0198 (2)
O120.48057 (11)0.20781 (14)0.60382 (8)0.0235 (2)
C210.20877 (12)0.33648 (16)0.33651 (9)0.0108 (2)
O210.27612 (9)0.37307 (12)0.25687 (7)0.0141 (2)
O220.12760 (9)0.18427 (12)0.34762 (7)0.0140 (2)
N310.02428 (10)0.67570 (14)0.36443 (8)0.0118 (2)
O310.04206 (9)0.82741 (13)0.37272 (8)0.0179 (2)
O320.00067 (10)0.55423 (13)0.29332 (7)0.0176 (2)
H40.10400.87930.53380.017*
H50.27300.80900.67160.020*
H60.40050.51980.66610.019*
H120.52220.10130.59750.035*
H220.14480.10260.29930.021*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0132 (6)0.0115 (6)0.0128 (6)0.0007 (4)0.0013 (4)0.0015 (4)
C20.0110 (5)0.0090 (5)0.0117 (5)0.0012 (4)0.0024 (4)0.0010 (4)
C30.0109 (5)0.0101 (5)0.0120 (6)0.0004 (4)0.0012 (4)0.0016 (4)
C40.0142 (6)0.0111 (5)0.0179 (6)0.0010 (4)0.0033 (5)0.0024 (5)
C50.0177 (6)0.0162 (6)0.0155 (6)0.0009 (5)0.0004 (5)0.0045 (5)
C60.0149 (6)0.0182 (6)0.0134 (6)0.0005 (5)0.0011 (5)0.0004 (5)
C110.0135 (6)0.0135 (6)0.0145 (6)0.0010 (4)0.0006 (4)0.0029 (4)
O110.0240 (5)0.0167 (5)0.0183 (5)0.0087 (4)0.0041 (4)0.0031 (4)
O120.0315 (5)0.0191 (5)0.0191 (5)0.0131 (4)0.0083 (4)0.0010 (4)
C210.0117 (5)0.0081 (5)0.0126 (6)0.0033 (4)0.0011 (4)0.0009 (4)
O210.0189 (4)0.0104 (4)0.0132 (4)0.0014 (3)0.0035 (3)0.0007 (3)
O220.0168 (4)0.0094 (4)0.0160 (4)0.0017 (3)0.0030 (3)0.0031 (3)
N310.0122 (5)0.0095 (5)0.0139 (5)0.0003 (4)0.0024 (4)0.0009 (4)
O310.0188 (4)0.0127 (4)0.0221 (5)0.0071 (3)0.0008 (4)0.0006 (3)
O320.0204 (5)0.0145 (4)0.0173 (5)0.0021 (3)0.0050 (4)0.0042 (3)
Geometric parameters (Å, º) top
C11—O111.2169 (16)C3—N311.4754 (15)
C11—O121.3171 (15)C4—C51.3853 (18)
C1—C111.4977 (16)C4—H40.95
C21—O211.2160 (15)C5—C61.3902 (18)
C21—O221.3130 (14)C5—H50.95
C2—C211.5148 (16)C6—H60.95
C1—C61.3992 (17)O12—H120.84
C1—C21.4054 (17)O22—H220.84
C2—C31.3947 (16)N31—O311.2281 (13)
C3—C41.3888 (17)N31—O321.2288 (13)
C2—C1—C6120.41 (11)C5—C6—C1120.53 (12)
C6—C1—C11120.37 (11)C5—C6—H6119.7
C2—C1—C11119.22 (11)C1—C6—H6119.7
C1—C2—C3117.19 (11)O11—C11—O12124.12 (11)
C3—C2—C21122.95 (10)O11—C11—C1121.93 (11)
C1—C2—C21119.71 (10)O12—C11—C1113.95 (10)
C2—C3—C4122.89 (11)C11—O12—H12109.5
C4—C3—N31117.66 (10)O21—C21—O22125.30 (11)
C2—C3—N31119.43 (10)O21—C21—C2121.09 (10)
C5—C4—C3118.93 (11)O22—C21—C2113.57 (10)
C5—C4—H4120.5C21—O22—H22109.5
C3—C4—H4120.5O31—N31—O32123.67 (10)
C4—C5—C6119.95 (11)O31—N31—C3118.42 (10)
C4—C5—H5120.0O32—N31—C3117.89 (9)
C6—C5—H5120.0
C6—C1—C2—C31.65 (17)C11—C1—C6—C5179.01 (11)
C11—C1—C2—C3178.28 (10)C6—C1—C11—O11173.77 (12)
C6—C1—C2—C21174.06 (10)C2—C1—C11—O116.30 (18)
C11—C1—C2—C216.02 (16)C6—C1—C11—O125.97 (17)
C1—C2—C3—C43.38 (17)C2—C1—C11—O12173.96 (11)
C21—C2—C3—C4172.17 (11)C3—C2—C21—O2183.34 (15)
C1—C2—C3—N31174.63 (10)C1—C2—C21—O2192.11 (14)
C21—C2—C3—N319.81 (16)C3—C2—C21—O2298.93 (13)
C2—C3—C4—C52.31 (18)C1—C2—C21—O2285.62 (13)
N31—C3—C4—C5175.74 (10)C4—C3—N31—O313.79 (16)
C3—C4—C5—C60.56 (18)C2—C3—N31—O31178.09 (10)
C4—C5—C6—C12.21 (19)C4—C3—N31—O32174.64 (10)
C2—C1—C6—C51.07 (18)C2—C3—N31—O323.48 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O11i0.841.862.6983 (13)172
O22—H22···O21ii0.841.892.6809 (12)155
C4—H4···O31iii0.952.413.2663 (15)150
Symmetry codes: (i) x+1, y, z+1; (ii) x+1/2, y1/2, z+1/2; (iii) x, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC8H5NO6
Mr211.13
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)9.4972 (2), 6.9014 (2), 12.3077 (3)
β (°) 92.0599 (11)
V3)806.17 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.15
Crystal size (mm)0.35 × 0.30 × 0.18
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(DENZO-SMN; Otwinowski & Minor, 1997)
Tmin, Tmax0.945, 0.972
No. of measured, independent and
observed [I > 2σ(I)] reflections
9456, 1827, 1641
Rint0.051
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.087, 1.07
No. of reflections1827
No. of parameters138
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.32, 0.33

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
C11—O111.2169 (16)C21—O211.2160 (15)
C11—O121.3171 (15)C21—O221.3130 (14)
C1—C111.4977 (16)C2—C211.5148 (16)
C2—C1—C6120.41 (11)C2—C3—C4122.89 (11)
C1—C2—C3117.19 (11)
C2—C1—C11—O116.30 (18)C2—C3—N31—O323.48 (15)
C1—C2—C21—O2192.11 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O12—H12···O11i0.841.862.6983 (13)172
O22—H22···O21ii0.841.892.6809 (12)155
C4—H4···O31iii0.952.413.2663 (15)150
Symmetry codes: (i) x+1, y, z+1; (ii) x+1/2, y1/2, z+1/2; (iii) x, y+2, z+1.
 

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