Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103002555/sk1616sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103002555/sk1616Isup2.hkl |
CCDC reference: 208025
A sample of 3-nitrophthalic acid (Aldrich) was crystallized by slow evaporation of a solution in ethanol.
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.
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).
C8H5NO6 | F(000) = 432 |
Mr = 211.13 | Dx = 1.740 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1827 reflections |
a = 9.4972 (2) Å | θ = 3.4–27.5° |
b = 6.9014 (2) Å | µ = 0.15 mm−1 |
c = 12.3077 (3) Å | T = 120 K |
β = 92.0599 (11)° | Block, brown |
V = 806.17 (3) Å3 | 0.35 × 0.30 × 0.18 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 1827 independent reflections |
Radiation source: rotating anode | 1641 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −12→12 |
Tmin = 0.945, Tmax = 0.972 | k = −8→8 |
9456 measured reflections | l = −15→15 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-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 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C8H5NO6 | V = 806.17 (3) Å3 |
Mr = 211.13 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.4972 (2) Å | µ = 0.15 mm−1 |
b = 6.9014 (2) Å | T = 120 K |
c = 12.3077 (3) Å | 0.35 × 0.30 × 0.18 mm |
β = 92.0599 (11)° |
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 = 0.972 | Rint = 0.051 |
9456 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.32 e Å−3 |
1827 reflections | Δρmin = −0.33 e Å−3 |
138 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.31621 (12) | 0.42340 (17) | 0.52082 (10) | 0.0125 (3) | |
C2 | 0.21751 (12) | 0.46514 (16) | 0.43625 (9) | 0.0105 (2) | |
C3 | 0.13797 (12) | 0.63375 (17) | 0.44588 (9) | 0.0110 (2) | |
C4 | 0.15784 (13) | 0.76347 (17) | 0.53133 (10) | 0.0143 (3) | |
C5 | 0.25745 (13) | 0.72129 (19) | 0.61288 (10) | 0.0165 (3) | |
C6 | 0.33469 (13) | 0.55049 (19) | 0.60876 (10) | 0.0155 (3) | |
C11 | 0.40129 (13) | 0.24112 (18) | 0.51580 (10) | 0.0139 (3) | |
O11 | 0.39628 (10) | 0.13587 (13) | 0.43643 (7) | 0.0198 (2) | |
O12 | 0.48057 (11) | 0.20781 (14) | 0.60382 (8) | 0.0235 (2) | |
C21 | 0.20877 (12) | 0.33648 (16) | 0.33651 (9) | 0.0108 (2) | |
O21 | 0.27612 (9) | 0.37307 (12) | 0.25687 (7) | 0.0141 (2) | |
O22 | 0.12760 (9) | 0.18427 (12) | 0.34762 (7) | 0.0140 (2) | |
N31 | 0.02428 (10) | 0.67570 (14) | 0.36443 (8) | 0.0118 (2) | |
O31 | −0.04206 (9) | 0.82741 (13) | 0.37272 (8) | 0.0179 (2) | |
O32 | −0.00067 (10) | 0.55423 (13) | 0.29332 (7) | 0.0176 (2) | |
H4 | 0.1040 | 0.8793 | 0.5338 | 0.017* | |
H5 | 0.2730 | 0.8090 | 0.6716 | 0.020* | |
H6 | 0.4005 | 0.5198 | 0.6661 | 0.019* | |
H12 | 0.5222 | 0.1013 | 0.5975 | 0.035* | |
H22 | 0.1448 | 0.1026 | 0.2993 | 0.021* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0132 (6) | 0.0115 (6) | 0.0128 (6) | 0.0007 (4) | 0.0013 (4) | 0.0015 (4) |
C2 | 0.0110 (5) | 0.0090 (5) | 0.0117 (5) | −0.0012 (4) | 0.0024 (4) | 0.0010 (4) |
C3 | 0.0109 (5) | 0.0101 (5) | 0.0120 (6) | −0.0004 (4) | 0.0012 (4) | 0.0016 (4) |
C4 | 0.0142 (6) | 0.0111 (5) | 0.0179 (6) | 0.0010 (4) | 0.0033 (5) | −0.0024 (5) |
C5 | 0.0177 (6) | 0.0162 (6) | 0.0155 (6) | −0.0009 (5) | 0.0004 (5) | −0.0045 (5) |
C6 | 0.0149 (6) | 0.0182 (6) | 0.0134 (6) | −0.0005 (5) | −0.0011 (5) | −0.0004 (5) |
C11 | 0.0135 (6) | 0.0135 (6) | 0.0145 (6) | 0.0010 (4) | −0.0006 (4) | 0.0029 (4) |
O11 | 0.0240 (5) | 0.0167 (5) | 0.0183 (5) | 0.0087 (4) | −0.0041 (4) | −0.0031 (4) |
O12 | 0.0315 (5) | 0.0191 (5) | 0.0191 (5) | 0.0131 (4) | −0.0083 (4) | −0.0010 (4) |
C21 | 0.0117 (5) | 0.0081 (5) | 0.0126 (6) | 0.0033 (4) | −0.0011 (4) | 0.0009 (4) |
O21 | 0.0189 (4) | 0.0104 (4) | 0.0132 (4) | 0.0014 (3) | 0.0035 (3) | 0.0007 (3) |
O22 | 0.0168 (4) | 0.0094 (4) | 0.0160 (4) | −0.0017 (3) | 0.0030 (3) | −0.0031 (3) |
N31 | 0.0122 (5) | 0.0095 (5) | 0.0139 (5) | 0.0003 (4) | 0.0024 (4) | 0.0009 (4) |
O31 | 0.0188 (4) | 0.0127 (4) | 0.0221 (5) | 0.0071 (3) | −0.0008 (4) | −0.0006 (3) |
O32 | 0.0204 (5) | 0.0145 (4) | 0.0173 (5) | 0.0021 (3) | −0.0050 (4) | −0.0042 (3) |
C11—O11 | 1.2169 (16) | C3—N31 | 1.4754 (15) |
C11—O12 | 1.3171 (15) | C4—C5 | 1.3853 (18) |
C1—C11 | 1.4977 (16) | C4—H4 | 0.95 |
C21—O21 | 1.2160 (15) | C5—C6 | 1.3902 (18) |
C21—O22 | 1.3130 (14) | C5—H5 | 0.95 |
C2—C21 | 1.5148 (16) | C6—H6 | 0.95 |
C1—C6 | 1.3992 (17) | O12—H12 | 0.84 |
C1—C2 | 1.4054 (17) | O22—H22 | 0.84 |
C2—C3 | 1.3947 (16) | N31—O31 | 1.2281 (13) |
C3—C4 | 1.3888 (17) | N31—O32 | 1.2288 (13) |
C2—C1—C6 | 120.41 (11) | C5—C6—C1 | 120.53 (12) |
C6—C1—C11 | 120.37 (11) | C5—C6—H6 | 119.7 |
C2—C1—C11 | 119.22 (11) | C1—C6—H6 | 119.7 |
C1—C2—C3 | 117.19 (11) | O11—C11—O12 | 124.12 (11) |
C3—C2—C21 | 122.95 (10) | O11—C11—C1 | 121.93 (11) |
C1—C2—C21 | 119.71 (10) | O12—C11—C1 | 113.95 (10) |
C2—C3—C4 | 122.89 (11) | C11—O12—H12 | 109.5 |
C4—C3—N31 | 117.66 (10) | O21—C21—O22 | 125.30 (11) |
C2—C3—N31 | 119.43 (10) | O21—C21—C2 | 121.09 (10) |
C5—C4—C3 | 118.93 (11) | O22—C21—C2 | 113.57 (10) |
C5—C4—H4 | 120.5 | C21—O22—H22 | 109.5 |
C3—C4—H4 | 120.5 | O31—N31—O32 | 123.67 (10) |
C4—C5—C6 | 119.95 (11) | O31—N31—C3 | 118.42 (10) |
C4—C5—H5 | 120.0 | O32—N31—C3 | 117.89 (9) |
C6—C5—H5 | 120.0 | ||
C6—C1—C2—C3 | −1.65 (17) | C11—C1—C6—C5 | 179.01 (11) |
C11—C1—C2—C3 | 178.28 (10) | C6—C1—C11—O11 | −173.77 (12) |
C6—C1—C2—C21 | 174.06 (10) | C2—C1—C11—O11 | 6.30 (18) |
C11—C1—C2—C21 | −6.02 (16) | C6—C1—C11—O12 | 5.97 (17) |
C1—C2—C3—C4 | 3.38 (17) | C2—C1—C11—O12 | −173.96 (11) |
C21—C2—C3—C4 | −172.17 (11) | C3—C2—C21—O21 | 83.34 (15) |
C1—C2—C3—N31 | −174.63 (10) | C1—C2—C21—O21 | −92.11 (14) |
C21—C2—C3—N31 | 9.81 (16) | C3—C2—C21—O22 | −98.93 (13) |
C2—C3—C4—C5 | −2.31 (18) | C1—C2—C21—O22 | 85.62 (13) |
N31—C3—C4—C5 | 175.74 (10) | C4—C3—N31—O31 | 3.79 (16) |
C3—C4—C5—C6 | −0.56 (18) | C2—C3—N31—O31 | −178.09 (10) |
C4—C5—C6—C1 | 2.21 (19) | C4—C3—N31—O32 | −174.64 (10) |
C2—C1—C6—C5 | −1.07 (18) | C2—C3—N31—O32 | 3.48 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O11i | 0.84 | 1.86 | 2.6983 (13) | 172 |
O22—H22···O21ii | 0.84 | 1.89 | 2.6809 (12) | 155 |
C4—H4···O31iii | 0.95 | 2.41 | 3.2663 (15) | 150 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C8H5NO6 |
Mr | 211.13 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 9.4972 (2), 6.9014 (2), 12.3077 (3) |
β (°) | 92.0599 (11) |
V (Å3) | 806.17 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.35 × 0.30 × 0.18 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.945, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9456, 1827, 1641 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 1.07 |
No. of reflections | 1827 |
No. of parameters | 138 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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).
C11—O11 | 1.2169 (16) | C21—O21 | 1.2160 (15) |
C11—O12 | 1.3171 (15) | C21—O22 | 1.3130 (14) |
C1—C11 | 1.4977 (16) | C2—C21 | 1.5148 (16) |
C2—C1—C6 | 120.41 (11) | C2—C3—C4 | 122.89 (11) |
C1—C2—C3 | 117.19 (11) | ||
C2—C1—C11—O11 | 6.30 (18) | C2—C3—N31—O32 | 3.48 (15) |
C1—C2—C21—O21 | −92.11 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
O12—H12···O11i | 0.84 | 1.86 | 2.6983 (13) | 172 |
O22—H22···O21ii | 0.84 | 1.89 | 2.6809 (12) | 155 |
C4—H4···O31iii | 0.95 | 2.41 | 3.2663 (15) | 150 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x, −y+2, −z+1. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
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).