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Polymorphism is a challenging phenomenon and the competitive packing alternatives which are characteristic for polymorphs may be encountered for essentially rigid mol­ecules. A second crystal form of the well known compound o-nitro­benzoic acid, C7H5NO4, an important inter­mediate in the production of dyes, pharmaceuticals and agrochemicals, is described. Although obtained serendipitously, its intra- and inter­molecular features match expectations from database searches and theoretical calculations. O-H...O hydrogen-bonded carb­oxy­lic acid dimers represent the building blocks in both polymorphs. For steric reasons and in agreement with a calculated potential energy surface, the carb­oxy­lic acid and nitro groups cannot simultaneously be coplanar with the benzene ring but have to tilt. In the well established crystal form, this out-of-plane torsion is more pronounced for the nitro substituent. In contrast, the new polymorph is characterized by a major tilt of the carb­oxy­lic acid group. The mol­ecules in both alternative crystal forms achieve a similar compromise with respect to acceptable intra­molecular O...O contacts.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229616009591/sk3630sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2053229616009591/sk3630Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229616009591/sk3630Isup5.cml
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616009591/sk3630sup3.pdf
supporting information: powder pattern of the (1beta) polymorph, details concerning potential energy surface calculation

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S2053229616009591/sk3630sup4.pdf
Supplementary material

CCDC reference: 1482497

Computing details top

Data collection: CrysAlis PRO (Agilent, 2009); cell refinement: CrysAlis PRO (Agilent, 2009); data reduction: CrysAlis PRO (Agilent, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

2-Nitrobenzoic acid top
Crystal data top
C7H5NO4F(000) = 344
Mr = 167.12Dx = 1.542 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybcCell parameters from 1107 reflections
a = 3.9356 (4) Åθ = 3.5–74.2°
b = 7.2005 (6) ŵ = 1.12 mm1
c = 25.410 (2) ÅT = 291 K
β = 90.578 (9)°Plate, colorless
V = 720.05 (11) Å30.23 × 0.15 × 0.02 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur Ruby
diffractometer
1472 independent reflections
Radiation source: Enhance (Cu) X-ray Source1031 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.038
Detector resolution: 10.2576 pixels mm-1θmax = 75.9°, θmin = 3.5°
ω scansh = 44
Absorption correction: multi-scan
SCALE3 ABSPACK
k = 69
Tmin = 0.919, Tmax = 1.000l = 2931
4635 measured reflections
Refinement top
Refinement on F21 restraint
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.144 w = 1/[σ2(Fo2) + (0.0601P)2 + 0.112P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1472 reflectionsΔρmax = 0.15 e Å3
113 parametersΔρmin = 0.20 e Å3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.4327 (6)0.7758 (3)0.48230 (7)0.0741 (6)
H20.700 (14)1.063 (6)0.4701 (14)0.17 (2)*
O20.7458 (6)0.9879 (3)0.44391 (8)0.0812 (7)
O30.3444 (6)0.9865 (3)0.35515 (10)0.0861 (7)
O40.6779 (8)0.9726 (4)0.28929 (9)0.1019 (9)
N10.5646 (5)0.9107 (3)0.33003 (8)0.0587 (5)
C10.7008 (5)0.6939 (3)0.40331 (9)0.0459 (5)
C20.7000 (6)0.7330 (3)0.34994 (9)0.0484 (5)
C30.8066 (7)0.6064 (4)0.31303 (10)0.0636 (7)
H30.80270.63630.27740.076*
C40.9192 (8)0.4346 (4)0.32961 (12)0.0714 (8)
H40.99480.34810.30520.086*
C50.9197 (7)0.3913 (3)0.38217 (12)0.0685 (7)
H50.99510.27520.39320.082*
C60.8094 (7)0.5184 (3)0.41869 (10)0.0586 (6)
H60.80760.48640.45410.070*
C70.6140 (6)0.8287 (3)0.44571 (8)0.0475 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.1094 (16)0.0585 (10)0.0550 (10)0.0188 (9)0.0346 (10)0.0104 (8)
O20.1195 (18)0.0555 (11)0.0692 (12)0.0298 (10)0.0392 (12)0.0213 (9)
O30.0830 (14)0.0660 (12)0.1096 (17)0.0170 (10)0.0173 (13)0.0051 (11)
O40.145 (2)0.1061 (18)0.0554 (12)0.0207 (15)0.0102 (14)0.0278 (12)
N10.0658 (13)0.0602 (12)0.0501 (12)0.0004 (10)0.0051 (10)0.0020 (9)
C10.0467 (11)0.0439 (11)0.0473 (11)0.0053 (8)0.0080 (9)0.0055 (9)
C20.0490 (12)0.0493 (11)0.0469 (12)0.0061 (9)0.0050 (9)0.0067 (9)
C30.0760 (17)0.0680 (16)0.0470 (13)0.0105 (12)0.0128 (12)0.0150 (11)
C40.0848 (19)0.0561 (15)0.0739 (18)0.0064 (13)0.0275 (15)0.0244 (13)
C50.0762 (17)0.0426 (12)0.087 (2)0.0016 (11)0.0197 (15)0.0080 (12)
C60.0715 (16)0.0477 (12)0.0569 (14)0.0028 (10)0.0118 (12)0.0000 (10)
C70.0554 (12)0.0464 (11)0.0408 (11)0.0023 (9)0.0054 (9)0.0022 (9)
Geometric parameters (Å, º) top
O1—C71.238 (3)C2—C31.377 (3)
O2—C71.259 (3)C3—C41.379 (4)
O2—H20.88 (2)C3—H30.9300
O3—N11.211 (3)C4—C51.371 (4)
O4—N11.216 (3)C4—H40.9300
N1—C21.474 (3)C5—C61.377 (3)
C1—C21.385 (3)C5—H50.9300
C1—C61.389 (3)C6—H60.9300
C1—C71.492 (3)
C7—O2—H2116 (3)C5—C4—C3119.9 (2)
O3—N1—O4123.6 (2)C5—C4—H4120.0
O3—N1—C2117.9 (2)C3—C4—H4120.0
O4—N1—C2118.4 (2)C4—C5—C6120.5 (3)
C2—C1—C6117.3 (2)C4—C5—H5119.7
C2—C1—C7125.2 (2)C6—C5—H5119.7
C6—C1—C7117.4 (2)C5—C6—C1120.9 (2)
C3—C2—C1122.3 (2)C5—C6—H6119.5
C3—C2—N1116.9 (2)C1—C6—H6119.5
C1—C2—N1120.66 (19)O1—C7—O2123.2 (2)
C2—C3—C4119.0 (3)O1—C7—C1118.71 (19)
C2—C3—H3120.5O2—C7—C1117.9 (2)
C4—C3—H3120.5
Crystal data, parameters of packing and intramolecular geometry in polymorphs (1α) (Portalone, 2009) and (1β) top
Crystal form(1α)(1β)
Space group (No.)P1 (2)P21/c (14)
a (Å)5.0147 (15)3.9356 (4)
b (Å)7.527 (2)7.2005 (6)
c (Å)10.620 (2)25.410 (2)
α (°)69.41 (2)90
β (°)86.07 (2)90.578 (9)
γ (°)71.01 (3)90
Z24
V/Z (Å)3177.09 (9)180.01 (3)
Density (Mg m-3)1.5671.542
Packing index (%) (Spek, 2009)72.370.8
θ1 (°)20.5 (4)46.9 (3)
θ2 (°)54.5 (3)28.4 (3)
O···O (Å)2.863 (3)2.741 (3)
 

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