3-Nitro­benzaldehyde

Engwerda, A.H.J.; Brugman, S.J.T.; Tinnemans, P.; Vlieg, E.

doi:10.1107/S2414314618000925

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180092

https://doi.org/10.1107/S2414314618000925

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3-Nitrobenzaldehyde

Antonius H.J. Engwerda,^a Sander J.T. Brugman,^a Paul Tinnemans ^a ^* and Elias Vlieg ^a

^aRadboud University, Institute for Molecules and Materials, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands
^*Correspondence e-mail: p.tinnemans@science.ru.nl

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 5 January 2018; accepted 15 January 2018; online 19 January 2018)

Polymorph I of the title compound, C₇H₅NO₃, is approximately planar: the dihedral angle between the benzene ring and the nitro group is 10.41 (4)° and the aldehyde O atom deviates from the ring plane by 0.165 (1) Å. In the crystal, aromatic π–π stacking interactions are observed [centroid–centroid separation = 3.7363 (5) Å].

Keywords: crystal structure; π–π stacking interactions; nitrobenzaldehyde.

CCDC reference: 1816967

Structure description

The existence of two polymorphic forms of the title compound, C₇H₅NO₃, has been known for almost eighty years (Lindpaintner, 1939 ); however, to date no crystal structure of the title compound has been reported. Here, we present the crystal structure of the stable polymorph (polymorph I). For the crystal structure of the closely related compound 2-nitrobenzaldehyde, see Coppens & Schmidt (1964 ) and Coppens (1964 ) and for the crystal structure of 4-nitrobenzalhyde, see Jackisch et al. (1989 ) and King & Bryant (1996 ).

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the benzene ring and the nitro group is 10.41 (4)° and the aldehyde O atom deviates from the ring plane by 0.165 (1) Å. In the crystal, aromatic π–π stacking interactions are observed [centroid–centroid separation = 3.7363 (5) Å].

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.

The melting point of the stable polymorph is 327 K, while the melting point of polymorph II is 322 K, as determined using the onset temperature of differential scanning calorimetry.

Synthesis and crystallization

A 100 mg mL⁻¹ solution of 3-nitrobenzaldehyde (Merck, no indication of purity given) in acetone was filtered to obtain a clear yellow solution. Slow evaporation of a 1:1 mixture of this solution and heptane resulted in large colourless needle-shaped crystals of the title compound after two days.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₇H₅NO₃
M_r	151.12
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	150
a, b, c (Å)	3.7363 (2), 7.0071 (3), 12.5877 (6)
β (°)	94.8144 (16)
V (Å³)	328.39 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.48 × 0.17 × 0.09

Data collection
Diffractometer	Bruker D8 Quest APEX3
Absorption correction	Multi-scan (SADABS; Bruker, 2011 )
T_min, T_max	0.713, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	18662, 4005, 3735
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.909

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.089, 1.05
No. of reflections	4005
No. of parameters	100
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.21
Absolute structure	Flack x determined using 1595 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	−0.02 (13)
Computer programs: APEX3 (Bruker, 2012 ), PEAKREF (Schreurs, 2013 ), SAINT (Bruker, 2012), SHELXT2014/4 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), PLATON (Spek, 2009 ) and ShelXLe (Hübschle et al., 2011 ).

Structural data

CCDC reference: 1816967

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000925/hb4202sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000925/hb4202Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618000925/hb4202Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2414314618000925/hb4202Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2012); cell refinement: PEAKREF (Schreurs, 2013); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT2014/4 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009) and ShelXLe (Hübschle et al., 2011).

3-Nitrobenzaldehyde top

Crystal data top

C₇H₅NO₃	D_x = 1.528 Mg m⁻³
M_r = 151.12	Melting point: 327 K
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 3.7363 (2) Å	Cell parameters from 9919 reflections
b = 7.0071 (3) Å	θ = 2.9–40.3°
c = 12.5877 (6) Å	µ = 0.12 mm⁻¹
β = 94.8144 (16)°	T = 150 K
V = 328.39 (3) Å³	Needle, colourless
Z = 2	0.48 × 0.17 × 0.09 mm
F(000) = 156

Data collection top

Bruker D8 Quest APEX3 diffractometer	4005 independent reflections
Radiation source: sealed tube	3735 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 10.4 pixels mm^-1	θ_max = 40.3°, θ_min = 3.3°
φ and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2011)	k = −12→12
T_min = 0.713, T_max = 0.748	l = −22→22
18662 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0643P)² + 0.0066P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
4005 reflections	Δρ_max = 0.38 e Å⁻³
100 parameters	Δρ_min = −0.21 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1595 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (13)

Special details top

Experimental. Polymorph I

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

	x	y	z	U_iso*/U_eq
O01	0.3805 (2)	0.36964 (11)	0.47803 (5)	0.02774 (14)
O02	0.5659 (2)	0.81726 (10)	0.79109 (6)	0.02858 (15)
O03	0.3141 (2)	0.75360 (14)	0.93565 (6)	0.03273 (17)
N01	0.39008 (18)	0.71338 (9)	0.84537 (5)	0.01838 (11)
C01	0.26607 (18)	0.52935 (9)	0.79964 (5)	0.01429 (10)
C02	0.1223 (2)	0.39635 (11)	0.86644 (6)	0.01736 (12)
H02	0.101303	0.424953	0.939430	0.021*
C03	0.0102 (2)	0.22081 (11)	0.82413 (6)	0.01891 (13)
H03	−0.087439	0.127606	0.868273	0.023*
C04	0.0419 (2)	0.18223 (10)	0.71667 (6)	0.01706 (12)
H04	−0.036577	0.062838	0.687503	0.020*
C05	0.18828 (17)	0.31822 (9)	0.65163 (5)	0.01416 (10)
C06	0.30344 (19)	0.49536 (10)	0.69286 (5)	0.01405 (10)
H06	0.403384	0.588642	0.649244	0.017*
C07	0.2287 (2)	0.26924 (11)	0.53892 (6)	0.01863 (12)
H07	0.129789	0.151915	0.512489	0.022*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O01	0.0390 (3)	0.0266 (3)	0.0188 (2)	−0.0037 (3)	0.0094 (2)	−0.0013 (2)
O02	0.0373 (3)	0.0184 (2)	0.0311 (3)	−0.0106 (3)	0.0088 (3)	−0.0032 (2)
O03	0.0461 (4)	0.0320 (3)	0.0209 (3)	−0.0065 (3)	0.0074 (3)	−0.0112 (3)
N01	0.0201 (3)	0.0162 (2)	0.0187 (2)	−0.00059 (19)	0.00057 (19)	−0.00306 (18)
C01	0.0145 (2)	0.0137 (2)	0.0148 (2)	−0.00082 (17)	0.00209 (18)	−0.00065 (17)
C02	0.0185 (3)	0.0190 (3)	0.0148 (2)	−0.0012 (2)	0.0030 (2)	0.00250 (19)
C03	0.0203 (3)	0.0171 (3)	0.0196 (3)	−0.0025 (2)	0.0034 (2)	0.0042 (2)
C04	0.0173 (3)	0.0139 (2)	0.0200 (3)	−0.00153 (19)	0.0015 (2)	0.0017 (2)
C05	0.0143 (2)	0.0129 (2)	0.0153 (2)	0.00052 (19)	0.00169 (18)	0.00008 (19)
C06	0.0148 (2)	0.0132 (2)	0.0145 (2)	−0.00045 (17)	0.00272 (17)	0.00045 (17)
C07	0.0216 (3)	0.0172 (2)	0.0174 (3)	0.0010 (2)	0.0028 (2)	−0.0031 (2)

Geometric parameters (Å, º) top

O01—C07	1.2152 (10)	C03—C04	1.3941 (10)
O02—N01	1.2262 (9)	C03—H03	0.9500
O03—N01	1.2271 (9)	C04—C05	1.3974 (9)
N01—C01	1.4711 (9)	C04—H04	0.9500
C01—C06	1.3836 (9)	C05—C06	1.3992 (10)
C01—C02	1.3928 (9)	C05—C07	1.4797 (9)
C02—C03	1.3909 (11)	C06—H06	0.9500
C02—H02	0.9500	C07—H07	0.9500

O03—N01—O02	123.79 (8)	C03—C04—C05	120.36 (6)
O03—N01—C01	118.29 (7)	C03—C04—H04	119.8
O02—N01—C01	117.92 (6)	C05—C04—H04	119.8
C06—C01—C02	123.15 (6)	C04—C05—C06	120.73 (6)
C06—C01—N01	118.48 (6)	C04—C05—C07	118.69 (6)
C02—C01—N01	118.36 (6)	C06—C05—C07	120.56 (6)
C03—C02—C01	118.65 (6)	C01—C06—C05	117.39 (6)
C03—C02—H02	120.7	C01—C06—H06	121.3
C01—C02—H02	120.7	C05—C06—H06	121.3
C02—C03—C04	119.72 (6)	O01—C07—C05	124.13 (7)
C02—C03—H03	120.1	O01—C07—H07	117.9
C04—C03—H03	120.1	C05—C07—H07	117.9

O03—N01—C01—C06	170.48 (8)	C03—C04—C05—C06	−0.38 (10)
O02—N01—C01—C06	−10.01 (10)	C03—C04—C05—C07	177.92 (7)
O03—N01—C01—C02	−10.63 (11)	C02—C01—C06—C05	0.25 (10)
O02—N01—C01—C02	168.88 (7)	N01—C01—C06—C05	179.09 (6)
C06—C01—C02—C03	−0.08 (11)	C04—C05—C06—C01	−0.02 (9)
N01—C01—C02—C03	−178.92 (7)	C07—C05—C06—C01	−178.30 (6)
C01—C02—C03—C04	−0.34 (11)	C04—C05—C07—O01	−173.33 (8)
C02—C03—C04—C05	0.56 (11)	C06—C05—C07—O01	4.98 (12)

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