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An appreciable degree of pyramidalization of the amine N atom is observed in the title compound. The existence of polar chains, induced by N—H...O synthons, is confirmed. C—H...O interactions, not noted in a previous X-ray study, were found to stabilize further the known head-to-tail assembling of the chains. The structure can be described as non-polar (101) layers, embodying chains interlinked by centrosymmetric dimers, connected by C(aryl)—H...π interactions. The latter are not present in m-nitroaniline, 2-methyl-4-nitroaniline and other related compounds with chains built from similar N—H...O synthons and assembled head-to-head. This finding implies that an obvious relationship between molecular recognition patterns and crystal structures should not be assumed.

Supporting information

cif

Crystallographic Information File (CIF)
Contains datablock 2M5NA

fcf

Structure factor file (CIF format)
Contains datablock 2m5na

pdf

Portable Document Format (PDF) file
Supplementary material

CCDC reference: 132061

Computing details top

Program(s) used to refine structure: SHELXL93 (Sheldrick, 1993).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
2-methyl-5-nitroaniline top
Crystal data top
C7H8N2O2Z = 4
Mr = 152.00F(000) = 187.744
Monoclinic, P21/nDx = 1.423 Mg m3
Hall symbol: -P 2ynNeutron radiation, λ = 0.5-5.0 Å
a = 9.369 (2) ÅCell parameters from 120 reflections
b = 5.563 (1) ŵ = 0.09 mm1
c = 13.626 (3) ÅT = 100 K
β = 92.36 (3)°Irregular prism, orange
V = 709.6 (2) Å35 × 3 × 2 mm
Data collection top
SXD
diffractometer
3386 independent reflections
Radiation source: ISIS spallation source3386 reflections with I > 2σ(I)
None monochromatorRint = 0.060
Time of flight LAUE diffraction scansθmax = 21.5°, θmin = 1.1°
Absorption correction: empirical (using intensity measurements)
The linear absorption coefficient is wavelength dependent and it is calculated as:
mu = 0.93 + 0.89 * lambda [cm-1]
h = 024
Tmin = 0.47, Tmax = 0.85k = 013
17278 measured reflectionsl = 3027
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.067All H-atom parameters refined
wR(F2) = 0.154Calculated w = 1/[σ2(Fo2) + (0.1119P)2 + 1.3458P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.001
3386 reflectionsΔρmax = 5.08 e Å3
172 parametersΔρmin = 2.01 e Å3
0 restraintsExtinction correction: Becker-Coppens Lorentzian model
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.325
Crystal data top
C7H8N2O2V = 709.6 (2) Å3
Mr = 152.00Z = 4
Monoclinic, P21/nNeutron radiation, λ = 0.5-5.0 Å
a = 9.369 (2) ŵ = 0.09 mm1
b = 5.563 (1) ÅT = 100 K
c = 13.626 (3) Å5 × 3 × 2 mm
β = 92.36 (3)°
Data collection top
SXD
diffractometer
3386 independent reflections
Absorption correction: empirical (using intensity measurements)
The linear absorption coefficient is wavelength dependent and it is calculated as:
mu = 0.93 + 0.89 * lambda [cm-1]
3386 reflections with I > 2σ(I)
Tmin = 0.47, Tmax = 0.85Rint = 0.060
17278 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0670 restraints
wR(F2) = 0.154All H-atom parameters refined
S = 1.14Δρmax = 5.08 e Å3
3386 reflectionsΔρmin = 2.01 e Å3
172 parameters
Special details top

Experimental. Because of the kind of experiment, it is not possible to give values of theta_min and theta_max for the cell determination. Instead, we can give values of cell_measurement_sin(theta)/lambda_min 0.145 cell_measurement_sin(theta)/lambda_max 0.660

The same applies for the wavelength used for the experiment. The range of wavelengths used was 0.5–5 Angstroms

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

Refinement. Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

The extinction coefficient reported in _refine_ls_extinction_coef is in this case the refined value of the mosaic spread in units of 10-4 rad-1

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C11.00918 (9)0.1891 (2)0.29213 (8)0.00944 (14)
C20.96433 (9)0.0194 (2)0.23937 (7)0.00990 (14)
C30.86971 (10)0.1782 (2)0.28168 (8)0.0116 (2)
C40.81377 (10)0.1356 (2)0.37340 (8)0.01124 (15)
C50.85647 (9)0.0742 (2)0.42127 (7)0.00891 (13)
C60.95266 (9)0.2355 (2)0.38383 (7)0.00966 (14)
C71.01863 (11)0.0674 (2)0.13949 (9)0.0164 (2)
N11.10806 (9)0.34293 (15)0.25496 (7)0.01679 (15)
N20.79435 (7)0.13194 (13)0.51505 (6)0.01191 (12)
O10.6994 (2)0.0025 (3)0.54424 (12)0.0237 (3)
O20.8377 (2)0.3094 (3)0.56024 (11)0.0207 (3)
H30.8379 (3)0.3399 (5)0.2419 (2)0.0298 (6)
H40.7401 (3)0.2593 (5)0.4065 (2)0.0314 (6)
H60.9826 (3)0.3960 (5)0.4244 (2)0.0281 (5)
H111.1247 (3)0.5013 (5)0.2891 (3)0.0329 (6)
H121.1320 (3)0.3373 (6)0.1841 (2)0.0324 (6)
H711.1340 (3)0.0916 (8)0.1416 (3)0.0405 (8)
H720.9955 (5)0.0843 (7)0.0895 (3)0.0425 (8)
H730.9713 (4)0.2277 (7)0.1067 (3)0.0407 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0104 (3)0.0105 (3)0.0076 (4)0.0012 (2)0.0023 (2)0.0004 (2)
C20.0105 (3)0.0118 (3)0.0075 (4)0.0007 (2)0.0009 (2)0.0021 (2)
C30.0123 (3)0.0108 (3)0.0118 (4)0.0013 (2)0.0009 (2)0.0031 (3)
C40.0121 (3)0.0106 (3)0.0111 (4)0.0022 (2)0.0019 (2)0.0007 (3)
C50.0102 (3)0.0097 (3)0.0070 (4)0.0010 (2)0.0020 (2)0.0000 (2)
C60.0117 (3)0.0101 (3)0.0074 (4)0.0022 (2)0.0022 (2)0.0013 (2)
C70.0168 (4)0.0219 (5)0.0109 (5)0.0010 (3)0.0035 (3)0.0054 (3)
N10.0200 (3)0.0174 (3)0.0135 (4)0.0063 (2)0.0073 (2)0.0012 (2)
N20.0129 (2)0.0148 (3)0.0083 (3)0.0015 (2)0.0036 (2)0.0005 (2)
O10.0284 (6)0.0262 (6)0.0176 (7)0.0106 (5)0.0132 (5)0.0025 (5)
O20.0252 (5)0.0231 (6)0.0144 (7)0.0067 (4)0.0084 (4)0.0074 (4)
H30.0349 (12)0.0244 (11)0.030 (2)0.0086 (9)0.0047 (10)0.0119 (9)
H40.0315 (11)0.0297 (12)0.034 (2)0.0133 (9)0.0101 (10)0.0006 (10)
H60.0357 (12)0.0254 (11)0.0237 (14)0.0090 (9)0.0063 (9)0.0085 (9)
H110.0408 (14)0.0246 (11)0.034 (2)0.0114 (10)0.0114 (11)0.0060 (10)
H120.0372 (13)0.0398 (15)0.0210 (14)0.0081 (11)0.0120 (11)0.0011 (10)
H710.0237 (11)0.059 (2)0.039 (2)0.0035 (12)0.0090 (11)0.011 (2)
H720.059 (2)0.047 (2)0.022 (2)0.008 (2)0.0091 (14)0.0050 (13)
H730.049 (2)0.041 (2)0.032 (2)0.0116 (14)0.0089 (13)0.0167 (13)
Geometric parameters (Å, º) top
C1—N11.3734 (11)C5—N21.4615 (12)
C1—C61.4011 (13)C6—H61.081 (3)
C1—C21.4187 (13)C7—H711.088 (3)
C2—C31.3934 (13)C7—H721.101 (4)
C2—C71.4964 (15)C7—H731.084 (3)
C3—C41.3953 (15)N1—H111.006 (3)
C3—H31.086 (3)N1—H121.001 (3)
C4—C51.3878 (14)N2—O11.2235 (15)
C4—H41.086 (3)N2—O21.224 (2)
C5—C61.3840 (12)
N1—C1—C6119.95 (9)C5—C6—C1119.00 (8)
N1—C1—C2120.85 (8)C5—C6—H6120.4 (2)
C6—C1—C2119.19 (8)C1—C6—H6120.6 (2)
C3—C2—C1119.27 (9)C2—C7—H71111.9 (2)
C3—C2—C7120.60 (9)C2—C7—H72111.1 (2)
C1—C2—C7120.13 (9)H71—C7—H72106.3 (3)
C2—C3—C4122.11 (9)C2—C7—H73111.9 (2)
C2—C3—H3119.0 (2)H71—C7—H73107.3 (3)
C4—C3—H3118.9 (2)H72—C7—H73108.0 (4)
C5—C4—C3116.90 (8)C1—N1—H11118.0 (2)
C5—C4—H4120.9 (2)C1—N1—H12121.2 (2)
C3—C4—H4122.2 (2)H11—N1—H12116.0 (3)
C6—C5—C4123.47 (9)O1—N2—O2122.79 (11)
C6—C5—N2117.95 (8)O1—N2—C5118.42 (10)
C4—C5—N2118.57 (8)O2—N2—C5118.78 (9)
H12—N1—C1—C215.9 (3)H11—N1—C1—C2170.2 (3)
H12—N1—C1—C6164.9 (3)H11—N1—C1—C610.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H12···O1i1.001 (3)2.219 (4)3.149 (2)154.0 (3)
N1—H12···O2i1.001 (3)2.738 (4)3.585 (2)142.7 (3)
N1—H11···O1ii1.004 (3)2.321 (3)3.199 (2)145.3 (3)
C3—H3···C(Ph)iii1.085 (3)2.608 (3)3.414 (1)130.5 (2)
C4—H4···O11.086 (3)2.418 (4)2.713 (2)93.7 (2)
C6—H6···O21.081 (3)2.389 (3)2.706 (2)94.9 (2)
C6—H6···O2ii1.081 (3)2.353 (3)3.275 (2)142.2 (2)
C7—H71···O2i1.088 (3)2.740 (4)3.525 (2)128.8 (3)
C7—H71···O1iv1.088 (3)2.725 (4)3.255 (2)109.5 (3)
C7—H73···O1iv1.084 (4)2.789 (4)3.255 (2)105.8 (2)
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+2, y+1, z+1; (iii) x+3/2, y1/2, z+1/2; (iv) x+1/2, y1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC7H8N2O2
Mr152.00
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)9.369 (2), 5.563 (1), 13.626 (3)
β (°) 92.36 (3)
V3)709.6 (2)
Z4
Radiation typeNeutron, λ = 0.5-5.0 Å
µ (mm1)0.09
Crystal size (mm)5 × 3 × 2
Data collection
DiffractometerSXD
diffractometer
Absorption correctionEmpirical (using intensity measurements)
The linear absorption coefficient is wavelength dependent and it is calculated as:

mu = 0.93 + 0.89 * lambda [cm-1]

Tmin, Tmax0.47, 0.85
No. of measured, independent and
observed [I > 2σ(I)] reflections
17278, 3386, 3386
Rint0.060
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.067, 0.154, 1.14
No. of reflections3386
No. of parameters172
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)5.08, 2.01

Computer programs: SHELXL93 (Sheldrick, 1993).

Selected geometric parameters (Å, º) top
C1—N11.3734 (11)C5—N21.4615 (12)
C1—C61.4011 (13)C6—H61.081 (3)
C1—C21.4187 (13)C7—H711.088 (3)
C2—C31.3934 (13)C7—H721.101 (4)
C2—C71.4964 (15)C7—H731.084 (3)
C3—C41.3953 (15)N1—H111.006 (3)
C3—H31.086 (3)N1—H121.001 (3)
C4—C51.3878 (14)N2—O11.2235 (15)
C4—H41.086 (3)N2—O21.224 (2)
C5—C61.3840 (12)
N1—C1—C6119.95 (9)C5—C6—C1119.00 (8)
N1—C1—C2120.85 (8)C5—C6—H6120.4 (2)
C6—C1—C2119.19 (8)C1—C6—H6120.6 (2)
C3—C2—C1119.27 (9)C2—C7—H71111.9 (2)
C3—C2—C7120.60 (9)C2—C7—H72111.1 (2)
C1—C2—C7120.13 (9)H71—C7—H72106.3 (3)
C2—C3—C4122.11 (9)C2—C7—H73111.9 (2)
C2—C3—H3119.0 (2)H71—C7—H73107.3 (3)
C4—C3—H3118.9 (2)H72—C7—H73108.0 (4)
C5—C4—C3116.90 (8)C1—N1—H11118.0 (2)
C5—C4—H4120.9 (2)C1—N1—H12121.2 (2)
C3—C4—H4122.2 (2)H11—N1—H12116.0 (3)
C6—C5—C4123.47 (9)O1—N2—O2122.79 (11)
C6—C5—N2117.95 (8)O1—N2—C5118.42 (10)
C4—C5—N2118.57 (8)O2—N2—C5118.78 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H12···O1i1.001 (3)2.219 (4)3.149 (2)154.0 (3)
N1—H12···O2i1.001 (3)2.738 (4)3.585 (2)142.7 (3)
N1—H11···O1ii1.004 (3)2.321 (3)3.199 (2)145.3 (3)
C3—H3···C(Ph)iii1.085 (3)2.608 (3)3.414 (1)130.5 (2)
C4—H4···O11.086 (3)2.418 (4)2.713 (2)93.7 (2)
C6—H6···O21.081 (3)2.389 (3)2.706 (2)94.9 (2)
C6—H6···O2ii1.081 (3)2.353 (3)3.275 (2)142.2 (2)
C7—H71···O2i1.088 (3)2.740 (4)3.525 (2)128.8 (3)
C7—H71···O1iv1.088 (3)2.725 (4)3.255 (2)109.5 (3)
C7—H73···O1iv1.084 (4)2.789 (4)3.255 (2)105.8 (2)
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+2, y+1, z+1; (iii) x+3/2, y1/2, z+1/2; (iv) x+1/2, y1/2, z1/2.
 
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