N-(4-Nitro­benz­yl)benzene-1,2-diamine

Silversides, J.D.; Sparke, A.E.; Archibald, S.J.

doi:10.1107/S1600536806050136

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 12| December 2006| Pages o5944-o5946

https://doi.org/10.1107/S1600536806050136

N-(4-Nitrobenzyl)benzene-1,2-diamine

Jon D. Silversides,^a Amanda E. Sparke ^a and Stephen J. Archibald ^a ^*

^aDepartment of Chemistry, University of Hull, Hull HU6 7RX, England
^*Correspondence e-mail: s.j.archibald@hull.ac.uk

(Received 8 November 2006; accepted 21 November 2006; online 30 November 2006)

In the crystal structure of the title compound, C₁₃H₁₃N₃O₂, one-dimensional chains of hydrogen-bonded dimers are linked by π–π stacking interactions.

Comment

The title compound, (I), has been prepared as part of a synthetic route towards N-substituted benzimidazoles. The crystal structure is characterized by hydrogen-bonded dimers (N1—H14⋯O1ⁱ and N2—H16⋯O2ⁱ; Table 2), locking the secondary amine group, containing atom N1, into a chiral form. The dimer comprises both enantiomeric forms of the molecule. The hydrogen bonding is combined with π–π stacking, resulting in one-dimensional chains running parallel to the b axis. The π–π stacking occurs between the benzene rings (mean plane–plane distance = 3.29 Å) of the nitrobenzyl groups of dimers in adjacent unit cells.

Table 1 lists geometric parameters that are of interest. The C11—N3 and C7—N1 bonds are substantially longer than the C1—N1 and C2—N2 bonds. The shorter bond distances are typical of aniline C—N bonds. The C1—N1—C7 angle of 119.3 (1)° is similar to that of previously reported related structures showing hydrogen bonding of the secondary amine. A nitrobenzyl-substituted aniline (Iwasaki et al., 1988 ) and a nitrobenzyl-substituted 2-iodoaniline (Glidewell et al., 2004 ) have bond angles of 118.9 and 121.4°, respectively. The latter has a long range N—H⋯I interaction and π–π stacking interactions, while the former has an N—H⋯O interaction, similar to that of (I). The hydrogen-bonding array in the structure of Iwasaki et al. also affords a hydrogen-bonded dimer, each dimer having two N—H⋯O bonds. However, this dimer does not show alignment of the π systems. It appears that the four hydrogen bonds in the dimeric unit of (I) align the π systems to allow the stacking interaction to extend throughout the structure.

The N1—C7 bond is twisted by only 9.2 (2)° from the plane of the diaminobenzene ring, a smaller angle than that observed in the two related structures of Iwasaki et al. (approximately 24°) and Glidewell et al. (approximately 15°). Although the amine groups of these structures are involved in hydrogen bonding, the additional hydrogen bonds in our structure constrain the orientation of the dimeric unit. A larger torsion angle of −64.4 (2)° is observed for N1—C7—C8—C13 in this structure than the equivalent atoms in the structures of Iwasaki et al. (1988) and Glidewell et al. (2004), where the twist is around 37°.

Figure 1
The molecular structure of (I)

, showing the atom labelling and 50% probability ellipsoids for non-H atoms.

Figure 2
The hydrogen-bonded (dashed lines) dimer and π–π stacking between dimeric units.

Figure 3
The packing, viewed along the b axis.

Experimental

The title compound was prepared by a modification of a previously published procedure (Schering, 1966 ). A solution of 4-nitrobenzyl bromide (5.00 g, 0.023 mol) in methanol (300 ml) was added dropwise to a stirred solution of 1,2-phenylenediamine (12.50 g, 0.12 mol) in methanol (400 ml), and the solution was stirred at room temperature for 6 h. The solvent was removed under reduced pressure and the resulting red solid was dissolved in hot ethanol. Upon cooling, the orange precipitate was collected by filtration. Purification by flash chromatography (Silica-gel 60, dichloromethane) yielded an orange–brown solid (yield 3.56 g, 60%). X-ray quality crystals of approximate size 1.5 × 0.5 × 0.5 mm were grown by evaporation of a solution in dichloromethane/diethyl ether (70:30) and cut to an appropriate size for data collection.

Crystal data

C₁₃H₁₃N₃O₂
M_r = 243.26
Monoclinic, P 2₁ /c
a = 10.503 (2) Å
b = 6.7427 (9) Å
c = 16.452 (3) Å
β = 94.032 (15)°
V = 1162.2 (3) Å³
Z = 4
D_x = 1.390 Mg m⁻³
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 150 (2) K
Block, clear brown
0.50 × 0.46 × 0.44 mm

Data collection

Stoe IPDS-II image-plate diffractometer
ω scans
Absorption correction: none
19826 measured reflections
4980 independent reflections
2648 reflections with I > 2σ(I)
R_int = 0.053
θ_max = 34.8°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.194
S = 1.03
4980 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.1093P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.065 (8)

Table 1
Selected geometric parameters (Å, °)

C1—N1	1.3961 (18)
C2—N2	1.3998 (19)
C7—N1	1.4570 (19)
C11—N3	1.4678 (18)
N3—O2	1.2242 (18)
N3—O1	1.2268 (17)

C1—N1—C7	119.22 (11)

N1—C7—C8—C13	−64.36 (17)
C6—C1—N1—C7	−9.2 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H14⋯O1ⁱ	0.92 (2)	2.43 (2)	3.3005 (18)	158.3 (15)
N2—H16⋯O2ⁱ	0.91 (2)	2.62 (2)	3.4277 (19)	148.0 (18)
Symmetry code: (i) -x+1, -y+2, -z.

Although all the H atoms were discernible in a difference Fourier map, those bonded to C were placed in calculated positions and refined using a riding model. The C—H distances were constrained to 0.95 and 0.99 Å for aryl and methylene C atoms, respectively, with U_iso(H) = 1.2U_eq of the carrier atom. H atoms of the amine groups were freely refined [final range of N—H = 0.91 (2)–0.92 (2) Å].

Data collection: X-AREA (Stoe & Cie, 2002 ); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806050136/fb2032sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806050136/fb2032Isup2.hkl

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and WinGX (Farrugia, 1999).

N-(4-Nitrobenzyl)benzene-1,2-diamine top

Crystal data top

C₁₃H₁₃N₃O₂	F(000) = 512
M_r = 243.26	D_x = 1.390 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 166 reflections
a = 10.503 (2) Å	θ = 4.0–30.2°
b = 6.7427 (9) Å	µ = 0.10 mm⁻¹
c = 16.452 (3) Å	T = 150 K
β = 94.032 (15)°	Block, clear brown
V = 1162.2 (3) Å³	0.50 × 0.46 × 0.44 mm
Z = 4

Data collection top

Stoe IPDS-II image-plate diffractometer	2648 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.053
Graphite monochromator	θ_max = 34.8°, θ_min = 2.5°
ω scans, 111 frames at 2° intervals, exposure time 1 minute	h = −16→16
19826 measured reflections	k = −10→8
4980 independent reflections	l = −26→26

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.059	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.194	w = 1/[σ²(F_o²) + (0.1093P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4980 reflections	Δρ_max = 0.39 e Å⁻³
176 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
40 constraints	Extinction coefficient: 0.065 (8)
Primary atom site location: structure-invariant direct methods

Special details top

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 of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.18885 (13)	0.8146 (2)	0.28361 (8)	0.0302 (3)
C2	0.12405 (13)	0.9926 (2)	0.29923 (8)	0.0315 (3)
C3	0.04788 (14)	1.0000 (2)	0.36524 (9)	0.0372 (3)
H3	0.0039	1.1191	0.3762	0.045*
C4	0.03528 (15)	0.8356 (3)	0.41534 (9)	0.0400 (4)
H4	−0.0162	0.8434	0.4605	0.048*
C5	0.09761 (15)	0.6615 (3)	0.39931 (9)	0.0387 (3)
H5	0.0884	0.5488	0.4330	0.046*
C6	0.17421 (14)	0.6508 (2)	0.33352 (8)	0.0342 (3)
H6	0.2168	0.5304	0.3227	0.041*
C7	0.34034 (15)	0.6369 (2)	0.20229 (8)	0.0345 (3)
H7A	0.2856	0.5190	0.1913	0.041*
H7B	0.3975	0.6103	0.2515	0.041*
C8	0.41860 (14)	0.6762 (2)	0.13054 (8)	0.0312 (3)
C9	0.55079 (14)	0.6911 (2)	0.14095 (8)	0.0333 (3)
H9	0.5925	0.6738	0.1936	0.040*
C10	0.62238 (14)	0.7311 (2)	0.07518 (8)	0.0332 (3)
H10	0.7128	0.7402	0.0819	0.040*
C11	0.55830 (14)	0.7574 (2)	−0.00059 (8)	0.0308 (3)
C12	0.42726 (14)	0.7436 (2)	−0.01328 (8)	0.0321 (3)
H12	0.3861	0.7616	−0.0661	0.038*
C13	0.35743 (14)	0.7027 (2)	0.05303 (8)	0.0327 (3)
H13	0.2671	0.6925	0.0458	0.039*
N1	0.26129 (12)	0.80980 (19)	0.21567 (7)	0.0325 (3)
H14	0.3008 (18)	0.929 (3)	0.2064 (10)	0.037 (4)*
N2	0.14345 (13)	1.1597 (2)	0.25113 (8)	0.0355 (3)
H16	0.147 (2)	1.127 (3)	0.1976 (12)	0.045 (5)*
H15	0.0876 (19)	1.262 (4)	0.2564 (12)	0.044 (5)*
N3	0.63296 (13)	0.80231 (19)	−0.07045 (7)	0.0353 (3)
O1	0.57547 (12)	0.82773 (19)	−0.13715 (6)	0.0437 (3)
O2	0.74923 (12)	0.8135 (2)	−0.05944 (8)	0.0499 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0285 (6)	0.0331 (6)	0.0289 (5)	−0.0012 (5)	0.0008 (4)	−0.0026 (5)
C2	0.0283 (6)	0.0339 (7)	0.0319 (6)	−0.0021 (5)	−0.0001 (5)	−0.0046 (5)
C3	0.0325 (7)	0.0407 (8)	0.0388 (7)	−0.0013 (6)	0.0050 (5)	−0.0107 (6)
C4	0.0359 (7)	0.0534 (10)	0.0315 (6)	−0.0082 (7)	0.0084 (5)	−0.0068 (6)
C5	0.0383 (7)	0.0464 (9)	0.0315 (6)	−0.0082 (7)	0.0030 (5)	0.0024 (6)
C6	0.0350 (7)	0.0350 (7)	0.0324 (6)	−0.0005 (6)	0.0018 (5)	0.0010 (5)
C7	0.0379 (7)	0.0327 (7)	0.0334 (6)	0.0036 (6)	0.0071 (5)	0.0010 (5)
C8	0.0349 (7)	0.0276 (6)	0.0316 (6)	0.0038 (5)	0.0060 (5)	−0.0018 (5)
C9	0.0362 (7)	0.0335 (7)	0.0300 (6)	0.0034 (6)	0.0000 (5)	−0.0013 (5)
C10	0.0309 (6)	0.0326 (7)	0.0361 (6)	0.0014 (5)	0.0024 (5)	−0.0012 (5)
C11	0.0352 (7)	0.0264 (6)	0.0315 (6)	0.0028 (5)	0.0064 (5)	−0.0015 (5)
C12	0.0353 (7)	0.0311 (6)	0.0297 (6)	0.0038 (5)	0.0007 (5)	−0.0011 (5)
C13	0.0307 (6)	0.0334 (7)	0.0340 (6)	0.0021 (5)	0.0022 (5)	−0.0008 (5)
N1	0.0356 (6)	0.0301 (6)	0.0324 (5)	0.0015 (5)	0.0078 (4)	0.0004 (4)
N2	0.0354 (6)	0.0309 (6)	0.0403 (6)	0.0037 (5)	0.0035 (5)	−0.0010 (5)
N3	0.0394 (7)	0.0310 (6)	0.0362 (6)	0.0047 (5)	0.0092 (5)	0.0012 (4)
O1	0.0525 (7)	0.0471 (7)	0.0321 (5)	0.0026 (5)	0.0068 (4)	0.0052 (4)
O2	0.0356 (6)	0.0631 (8)	0.0526 (6)	0.0053 (6)	0.0138 (5)	0.0082 (6)

Geometric parameters (Å, º) top

C1—C6	1.391 (2)	C8—C9	1.391 (2)
C1—N1	1.3961 (18)	C8—C13	1.3984 (19)
C1—C2	1.412 (2)	C9—C10	1.387 (2)
C2—C3	1.394 (2)	C9—H9	0.9500
C2—N2	1.3998 (19)	C10—C11	1.3858 (19)
C3—C4	1.394 (2)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.381 (2)
C4—C5	1.378 (2)	C11—N3	1.4678 (18)
C4—H4	0.9500	C12—C13	1.384 (2)
C5—C6	1.395 (2)	C12—H12	0.9500
C5—H5	0.9500	C13—H13	0.9500
C6—H6	0.9500	N1—H14	0.92 (2)
C7—N1	1.4570 (19)	N2—H16	0.91 (2)
C7—C8	1.5085 (19)	N2—H15	0.91 (2)
C7—H7A	0.9900	N3—O2	1.2242 (18)
C7—H7B	0.9900	N3—O1	1.2268 (17)

C6—C1—N1	122.91 (13)	C13—C8—C7	119.69 (13)
C6—C1—C2	119.50 (13)	C10—C9—C8	120.62 (13)
N1—C1—C2	117.54 (12)	C10—C9—H9	119.7
C3—C2—N2	121.72 (13)	C8—C9—H9	119.7
C3—C2—C1	118.86 (13)	C11—C10—C9	118.10 (13)
N2—C2—C1	119.32 (12)	C11—C10—H10	120.9
C4—C3—C2	121.04 (14)	C9—C10—H10	120.9
C4—C3—H3	119.5	C12—C11—C10	122.91 (13)
C2—C3—H3	119.5	C12—C11—N3	118.51 (12)
C5—C4—C3	119.88 (13)	C10—C11—N3	118.58 (13)
C5—C4—H4	120.1	C11—C12—C13	118.17 (12)
C3—C4—H4	120.1	C11—C12—H12	120.9
C4—C5—C6	120.00 (14)	C13—C12—H12	120.9
C4—C5—H5	120.0	C12—C13—C8	120.60 (13)
C6—C5—H5	120.0	C12—C13—H13	119.7
C1—C6—C5	120.71 (14)	C8—C13—H13	119.7
C1—C6—H6	119.6	C1—N1—C7	119.22 (11)
C5—C6—H6	119.6	C1—N1—H14	112.9 (11)
N1—C7—C8	108.98 (12)	C7—N1—H14	113.9 (12)
N1—C7—H7A	109.9	C2—N2—H16	111.6 (14)
C8—C7—H7A	109.9	C2—N2—H15	115.6 (13)
N1—C7—H7B	109.9	H16—N2—H15	110.2 (18)
C8—C7—H7B	109.9	O2—N3—O1	123.16 (13)
H7A—C7—H7B	108.3	O2—N3—C11	118.63 (12)
C9—C8—C13	119.59 (13)	O1—N3—C11	118.22 (13)
C9—C8—C7	120.70 (12)

C6—C1—C2—C3	0.7 (2)	C8—C9—C10—C11	0.6 (2)
N1—C1—C2—C3	178.11 (12)	C9—C10—C11—C12	−0.7 (2)
C6—C1—C2—N2	177.18 (13)	C9—C10—C11—N3	179.23 (13)
N1—C1—C2—N2	−5.45 (19)	C10—C11—C12—C13	0.4 (2)
N2—C2—C3—C4	−176.32 (14)	N3—C11—C12—C13	−179.52 (12)
C1—C2—C3—C4	0.0 (2)	C11—C12—C13—C8	0.0 (2)
C2—C3—C4—C5	−0.7 (2)	C9—C8—C13—C12	0.0 (2)
C3—C4—C5—C6	0.7 (2)	C7—C8—C13—C12	178.46 (14)
N1—C1—C6—C5	−178.04 (13)	C6—C1—N1—C7	−9.2 (2)
C2—C1—C6—C5	−0.8 (2)	C2—C1—N1—C7	173.52 (13)
C4—C5—C6—C1	0.1 (2)	C8—C7—N1—C1	−174.31 (12)
N1—C7—C8—C9	114.11 (15)	C12—C11—N3—O2	−179.56 (14)
N1—C7—C8—C13	−64.36 (17)	C10—C11—N3—O2	0.5 (2)
C13—C8—C9—C10	−0.3 (2)	C12—C11—N3—O1	0.7 (2)
C7—C8—C9—C10	−178.74 (13)	C10—C11—N3—O1	−179.15 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H14···O1ⁱ	0.92 (2)	2.43 (2)	3.3005 (18)	158.3 (15)
N2—H16···O2ⁱ	0.91 (2)	2.62 (2)	3.4277 (19)	148.0 (18)

Symmetry code: (i) −x+1, −y+2, −z.

Acknowledgements

We thank the EPSRC for student funding and funds which enabled the purchase of the diffractometer on which the X-ray data were collected. We acknowledge the use of the EPSRC's Chemical Database Service at Daresbury (Fletcher et al., 1996 ).

References

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Fletcher, D. A., McMeeking, R. F. & Parkin, D. (1996). J. Chem. Inf. Comput. Sci. 36, 746-749. CrossRef CAS Web of Science Google Scholar
Glidewell, C., Low, J. N., Skakle, J. M. S., Wardell, S. M. S. V. & Wardell, J. L. (2004). Acta Cryst. B60, 472–480. Web of Science CSD CrossRef IUCr Journals Google Scholar
Iwasaki, F., Masuko, Y., Monma, S., Watanabe, T. & Mutai, K. (1988). Bull. Chem. Soc. Jpn, 61, 1085-1090. CrossRef CAS Web of Science Google Scholar
Schering, A. G. (1966). Patent BE 667333; Chem. Abstr. 65, 7183-7184. Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Stoe & Cie (2002). X-AREA and X-RED32. Stoe & Cie GmbH, Darmstadt, Germany. Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.