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All atoms except for the two O atoms in the title compound, C13H9N5O2, are essentially coplanar as the nitro group is twisted by 12.0 (3)° with respect to its phenyl ring. The near planarity of the entire system is stabilized by an intramolecular hydrogen bond involving the nitro group which also limits the possible resonance forms of this mol­ecule. The cyano group is slightly bent.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101443X/bt6074sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680101443X/bt6074Isup2.hkl
Contains datablock I

CCDC reference: 175352

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.058
  • wR factor = 0.159
  • Data-to-parameter ratio = 12.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(8) - C(13) = 1.44 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The structure of the title compound, (I), was undertaken to establish its structure as a precursor in the synthesis of a larger molecule. Specifically, a new route was sought to form a bond between an N and an aromatic C atom Confirmation by X-ray analysis was deemed to be useful.

The rings in this molecule stack alternately via the inversion and translation along the a axis at interplanar distances which are consistent with π interactions; the distances correspond to the thickness (3.4 Å) of an aromatic ring (Pauling, 1960). The distance from the least-squares plane of the C7—C12 ring to the atoms in the C1—C6 ring (via inversion and translation of +1 in x) is 3.50 (3) Å; similarly, from the C1—C6 ring to C7—C12, 3.46 (3) Å.

The molecular skeleton is nearly planar as the maximum deviation from a least-squares plane involving all C and N atoms is 0.039 (3) Å for C12. The r.m.s. deviation for these fitted atoms is 0.020 Å. O1 lies 0.277 (4) Å above the plane; O2, 0.174 (4) Å below. The C2/N1/O1/O2 group has an r.m.s. deviation of 0.001 Å, while the plane of the nitro group is at an angle of 12.0 (3)° to the least-squares plane of the C1—C6 ring.

The cyano group is significantly (~8σ) bent from ideality [C8—C13—N5 = 176.7 (4)°]. This is likely due to intermolecular hydrogen bonds or dipole–dipole interactions (see Table 2) with O1, O2 and N5 and ring H atoms in adjoining molecules in the bc plane.

The intramolecular hydrogen bond between H2a and O2 (cf. Tables 1 and 2) restricts not only the rotation of the nitro group, but, as H2a is on N2, the probability of other resonance structures. It is likely that only the resonance structure shown in the Scheme makes a significant contribution as is supported by the long N2—N3 bond length [1.337 (3) Å] and the short N3—N4 bond length [1.258 (3) Å]. N2—N3 is primarily a single bond; N3—N4, a double bond. To a lesser degree this is further coroborated by the O1—N1 bond length [1.220 (3) Å] being 5σ shorter than the O2—N1 bond [1.235 (3) Å], although this difference likely is not sufficient to prove that these bonds are localized double and single bonds, respectively. Presence of the intramolecular hydrogen bond is also supported by 1H NMR, which shows a shift of 12.2 p.p.m. for H2a, indicating a high degree of deshielding. An additional consequence of the intramolecular hydrogen bond is that N1 is slightly off the center line from C5 to C2 [C5···C2—N1 = 177.0 (2)°].

In both rings a pattern of CC bond length differences is consistent with the proximity of the three electron-withdrawing groups. The bonds involving C1 and C2 (C1—C2, C1—C6 and C2—C3) are significantly (>5σ) longer than those which are two bonds away from the groups involving N1 and N2 (e.g. C3—C4 and C5—C6). Similarly, bonds involving C7 and C8 (C7—C8, C7—C12 and C8—C9) are significantly (>5σ) longer than C9—C10, C10—C11 and C11—C12. In both rings the longest CC bond lengths are adjacent to a substituent, while the shortest lengths are two bonds away from the nearest substituent.

Experimental top

Following a standard synthesis (Furniss et al., 1989), the diazonium salt formed by the reaction of m-nitroaniline with sodium nitrite was allowed to react with anthranilonitrile (2-aminobenzonitrile). The bright yellow product formed was purified via chromatography (silica gel with chloroform as the eluent) and recrystallized by vapor diffusion of Et2O into a CHCl3 solution of the product. Analysis of the product by 1H NMR was consistent with the formation of the desired C—N bond. MS data indicated that the mass of the title compound was 28 Daltons greater than what was originally expected, prior to the X-ray study, for a compound with but one N atom between the rings.

Refinement top

Constrained bond lengths C—H 0.96 Å; N—H 0.90 Å. H2a was first located in a difference map, then placed into an ideal position. All other H's were placed in ideal positions (riding H).

Computing details top

Data collection: P3/P4-PC Diffractometer Program (Siemens, 1991a); cell refinement: P3/P4-PC Diffractometer Program (Siemens, 1991a); data reduction: XDISK (Siemens, 1991b); program(s) used to solve structure: SHELXS90 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SHELXTL/PC (Sheldrick, 1990b); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 1990b) & SHELXL93 (Sheldrick, 1993).

Figures top
[Figure 1] Fig. 1. View of the title molecule showing the labeling of the non-H atoms. Thermal ellipsoids are shown at 50% probability levels; H atoms are drawn as small spheres of arbitrary radius.
2-cyano-2'-nitrodiazoaminobenzene top
Crystal data top
C13H9N5O2Z = 2
Mr = 267.25F(000) = 276
Triclinic, P1Dx = 1.397 Mg m3
a = 7.208 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.0106 (12) ÅCell parameters from 100 reflections
c = 12.256 (2) Åθ = 5.2–12.5°
α = 79.099 (7)°µ = 0.10 mm1
β = 74.695 (4)°T = 293 K
γ = 69.379 (6)°Triangular plate, yellow
V = 635.2 (2) Å30.55 × 0.40 × 0.18 mm
Data collection top
Siemens Bruker P4
diffractometer
Rint = 0.030
Radiation source: normal-focus sealed tubeθmax = 25.0°, θmin = 2.7°
Graphite monochromatorh = 18
θ/2θ scansk = 99
2825 measured reflectionsl = 1414
2247 independent reflections3 standard reflections every 100 reflections
1303 reflections with I > 2σ(I) intensity decay: 2.0%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.058Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0913P)2 + 0.1553P]
where P = (Fo2 + 2Fc2)/3
2233 reflections(Δ/σ)max < 0.001
181 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C13H9N5O2γ = 69.379 (6)°
Mr = 267.25V = 635.2 (2) Å3
Triclinic, P1Z = 2
a = 7.208 (1) ÅMo Kα radiation
b = 8.0106 (12) ŵ = 0.10 mm1
c = 12.256 (2) ÅT = 293 K
α = 79.099 (7)°0.55 × 0.40 × 0.18 mm
β = 74.695 (4)°
Data collection top
Siemens Bruker P4
diffractometer
Rint = 0.030
2825 measured reflections3 standard reflections every 100 reflections
2247 independent reflections intensity decay: 2.0%
1303 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0580 restraints
wR(F2) = 0.159H-atom parameters constrained
S = 1.06Δρmax = 0.49 e Å3
2233 reflectionsΔρmin = 0.16 e Å3
181 parameters
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 on F2 for ALL reflections except for 14 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.3083 (5)0.6944 (3)0.2649 (2)0.0874 (9)
O20.2033 (5)0.5725 (3)0.1002 (2)0.0883 (10)
N10.2658 (4)0.5679 (4)0.2040 (2)0.0562 (7)
N20.2488 (4)0.2286 (3)0.0713 (2)0.0495 (7)
H2a0.2288 (4)0.3225 (3)0.0344 (2)0.080*
N30.2477 (4)0.0702 (3)0.0127 (2)0.0463 (7)
N40.2169 (4)0.0749 (3)0.0928 (2)0.0518 (7)
N50.1155 (6)0.1816 (5)0.3704 (3)0.0952 (12)
C10.2831 (4)0.2480 (4)0.1885 (2)0.0402 (7)
C20.2911 (4)0.4098 (4)0.2553 (2)0.0429 (7)
C30.3264 (5)0.4244 (4)0.3731 (3)0.0516 (8)
H30.3310 (5)0.5365 (4)0.4171 (3)0.080*
C40.3542 (5)0.2809 (4)0.4278 (3)0.0565 (9)
H40.3799 (5)0.2912 (4)0.5093 (3)0.080*
C50.3464 (5)0.1190 (4)0.3631 (3)0.0553 (9)
H50.3648 (5)0.0184 (4)0.4012 (3)0.080*
C60.3139 (5)0.1017 (4)0.2468 (3)0.0495 (8)
H60.3096 (5)0.0111 (4)0.2040 (3)0.080*
C70.2128 (5)0.0914 (4)0.1567 (2)0.0459 (8)
C80.1724 (5)0.0952 (4)0.2751 (3)0.0476 (8)
C90.1613 (5)0.2514 (4)0.3447 (3)0.0563 (9)
H90.1352 (5)0.2532 (4)0.4258 (3)0.080*
C100.1906 (5)0.4028 (5)0.2980 (3)0.0618 (9)
H100.1793 (5)0.5098 (5)0.3466 (3)0.080*
C110.2325 (6)0.4011 (4)0.1813 (3)0.0625 (10)
H110.2538 (6)0.5083 (4)0.1492 (3)0.080*
C120.2428 (5)0.2470 (4)0.1107 (3)0.0553 (9)
H120.2725 (5)0.2468 (4)0.0296 (3)0.080*
C130.1418 (5)0.0627 (5)0.3260 (3)0.0544 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.126 (3)0.0521 (15)0.094 (2)0.045 (2)0.021 (2)0.0006 (14)
O20.140 (3)0.063 (2)0.064 (2)0.034 (2)0.011 (2)0.0227 (13)
N10.069 (2)0.0438 (15)0.058 (2)0.0200 (14)0.0146 (15)0.0053 (13)
N20.066 (2)0.0446 (15)0.0410 (14)0.0227 (13)0.0088 (13)0.0062 (11)
N30.051 (2)0.048 (2)0.0421 (14)0.0187 (12)0.0088 (12)0.0043 (11)
N40.064 (2)0.051 (2)0.0409 (15)0.0205 (14)0.0110 (13)0.0041 (12)
N50.124 (3)0.079 (2)0.080 (2)0.024 (2)0.018 (2)0.023 (2)
C10.040 (2)0.044 (2)0.038 (2)0.0166 (13)0.0036 (13)0.0067 (13)
C20.045 (2)0.039 (2)0.049 (2)0.0168 (13)0.0102 (14)0.0053 (13)
C30.056 (2)0.053 (2)0.044 (2)0.020 (2)0.0083 (15)0.0011 (14)
C40.068 (2)0.068 (2)0.036 (2)0.026 (2)0.008 (2)0.008 (2)
C50.065 (2)0.055 (2)0.050 (2)0.021 (2)0.009 (2)0.015 (2)
C60.060 (2)0.044 (2)0.047 (2)0.021 (2)0.007 (2)0.0063 (14)
C70.046 (2)0.048 (2)0.045 (2)0.0166 (14)0.0103 (14)0.0035 (14)
C80.047 (2)0.050 (2)0.046 (2)0.0158 (15)0.0130 (14)0.0010 (14)
C90.056 (2)0.062 (2)0.048 (2)0.020 (2)0.013 (2)0.004 (2)
C100.066 (2)0.052 (2)0.070 (2)0.026 (2)0.023 (2)0.013 (2)
C110.076 (3)0.048 (2)0.074 (2)0.025 (2)0.028 (2)0.005 (2)
C120.065 (2)0.057 (2)0.049 (2)0.024 (2)0.015 (2)0.007 (2)
C130.068 (2)0.053 (2)0.039 (2)0.016 (2)0.008 (2)0.008 (2)
Geometric parameters (Å, º) top
O1—N11.220 (3)C3—C41.367 (4)
O2—N11.235 (3)C4—C51.397 (4)
N1—C21.453 (4)C5—C61.370 (4)
N2—N31.337 (3)C7—C121.390 (4)
N2—C11.380 (4)C7—C81.399 (4)
N3—N41.258 (3)C8—C91.389 (4)
N4—C71.418 (4)C8—C131.438 (5)
N5—C131.119 (4)C9—C101.364 (5)
C1—C21.407 (4)C10—C111.380 (5)
C1—C61.408 (4)C11—C121.380 (4)
C2—C31.389 (4)
O1—N1—O2121.0 (3)C5—C6—C1120.9 (3)
O1—N1—C2119.0 (3)C12—C7—C8118.6 (3)
O2—N1—C2120.0 (3)C12—C7—N4125.0 (3)
N3—N2—C1120.1 (2)C8—C7—N4116.4 (3)
N4—N3—N2112.0 (2)C9—C8—C7120.4 (3)
N3—N4—C7113.0 (2)C9—C8—C13119.4 (3)
N2—C1—C2122.9 (3)C7—C8—C13120.2 (3)
N2—C1—C6120.2 (3)C10—C9—C8120.2 (3)
C2—C1—C6116.9 (3)C9—C10—C11119.9 (3)
C3—C2—C1121.4 (3)C10—C11—C12120.9 (3)
C3—C2—N1117.1 (3)C11—C12—C7120.1 (3)
C1—C2—N1121.5 (3)C5—C2—N1177.0 (2)
C4—C3—C2120.6 (3)N5—C13—C8176.7 (4)
C3—C4—C5118.9 (3)N1—O2—H2a106
C6—C5—C4121.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2a···O20.901.982.622 (3)128
C5—H5···O1i0.962.903.468 (4)119
C6—H6···O1i0.962.613.327 (4)132
C9—H9···N5ii0.962.703.573 (5)152
C10—H10···N5i0.962.623.473 (5)148
C11—H11···O2i0.963.093.562 (5)112
C12—H12···O2i0.962.583.308 (4)133
Symmetry codes: (i) x, y1, z; (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC13H9N5O2
Mr267.25
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)7.208 (1), 8.0106 (12), 12.256 (2)
α, β, γ (°)79.099 (7), 74.695 (4), 69.379 (6)
V3)635.2 (2)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.55 × 0.40 × 0.18
Data collection
DiffractometerSiemens Bruker P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2825, 2247, 1303
Rint0.030
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.058, 0.159, 1.06
No. of reflections2233
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.49, 0.16

Computer programs: P3/P4-PC Diffractometer Program (Siemens, 1991a), XDISK (Siemens, 1991b), SHELXS90 (Sheldrick, 1990a), SHELXTL/PC (Sheldrick, 1990b) & SHELXL93 (Sheldrick, 1993).

Selected geometric parameters (Å, º) top
O1—N11.220 (3)C3—C41.367 (4)
O2—N11.235 (3)C4—C51.397 (4)
N1—C21.453 (4)C5—C61.370 (4)
N2—N31.337 (3)C7—C121.390 (4)
N2—C11.380 (4)C7—C81.399 (4)
N3—N41.258 (3)C8—C91.389 (4)
N4—C71.418 (4)C8—C131.438 (5)
N5—C131.119 (4)C9—C101.364 (5)
C1—C21.407 (4)C10—C111.380 (5)
C1—C61.408 (4)C11—C121.380 (4)
C2—C31.389 (4)
O1—N1—O2121.0 (3)C3—C2—N1117.1 (3)
O1—N1—C2119.0 (3)C1—C2—N1121.5 (3)
O2—N1—C2120.0 (3)C12—C7—C8118.6 (3)
N3—N2—C1120.1 (2)C12—C7—N4125.0 (3)
N4—N3—N2112.0 (2)C5—C2—N1177.0 (2)
N3—N4—C7113.0 (2)N5—C13—C8176.7 (4)
N2—C1—C2122.9 (3)N1—O2—H2a106
N2—C1—C6120.2 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2a···O20.901.982.622 (3)128
C5—H5···O1i0.962.903.468 (4)119
C6—H6···O1i0.962.613.327 (4)132
C9—H9···N5ii0.962.703.573 (5)152
C10—H10···N5i0.962.623.473 (5)148
C11—H11···O2i0.963.093.562 (5)112
C12—H12···O2i0.962.583.308 (4)133
Symmetry codes: (i) x, y1, z; (ii) x, y, z+1.
 

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