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ISSN: 2056-9890

3,4-Di­amino­benzo­nitrile

aDepartment of Chemistry, State University of New York-College at Geneseo, 1 College Circle, Geneseo, NY 14454, USA
*Correspondence e-mail: geiger@geneseo.edu

(Received 18 February 2013; accepted 22 February 2013; online 28 February 2013)

The non-H atoms in the structure of the title mol­ecule, C7H7N3, are almost coplanar (r.m.s. deviation = 0.018 Å). The two amine groups each donate two and accept one weak N—H⋯N hydrogen bonds. N—H⋯N hydrogen bonding between the amine and nitrile groups results in chains parallel to [101] in the crystal structure. The chains are cross-linked by N—H⋯N hydrogen bonds between amine groups, giving rise to an infinite three-dimensional network.

Related literature

For the crystal structures of related compounds, see: Czapik & Gdaniec (2010[Czapik, A. & Gdaniec, M. (2010). Acta Cryst. C66, o198-o201.]); Stålhandske (1981[Stålhandske, C. (1981). Cryst. Struct. Commun. 10, 1081-1086.]).

[Scheme 1]

Experimental

Crystal data
  • C7H7N3

  • Mr = 133.16

  • Monoclinic, P 21 /c

  • a = 8.858 (3) Å

  • b = 10.536 (4) Å

  • c = 8.160 (3) Å

  • β = 116.213 (12)°

  • V = 683.2 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 200 K

  • 0.50 × 0.20 × 0.10 mm

Data collection
  • Bruker SMART X2S CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2010[Bruker (2010). APEX2, SAINT, SADABS and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.85, Tmax = 0.99

  • 2149 measured reflections

  • 1188 independent reflections

  • 662 reflections with I > 2σ(I)

  • Rint = 0.039

Refinement
  • R[F2 > 2σ(F2)] = 0.052

  • wR(F2) = 0.128

  • S = 0.96

  • 1188 reflections

  • 107 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.18 e Å−3

  • Δρmin = −0.19 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯N2i 0.89 (3) 2.37 (3) 3.251 (4) 168 (3)
N1—H1B⋯N3ii 0.91 (3) 2.31 (3) 3.147 (4) 154 (3)
N2—H2A⋯N1iii 0.90 (3) 2.36 (3) 3.246 (4) 173 (2)
N2—H2B⋯N3ii 0.93 (3) 2.42 (3) 3.303 (4) 159 (3)
Symmetry codes: (i) [-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (ii) x+1, y, z+1; (iii) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2010[Bruker (2010). APEX2, SAINT, SADABS and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2010[Bruker (2010). APEX2, SAINT, SADABS and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XSHELL (Bruker, 2010[Bruker (2010). APEX2, SAINT, SADABS and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Single crystals of the title compound were obtained during its purification by recrystallization for use in the synthesis of an organometallic complex. Figure 1 shows a view of the title molecule with the atom numbering scheme. The non-hydrogen atoms are planar with a r. m. s. deviation of 0.018 Å. The maximum deviation is for C1, which is 0.034 (2) Å out of the plane. The benzene ring is planar with a maximum deviation of 0.008 (2) Å for C4. The amine nitrogens are decidely pyramidal with H-N-H angles of 113 (3)° and 112 (2)° for N1 and N2, respectively. N1 and N2 are 0.056 (4) and 0.073 (4) Å, respectively, below the benzene plane. All four of the hydrogen atoms of the amine groups are on the opposite side of the benzene plane from the amine nitrogen atoms. The nitrile group carbon and nitrogen atoms are 0.046 (4) and 0.086 (5) Å, respectively, out of the benzene plane and are on the opposite side as the amine nitrogens. The nitrile is linear (C4-C7-N = 179.2 (3)°).

There are two known crystalline forms of 1,2-diaminobenzene (Stålhandske, 1981; Czapik & Gdaniec, 2010). In both forms, one of the N-H bonds of each amine group is coplanar with the benzene ring and an intramolecular N-H···N interaction is exhibited. Intermolecular hydrogen bonding results in layers that are joined by additional hydrogen-bonding interactions. The two forms are isostructural in two dimensions, but differ in the stacking of the layers (Czapik & Gdaniec, 2010). Figure 2 shows the hydrogen-bonding network exhibited by the title compound. In contrast to 1,2-diaminobenzene, no intramolecular hydrogen-bonding is observed. Parallel chains of molecules with an interplanar spacing of 3.32Å are formed by hydrogen-bonds involving one hydrogen atom from each of the amines and the nitrile group on adjacent molecules. The chains run parallel to [101] and are crosslinkeded by hydrogen bonds between amine groups.

Related literature top

For the crystal structures of related compounds, see: Czapik & Gdaniec (2010); Stålhandske (1981).

Experimental top

The compound was obtained commercially (Sigma-Aldrich). Single crystals were grown by slow evaporation of an ethanolic solution.

Refinement top

The H atoms bonded to carbon were refined using a riding model with C—H = 0.95 Å and Uiso = 1.2Ueq(C). The coordinates and isotropic thermal parameters of the amine H atoms were refined freely.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XSHELL (Bruker, 2010) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Perspective view of the title molecule. Displacement ellipsoids of the nonhydrogen atoms are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of the unit cell showing the chains parallel to [101] resulting from H-bonding between amine and nitrile groups and the cross-linking H-bonds between amine groups. Displacement ellipsoids of the nonhydrogen atoms are drawn at the 25% probability level.
3,4-Diaminobenzonitrile top
Crystal data top
C7H7N3F(000) = 280
Mr = 133.16Dx = 1.294 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 516 reflections
a = 8.858 (3) Åθ = 2.6–21.2°
b = 10.536 (4) ŵ = 0.08 mm1
c = 8.160 (3) ÅT = 200 K
β = 116.213 (12)°Prism, colourless
V = 683.2 (4) Å30.50 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART X2S CCD
diffractometer
1188 independent reflections
Radiation source: fine-focus sealed tube662 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.039
Detector resolution: 8.33 pixels mm-1θmax = 25.2°, θmin = 3.2°
ω scansh = 1010
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
k = 1211
Tmin = 0.85, Tmax = 0.99l = 59
2149 measured reflections
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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 0.96 w = 1/[σ2(Fo2) + (0.0526P)2]
where P = (Fo2 + 2Fc2)/3
1188 reflections(Δ/σ)max < 0.001
107 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.19 e Å3
Crystal data top
C7H7N3V = 683.2 (4) Å3
Mr = 133.16Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.858 (3) ŵ = 0.08 mm1
b = 10.536 (4) ÅT = 200 K
c = 8.160 (3) Å0.50 × 0.20 × 0.10 mm
β = 116.213 (12)°
Data collection top
Bruker SMART X2S CCD
diffractometer
1188 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
662 reflections with I > 2σ(I)
Tmin = 0.85, Tmax = 0.99Rint = 0.039
2149 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.18 e Å3
1188 reflectionsΔρmin = 0.19 e Å3
107 parameters
Special details top

Experimental. 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 > 2sigma(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.

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
xyzUiso*/Ueq
N11.0289 (3)0.4587 (3)0.7729 (3)0.0317 (7)
H1A1.025 (3)0.538 (3)0.809 (4)0.053 (10)*
H1B1.135 (4)0.433 (3)0.798 (4)0.063 (11)*
N30.3764 (3)0.3161 (2)0.0415 (3)0.0495 (8)
N21.0370 (3)0.2330 (2)0.5881 (3)0.0327 (7)
H2A1.044 (3)0.180 (3)0.507 (4)0.035 (8)*
H2B1.142 (4)0.264 (3)0.670 (4)0.068 (11)*
C10.8972 (3)0.4302 (2)0.6030 (3)0.0259 (7)
C20.9008 (3)0.3168 (2)0.5098 (3)0.0253 (7)
C30.7650 (3)0.2879 (2)0.3464 (3)0.0276 (7)
H30.76640.21220.28380.033*
C40.6251 (3)0.3686 (3)0.2712 (3)0.0298 (7)
C70.4877 (3)0.3387 (3)0.0985 (4)0.0366 (8)
C50.6212 (3)0.4783 (3)0.3641 (3)0.0323 (8)
H50.52620.53290.31500.039*
C60.7562 (3)0.5071 (3)0.5275 (3)0.0305 (7)
H60.75250.58200.59050.037*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0325 (16)0.0300 (17)0.0274 (13)0.0019 (12)0.0086 (13)0.0039 (12)
N30.0410 (15)0.0481 (18)0.0418 (15)0.0042 (13)0.0022 (14)0.0047 (13)
N20.0311 (14)0.0309 (15)0.0300 (13)0.0049 (12)0.0080 (12)0.0032 (12)
C10.0271 (15)0.0256 (16)0.0251 (14)0.0025 (12)0.0115 (13)0.0030 (12)
C20.0233 (14)0.0259 (16)0.0268 (14)0.0006 (12)0.0111 (13)0.0047 (13)
C30.0278 (14)0.0264 (17)0.0258 (14)0.0028 (12)0.0092 (13)0.0008 (12)
C40.0237 (14)0.0338 (18)0.0277 (15)0.0037 (13)0.0074 (13)0.0011 (13)
C70.0305 (16)0.036 (2)0.0387 (17)0.0015 (13)0.0108 (16)0.0062 (14)
C50.0272 (15)0.0324 (19)0.0366 (16)0.0020 (13)0.0134 (14)0.0036 (13)
C60.0345 (16)0.0252 (16)0.0327 (16)0.0016 (13)0.0156 (14)0.0015 (12)
Geometric parameters (Å, º) top
N1—C11.395 (3)C2—C31.379 (3)
N1—H1A0.89 (3)C3—C41.401 (3)
N1—H1B0.91 (3)C3—H30.9500
N3—C71.157 (3)C4—C51.392 (4)
N2—C21.401 (3)C4—C71.432 (3)
N2—H2A0.90 (3)C5—C61.375 (3)
N2—H2B0.93 (3)C5—H50.9500
C1—C61.384 (3)C6—H60.9500
C1—C21.424 (3)
C1—N1—H1A113.1 (17)C2—C3—H3119.5
C1—N1—H1B119 (2)C4—C3—H3119.5
H1A—N1—H1B113 (3)C5—C4—C3119.7 (2)
C2—N2—H2A112.9 (16)C5—C4—C7120.2 (2)
C2—N2—H2B119 (2)C3—C4—C7120.0 (2)
H2A—N2—H2B112 (2)N3—C7—C4179.2 (3)
C6—C1—N1120.7 (3)C6—C5—C4119.4 (2)
C6—C1—C2118.8 (2)C6—C5—H5120.3
N1—C1—C2120.4 (2)C4—C5—H5120.3
C3—C2—N2120.6 (2)C5—C6—C1122.0 (3)
C3—C2—C1119.1 (2)C5—C6—H6119.0
N2—C2—C1120.2 (2)C1—C6—H6119.0
C2—C3—C4121.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.89 (3)2.37 (3)3.251 (4)168 (3)
N1—H1B···N3ii0.91 (3)2.31 (3)3.147 (4)154 (3)
N2—H2A···N1iii0.90 (3)2.36 (3)3.246 (4)173 (2)
N2—H2B···N3ii0.93 (3)2.42 (3)3.303 (4)159 (3)
Symmetry codes: (i) x+2, y+1/2, z+3/2; (ii) x+1, y, z+1; (iii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC7H7N3
Mr133.16
Crystal system, space groupMonoclinic, P21/c
Temperature (K)200
a, b, c (Å)8.858 (3), 10.536 (4), 8.160 (3)
β (°) 116.213 (12)
V3)683.2 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.50 × 0.20 × 0.10
Data collection
DiffractometerBruker SMART X2S CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2010)
Tmin, Tmax0.85, 0.99
No. of measured, independent and
observed [I > 2σ(I)] reflections
2149, 1188, 662
Rint0.039
(sin θ/λ)max1)0.600
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.128, 0.96
No. of reflections1188
No. of parameters107
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.18, 0.19

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XSHELL (Bruker, 2010) and Mercury (Macrae et al., 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N2i0.89 (3)2.37 (3)3.251 (4)168 (3)
N1—H1B···N3ii0.91 (3)2.31 (3)3.147 (4)154 (3)
N2—H2A···N1iii0.90 (3)2.36 (3)3.246 (4)173 (2)
N2—H2B···N3ii0.93 (3)2.42 (3)3.303 (4)159 (3)
Symmetry codes: (i) x+2, y+1/2, z+3/2; (ii) x+1, y, z+1; (iii) x, y+1/2, z1/2.
 

Acknowledgements

This work was supported by a Congressionally directed grant from the US Department of Education (grant No. P116Z100020) for the X-ray diffractometer

References

First citationBruker (2010). APEX2, SAINT, SADABS and XSHELL. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationCzapik, A. & Gdaniec, M. (2010). Acta Cryst. C66, o198–o201.  Web of Science CSD CrossRef CAS IUCr Journals
First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CrossRef CAS IUCr Journals
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationStålhandske, C. (1981). Cryst. Struct. Commun. 10, 1081–1086.
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals

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ISSN: 2056-9890
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