2,2′-[1,2-Phenyl­enebis(aza­nedi­yl)]di­aceto­nitrile

Rivera, A.; Jiménez-Cruz, L.; Maldonado, M.; Kučeráková, M.; Dušek, M.

doi:10.1107/S1600536812047538

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3429

doi:10.1107/S1600536812047538

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2,2′-[1,2-Phenylenebis(azanediyl)]diacetonitrile

Augusto Rivera,^a ^* Leonardo Jiménez-Cruz,^a Mauricio Maldonado,^a Monika Kučeráková ^b and Michal Dušek ^b

^aUniversidad Nacional de Colombia, Sede Bogotá, Facultad de Ciencias, Departamento de Química, Cra 30 No. 45-03, Bogotá, Código Postal 111321, Colombia, and ^bInstitute of Physics ASCR, v.v.i., Na Slovance 2, 182 21 Praha 8, Czech Republic
^*Correspondence e-mail: ariverau@unal.edu.co

(Received 17 November 2012; accepted 19 November 2012; online 24 November 2012)

The title compound, C₁₀H₁₀N₄, shows chemical but not crystallographic C₂ symmetry. The two cyanomethyl groups are located in an anti position with respect to the aromatic ring. In the crystal, molecules form parallel ladder-like tapes linked through two N—H⋯N hydrogen bonds. Further weak intramolecular N—H⋯N hydrogen bonding is responsible for the elongation of one of the C_aromatic—N bonds.

Related literature

For general background to the title compound, see: Rivera et al. (2010 ). For related structures, see: Rivera et al. (2010, 2011 ); Silversides et al. (2006 ).

Experimental

Crystal data

C₁₀H₁₀N₄
M_r = 186.2
Orthorhombic, P b c a
a = 7.6404 (3) Å
b = 15.1703 (7) Å
c = 15.9168 (7) Å
V = 1844.87 (14) Å³
Z = 8
Cu Kα radiation
μ = 0.69 mm⁻¹
T = 120 K
0.17 × 0.15 × 0.10 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.68, T_max = 1
9893 measured reflections
1641 independent reflections
1359 reflections with I > 3σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.104
S = 1.55
1641 reflections
133 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4ⁱ	0.935 (18)	2.202 (19)	3.0946 (19)	159.2 (16)
N2—H2⋯N1	0.889 (18)	2.427 (18)	2.7524 (18)	102.0 (13)
N2—H2⋯N1ⁱⁱ	0.889 (18)	2.494 (17)	3.2536 (16)	143.8 (15)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z.

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: JANA2006.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812047538/bt6866sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812047538/bt6866Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812047538/bt6866Isup3.cml

checkCIF report

Comment top

The reaction of N¹,N²-bis((1H-benzotriazol-1-yl)methyl)benzene-1,2-diamine with potassium cyanide in DMSO at room temperature gives the title compound in high yield. The two cyanomethyl groups are both anti with respect to the planar aromatic ring, no doubt in order to favour intermolecular N—H···N interactions. Intermolecular amine-to-amine and amine-to-cyano hydrogen bonding interactions established "ladder-like" parallel tapes in the crystalline solid (Fig. 2).

The molecular structure and atom numbering scheme for the title compound are shown in Fig. 1. Its X-ray structure confirms the presence of intramolecular hydrogen bond between the amino groups [N–H, 2.426 (18) Å]. Furthermore the observed C3—N1 bond length [1.4357 (17) Å] is considerably elongated in relation to related structures [1.404 (3) Å] (Rivera et al., 2010), [1.3961 (18) Å] (Silversides et al., 2006) and is longer than the C4—N2 bond [1.4016 (16) Å]. Thus, these results indicate that the intramolecular interaction is responsible for the C3—N1 bond elongation. This is confirmed by the N1—C7 bond length [1.4648 (18) Å] that is longer than N2—C5 bond [1.4457 (19) Å]. Besides, the hybridization of both N1 and N2 atoms are slightly different. In fact, N1 has more sp² character [Sα = 347.25°] than N2 [Sα = 330.39°] if compared to sp³-hybridization [Sα = 328.50°] angle value. Other bond distances and bond angles are in good agreement with the standard values.

Related literature top

For general background to the title compound, see: Rivera et al. (2010). For related structures, see: Rivera et al. (2010, 2011); Silversides et al. (2006).

Experimental top

A mixture of potassium cyanide (0.260 g, 4.00 mmol) and N¹,N²-bis((1H-benzotriazol-1-yl)methyl)benzene-1,2-diamine (0.370 g, 1.00 mmol) was stirred at room temperature in DMSO (5 ml) for 6 h. After quenching by addition of aqueous ammonium chloride a solid formed which was separated and extracted with ethyl acetate.The organic extract was sequentially washed with saturated Na₂CO₃ solution and water, then dried (Na₂SO₄), filtered, and concentrated to give a solid homogeneous by TLC (80% EtOAc/benzene) in 82% yield. Single crystals were obtained by recrystallization from chloroform/methanol by slow evaporation of the solvent at room temperaature, m.p. 399–400 K.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006).

Figures top

	Fig. 1. A view of the crystal structure of the tittle compund (I) with the numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing of the molecules of the title compound view along a axis. N—H···CN and N—H···N hydrogen bonds are drawn as dashed lines.

2,2'-[1,2-Phenylenebis(azanediyl)]diacetonitrile top

Crystal data top

C₁₀H₁₀N₄	D_x = 1.341 Mg m⁻³
M_r = 186.2	Melting point: 399 K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4237 reflections
a = 7.6404 (3) Å	θ = 4.0–67.0°
b = 15.1703 (7) Å	µ = 0.69 mm⁻¹
c = 15.9168 (7) Å	T = 120 K
V = 1844.87 (14) Å³	Polygon shape, white
Z = 8	0.17 × 0.15 × 0.10 mm
F(000) = 784

Data collection top

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	1641 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1359 reflections with I > 3σ(I)
Mirror monochromator	R_int = 0.061
Detector resolution: 10.3784 pixels mm^-1	θ_max = 67.2°, θ_min = 5.6°
ω scans	h = −7→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −18→18
T_min = 0.68, T_max = 1	l = −18→16
9893 measured reflections

Refinement top

Refinement on F²	34 constraints
R[F² > 2σ(F²)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.104	Weighting scheme based on measured s.u.'s w = 1/(σ²(I) + 0.0016I²)
S = 1.55	(Δ/σ)_max = 0.005
1641 reflections	Δρ_max = 0.16 e Å⁻³
133 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints

Crystal data top

C₁₀H₁₀N₄	V = 1844.87 (14) Å³
M_r = 186.2	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 7.6404 (3) Å	µ = 0.69 mm⁻¹
b = 15.1703 (7) Å	T = 120 K
c = 15.9168 (7) Å	0.17 × 0.15 × 0.10 mm

Data collection top

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	1641 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	1359 reflections with I > 3σ(I)
T_min = 0.68, T_max = 1	R_int = 0.061
9893 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.55	Δρ_max = 0.16 e Å⁻³
1641 reflections	Δρ_min = −0.20 e Å⁻³
133 parameters

Special details top

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F² for refinement carried out on F and F², respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details, that does not force S to be one. Therefore the values of S are usually larger than the ones from the SHELX program.

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

	x	y	z	U_iso*/U_eq
N1	0.67776 (14)	0.46314 (7)	0.09105 (8)	0.0197 (3)
N2	0.59009 (13)	0.37473 (8)	−0.05397 (8)	0.0182 (3)
N3	0.75959 (16)	0.31452 (9)	0.25065 (9)	0.0316 (4)
N4	0.68740 (17)	0.42625 (9)	−0.25896 (9)	0.0314 (4)
C1	0.67383 (17)	0.35295 (9)	0.20428 (10)	0.0228 (4)
C2	0.62292 (17)	0.38628 (9)	−0.20642 (10)	0.0227 (4)
C3	0.81190 (16)	0.41747 (8)	0.04529 (9)	0.0179 (4)
C4	0.76583 (16)	0.37282 (8)	−0.02878 (9)	0.0176 (4)
C5	0.54231 (16)	0.33892 (9)	−0.13496 (9)	0.0200 (4)
C6	0.89448 (16)	0.32671 (9)	−0.07229 (10)	0.0203 (4)
C7	0.57084 (17)	0.40361 (9)	0.14220 (10)	0.0215 (4)
C8	1.11225 (17)	0.37219 (9)	0.02841 (11)	0.0248 (4)
C9	0.98466 (17)	0.41713 (9)	0.07282 (10)	0.0224 (4)
C10	1.06689 (17)	0.32645 (10)	−0.04320 (10)	0.0238 (4)
H1c5	0.417265	0.339719	−0.140823	0.024*
H2c5	0.57431	0.277778	−0.137292	0.024*
H1c6	0.864639	0.294979	−0.122465	0.0244*
H1c7	0.508788	0.363609	0.106188	0.0258*
H2c7	0.481985	0.436862	0.17073	0.0258*
H1c8	1.23154	0.372856	0.047341	0.0298*
H1c9	1.015681	0.44837	0.123117	0.0268*
H1c10	1.154716	0.294105	−0.073369	0.0286*
H1	0.732 (2)	0.5050 (12)	0.1255 (12)	0.0237*
H2	0.536 (2)	0.4245 (12)	−0.0403 (12)	0.0219*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0140 (5)	0.0231 (6)	0.0221 (7)	0.0001 (4)	−0.0013 (5)	−0.0013 (5)
N2	0.0087 (5)	0.0257 (6)	0.0202 (7)	0.0023 (4)	0.0000 (5)	−0.0013 (5)
N3	0.0229 (6)	0.0399 (7)	0.0319 (8)	−0.0047 (6)	−0.0020 (6)	0.0091 (6)
N4	0.0267 (6)	0.0389 (7)	0.0287 (8)	0.0053 (6)	0.0054 (6)	0.0065 (6)
C1	0.0167 (7)	0.0287 (7)	0.0231 (8)	−0.0035 (6)	0.0041 (6)	−0.0004 (6)
C2	0.0154 (6)	0.0286 (7)	0.0241 (9)	0.0052 (6)	−0.0007 (6)	−0.0013 (6)
C3	0.0117 (6)	0.0210 (6)	0.0210 (8)	−0.0002 (5)	0.0014 (5)	0.0041 (5)
C4	0.0101 (6)	0.0217 (6)	0.0211 (8)	−0.0006 (5)	0.0001 (5)	0.0045 (5)
C5	0.0124 (6)	0.0268 (7)	0.0208 (8)	−0.0011 (5)	−0.0006 (6)	0.0008 (5)
C6	0.0131 (6)	0.0249 (7)	0.0229 (8)	0.0011 (5)	0.0019 (6)	0.0012 (6)
C7	0.0137 (6)	0.0285 (7)	0.0223 (8)	0.0013 (5)	0.0007 (6)	−0.0007 (6)
C8	0.0094 (6)	0.0300 (7)	0.0350 (9)	−0.0019 (5)	−0.0030 (6)	0.0081 (6)
C9	0.0153 (6)	0.0262 (7)	0.0256 (9)	−0.0038 (5)	−0.0042 (6)	0.0051 (6)
C10	0.0107 (6)	0.0284 (7)	0.0324 (9)	0.0028 (5)	0.0043 (6)	0.0064 (6)

Geometric parameters (Å, º) top

N1—C3	1.4357 (17)	C4—C6	1.3911 (19)
N1—C7	1.4648 (18)	C5—H1c5	0.96
N1—H1	0.935 (18)	C5—H2c5	0.96
N2—C4	1.4016 (16)	C6—C10	1.3963 (18)
N2—C5	1.4457 (19)	C6—H1c6	0.96
N2—H2	0.889 (18)	C7—H1c7	0.96
N3—C1	1.146 (2)	C7—H2c7	0.96
N4—C2	1.144 (2)	C8—C9	1.384 (2)
C1—C7	1.479 (2)	C8—C10	1.379 (2)
C2—C5	1.480 (2)	C8—H1c8	0.96
C3—C4	1.404 (2)	C9—H1c9	0.96
C3—C9	1.3908 (18)	C10—H1c10	0.96

C3—N1—C7	112.49 (10)	H1c5—C5—H2c5	105.18
C3—N1—H1	108.1 (10)	C4—C6—C10	120.20 (14)
C7—N1—H1	109.8 (11)	C4—C6—H1c6	119.9
C4—N2—C5	119.29 (11)	C10—C6—H1c6	119.9
C4—N2—H2	113.2 (11)	N1—C7—C1	113.27 (11)
C5—N2—H2	114.8 (12)	N1—C7—H1c7	109.47
N3—C1—C7	177.27 (15)	N1—C7—H2c7	109.47
N4—C2—C5	176.55 (16)	C1—C7—H1c7	109.47
N1—C3—C4	118.67 (11)	C1—C7—H2c7	109.47
N1—C3—C9	121.29 (13)	H1c7—C7—H2c7	105.38
C4—C3—C9	120.04 (12)	C9—C8—C10	119.55 (13)
N2—C4—C3	118.05 (12)	C9—C8—H1c8	120.22
N2—C4—C6	123.02 (13)	C10—C8—H1c8	120.22
C3—C4—C6	118.90 (12)	C3—C9—C8	120.63 (14)
N2—C5—C2	113.45 (11)	C3—C9—H1c9	119.69
N2—C5—H1c5	109.47	C8—C9—H1c9	119.69
N2—C5—H2c5	109.47	C6—C10—C8	120.65 (13)
C2—C5—H1c5	109.47	C6—C10—H1c10	119.67
C2—C5—H2c5	109.47	C8—C10—H1c10	119.67

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.935 (18)	2.202 (19)	3.0946 (19)	159.2 (16)
N2—H2···N1	0.889 (18)	2.427 (18)	2.7524 (18)	102.0 (13)
N2—H2···N1ⁱⁱ	0.889 (18)	2.494 (17)	3.2536 (16)	143.8 (15)

Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄
M_r	186.2
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	7.6404 (3), 15.1703 (7), 15.9168 (7)
V (Å³)	1844.87 (14)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.17 × 0.15 × 0.10

Data collection
Diffractometer	Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.68, 1
No. of measured, independent and observed [I > 3σ(I)] reflections	9893, 1641, 1359
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.104, 1.55
No. of reflections	1641
No. of parameters	133
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20

Computer programs: CrysAlis PRO (Agilent, 2012), SUPERFLIP (Palatinus & Chapuis, 2007), JANA2006 (Petříček et al., 2006), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4ⁱ	0.935 (18)	2.202 (19)	3.0946 (19)	159.2 (16)
N2—H2···N1	0.889 (18)	2.427 (18)	2.7524 (18)	102.0 (13)
N2—H2···N1ⁱⁱ	0.889 (18)	2.494 (17)	3.2536 (16)	143.8 (15)

Symmetry codes: (i) −x+3/2, −y+1, z+1/2; (ii) −x+1, −y+1, −z.

Acknowledgements

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia, for financial support of this work, as well the Praemium Academiae project of the Academy of Sciences of the Czech Republic. LJ—C acknowledges the Vicerrectoría Académica de la Universidad Nacional de Colombia for a fellowship.

References

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