2,2′-Dimethyl-2,2′-(m-phenyl­ene­dimethyl­ene)propane­dinitrile

Zhao, J.; Böhmer, V.; Bolte, M.

doi:10.1107/S1600536809023344

organic compounds

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Volume 65| Part 7| July 2009| Page o1658

doi:10.1107/S1600536809023344

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2,2′-Dimethyl-2,2′-(m-phenylenedimethylene)propanedinitrile

Junmei Zhao,^a Volker Böhmer ^a and Michael Bolte ^b ^*

^aFachbereich Chemie, Pharmazie und Geowissenschaften, Abteilung Lehramt Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55099 Mainz, Germany, and ^bInstitut für Anorganische Chemie, Johann Wolfgang Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
^*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

(Received 16 June 2009; accepted 17 June 2009; online 20 June 2009)

The title compound, C₁₆H₁₄N₄, features an aromatic ring with two 2,2′-dicyanopropyl residues in positions 1 and 3, which are located above and below the ring plane. The two residues differ in their conformation with respect to the aromatic ring: whereas one of the C_methyl—C—C_methylene—C_aromatic torsion angles is gauche [68.93 (12)°], the other one is fully staggered [177.63 (9)°]. The crystal structure is stabilized by C—H⋯N hydrogen-bonding interactions.

Related literature

Calix[4]arenes, fixed in their cone conformation, offer a platform to attach various ligating functions via amide bonds to their wide or narrow rim, see: Arnaud-Neu et al. (1996 ); Barboso et al. (1999 ); Casnati et al. (2005 ); Danila et al. (2005a ,b ). Tetranitriles are suitable precursors for the attachment to the narrow rim. The title compound was envisaged as another potential tetranitrile. It is readily available by alkylation of methylmalonodinitrile with 1,3-bis-chloromethylbenzene.

Experimental

Crystal data

C₁₆H₁₄N₄
M_r = 262.31
Monoclinic, P 2₁ /c
a = 11.6475 (10) Å
b = 13.3751 (13) Å
c = 9.4691 (9) Å
β = 99.020 (7)°
V = 1456.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 173 K
0.47 × 0.24 × 0.22 mm

Data collection

Stoe IPDS-II two-circle diffractometer
Absorption correction: none
8679 measured reflections
2725 independent reflections
2410 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.101
S = 1.04
2725 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯N24ⁱ	0.99	2.49	3.4028 (17)	153
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023344/at2821sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809023344/at2821Isup2.hkl

checkCIF report

Comment top

Calix[4]arenes, fixed in their cone conformation, offer a platform to attach various ligating functions via amide bonds to their wide or narrow rim [e.g. CMPO-groups (Arnaud-Neu et al., 1996; Barboso et al., 1999), picolinamides (Casnati et al., 2005)]. Suitable precursors for the attachment to the narrow rim are tetranitriles obtained by O-alkylation with ω-bromoalkyl nitriles, which can be easily reduced to the respective tetraamines (Danila et al., 2005a,b). The title compound, 1,3-bis-(2,2'-dicyano)propyl benzene, (Fig. 1), was envisaged as another potential tetranitrile. It is readily available by alkylation of methylmalonodinitrile with 1,3-bis-chloromethylbenzene.

The title compound features an aromatic ring with two 2,2'-dicyano-propyl residues in positions 1 and 3, which are located above and below the ring plane. The two residues differ in their conformation with respect to the aromatic ring: whereas one of the C_methyl-C-C_methylene-C_aromatic torsion angles is gauche [68.93 (12)\%], the other one is fully staggered [177.63 (9)\%]. The crystal structure is stabilized by C—H···N hydrogen-bonding interactions (Table 1).

Related literature top

Experimental top

A solution of methylmalonodinitrile (1.59 g, 13.9 mmol) in dry acetone (10 ml) was added to a suspension of K₂CO₃ (3.95 g, 28.6 mmol) in 20 ml acetone. The mixture was stirred for 30 min. Then 1,3-bischloromethylbenzene (500 mg, 2.86 mmol) and KI (80.5 g) were added and the mixture was stirred 10 h under reflux. The solvent was evaporated to dryness and the residue taken up with CHCl₃ (50 ml), washed with 1 M HCl, (2 x 30 ml), water and brine and dried over MgSO₄. Evaporation of the solvent and purification by column chromatography (hexane/ethylacetate 5:1) gave 530 mg (71%) of 1,3-bis-(2,2'-dicyano)propyl benzene, m.p. 130–131°C; ¹H NMR (400 MHz, CDCl₃): δ / p.p.m.: 1.82 (s, 6H), 3.23 (s, 4H), 7.34 (d, 1H), 7.4–7.5 (m, 3H); MS(FD): m/z 262.3 (100%, M⁺).

Single crystals were obtained by slow evaporation of a solution in hexane/chloroform.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are at the 50% probability level.

2,2'-Dimethyl-2,2'-(m-phenylenedimethylene)propanedinitrile top

Crystal data top

C₁₆H₁₄N₄	F(000) = 552
M_r = 262.31	D_x = 1.196 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8902 reflections
a = 11.6475 (10) Å	θ = 3.5–25.7°
b = 13.3751 (13) Å	µ = 0.07 mm⁻¹
c = 9.4691 (9) Å	T = 173 K
β = 99.020 (7)°	Block, colourless
V = 1456.9 (2) Å³	0.47 × 0.24 × 0.22 mm
Z = 4

Data collection top

Stoe IPDS-II two-circle diffractometer	2410 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 25.6°, θ_min = 3.5°
ω scans	h = −14→14
8679 measured reflections	k = −16→16
2725 independent reflections	l = −11→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0522P)² + 0.3439P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2725 reflections	Δρ_max = 0.22 e Å⁻³
182 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.035 (4)

Crystal data top

C₁₆H₁₄N₄	V = 1456.9 (2) Å³
M_r = 262.31	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.6475 (10) Å	µ = 0.07 mm⁻¹
b = 13.3751 (13) Å	T = 173 K
c = 9.4691 (9) Å	0.47 × 0.24 × 0.22 mm
β = 99.020 (7)°

Data collection top

Stoe IPDS-II two-circle diffractometer	2410 reflections with I > 2σ(I)
8679 measured reflections	R_int = 0.038
2725 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
2725 reflections	Δρ_min = −0.16 e Å⁻³
182 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 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	0.24600 (9)	0.73229 (9)	0.32550 (12)	0.0222 (3)
C2	0.32892 (9)	0.68926 (8)	0.43145 (12)	0.0225 (3)
H2	0.3344	0.6185	0.4382	0.027*
C3	0.40374 (9)	0.74802 (8)	0.52747 (12)	0.0217 (3)
C4	0.39613 (10)	0.85248 (9)	0.51626 (12)	0.0256 (3)
H4	0.4461	0.8935	0.5809	0.031*
C5	0.31502 (10)	0.89599 (9)	0.41008 (13)	0.0285 (3)
H5	0.3107	0.9667	0.4019	0.034*
C6	0.24024 (10)	0.83659 (9)	0.31583 (12)	0.0262 (3)
H6	0.1849	0.8672	0.2445	0.031*
C11	0.16383 (10)	0.66726 (9)	0.22412 (12)	0.0242 (3)
H11A	0.2093	0.6129	0.1883	0.029*
H11B	0.1300	0.7083	0.1409	0.029*
C12	0.06227 (10)	0.61940 (9)	0.29147 (12)	0.0240 (3)
C13	−0.00481 (10)	0.69976 (10)	0.35020 (14)	0.0313 (3)
N13	−0.05588 (11)	0.76326 (11)	0.39209 (16)	0.0516 (4)
C14	0.10897 (10)	0.55154 (10)	0.41158 (13)	0.0280 (3)
N14	0.14425 (10)	0.49664 (10)	0.50128 (13)	0.0423 (3)
C15	−0.01964 (11)	0.55815 (10)	0.17831 (13)	0.0328 (3)
H15A	0.0249	0.5053	0.1399	0.049*
H15B	−0.0539	0.6024	0.1005	0.049*
H15C	−0.0817	0.5280	0.2231	0.049*
C21	0.48821 (9)	0.69770 (9)	0.64449 (12)	0.0233 (3)
H21A	0.4519	0.6357	0.6740	0.028*
H21B	0.5017	0.7426	0.7285	0.028*
C22	0.60898 (9)	0.67039 (9)	0.59992 (12)	0.0227 (3)
C23	0.59040 (10)	0.60957 (9)	0.46639 (12)	0.0262 (3)
N23	0.57367 (10)	0.56598 (9)	0.36058 (12)	0.0371 (3)
C24	0.67231 (10)	0.60763 (9)	0.71679 (12)	0.0256 (3)
N24	0.71923 (10)	0.56270 (8)	0.81204 (12)	0.0376 (3)
C25	0.68272 (11)	0.76360 (10)	0.57854 (14)	0.0325 (3)
H25A	0.6947	0.8033	0.6666	0.049*
H25B	0.6420	0.8042	0.5001	0.049*
H25C	0.7582	0.7425	0.5554	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0200 (5)	0.0253 (6)	0.0232 (5)	0.0021 (4)	0.0095 (4)	0.0013 (4)
C2	0.0205 (5)	0.0209 (5)	0.0280 (6)	0.0022 (4)	0.0095 (4)	0.0023 (4)
C3	0.0190 (5)	0.0245 (6)	0.0236 (6)	0.0023 (4)	0.0100 (4)	0.0006 (4)
C4	0.0249 (6)	0.0243 (6)	0.0293 (6)	0.0005 (5)	0.0090 (5)	−0.0036 (5)
C5	0.0318 (6)	0.0207 (6)	0.0350 (6)	0.0053 (5)	0.0112 (5)	0.0014 (5)
C6	0.0257 (6)	0.0261 (6)	0.0280 (6)	0.0075 (5)	0.0083 (5)	0.0049 (5)
C11	0.0245 (5)	0.0275 (6)	0.0214 (5)	0.0026 (5)	0.0064 (4)	0.0009 (4)
C12	0.0224 (5)	0.0279 (6)	0.0218 (6)	0.0015 (5)	0.0042 (4)	−0.0024 (4)
C13	0.0207 (5)	0.0397 (7)	0.0335 (6)	−0.0011 (5)	0.0047 (5)	−0.0086 (5)
N13	0.0343 (6)	0.0557 (8)	0.0666 (9)	0.0067 (6)	0.0131 (6)	−0.0225 (7)
C14	0.0217 (5)	0.0377 (7)	0.0258 (6)	−0.0038 (5)	0.0071 (5)	0.0008 (5)
N14	0.0298 (6)	0.0580 (8)	0.0390 (6)	−0.0046 (5)	0.0051 (5)	0.0170 (6)
C15	0.0347 (6)	0.0351 (7)	0.0268 (6)	−0.0059 (5)	−0.0005 (5)	−0.0038 (5)
C21	0.0225 (5)	0.0265 (6)	0.0224 (5)	0.0015 (4)	0.0077 (4)	0.0004 (4)
C22	0.0216 (5)	0.0239 (6)	0.0233 (5)	0.0021 (4)	0.0056 (4)	0.0013 (4)
C23	0.0249 (6)	0.0286 (6)	0.0259 (6)	0.0067 (5)	0.0064 (5)	0.0034 (5)
N23	0.0407 (6)	0.0402 (6)	0.0303 (6)	0.0102 (5)	0.0054 (5)	−0.0049 (5)
C24	0.0257 (6)	0.0251 (6)	0.0265 (6)	0.0031 (5)	0.0056 (5)	−0.0025 (5)
N24	0.0444 (7)	0.0345 (6)	0.0323 (6)	0.0110 (5)	0.0011 (5)	0.0017 (5)
C25	0.0271 (6)	0.0327 (7)	0.0391 (7)	−0.0043 (5)	0.0096 (5)	0.0042 (5)

Geometric parameters (Å, º) top

C1—C6	1.3989 (16)	C12—C15	1.5521 (16)
C1—C2	1.4024 (16)	C13—N13	1.1431 (18)
C1—C11	1.5185 (16)	C14—N14	1.1489 (17)
C2—C3	1.3983 (16)	C15—H15A	0.9800
C2—H2	0.9500	C15—H15B	0.9800
C3—C4	1.4029 (16)	C15—H15C	0.9800
C3—C21	1.5189 (15)	C21—C22	1.5737 (15)
C4—C5	1.3944 (17)	C21—H21A	0.9900
C4—H4	0.9500	C21—H21B	0.9900
C5—C6	1.3938 (17)	C22—C24	1.4891 (16)
C5—H5	0.9500	C22—C23	1.4905 (16)
C6—H6	0.9500	C22—C25	1.5452 (16)
C11—C12	1.5661 (16)	C23—N23	1.1491 (16)
C11—H11A	0.9900	C24—N24	1.1483 (16)
C11—H11B	0.9900	C25—H25A	0.9800
C12—C13	1.4870 (17)	C25—H25B	0.9800
C12—C14	1.4898 (16)	C25—H25C	0.9800

C6—C1—C2	118.46 (11)	C15—C12—C11	110.88 (9)
C6—C1—C11	120.72 (10)	N13—C13—C12	178.01 (15)
C2—C1—C11	120.82 (10)	N14—C14—C12	177.80 (14)
C3—C2—C1	121.57 (10)	C12—C15—H15A	109.5
C3—C2—H2	119.2	C12—C15—H15B	109.5
C1—C2—H2	119.2	H15A—C15—H15B	109.5
C2—C3—C4	119.01 (10)	C12—C15—H15C	109.5
C2—C3—C21	119.45 (10)	H15A—C15—H15C	109.5
C4—C3—C21	121.50 (10)	H15B—C15—H15C	109.5
C5—C4—C3	119.86 (11)	C3—C21—C22	114.28 (9)
C5—C4—H4	120.1	C3—C21—H21A	108.7
C3—C4—H4	120.1	C22—C21—H21A	108.7
C6—C5—C4	120.56 (11)	C3—C21—H21B	108.7
C6—C5—H5	119.7	C22—C21—H21B	108.7
C4—C5—H5	119.7	H21A—C21—H21B	107.6
C5—C6—C1	120.52 (11)	C24—C22—C23	108.18 (9)
C5—C6—H6	119.7	C24—C22—C25	109.35 (9)
C1—C6—H6	119.7	C23—C22—C25	109.81 (10)
C1—C11—C12	114.71 (9)	C24—C22—C21	106.92 (9)
C1—C11—H11A	108.6	C23—C22—C21	109.70 (9)
C12—C11—H11A	108.6	C25—C22—C21	112.74 (9)
C1—C11—H11B	108.6	N23—C23—C22	177.17 (12)
C12—C11—H11B	108.6	N24—C24—C22	176.36 (12)
H11A—C11—H11B	107.6	C22—C25—H25A	109.5
C13—C12—C14	107.77 (10)	C22—C25—H25B	109.5
C13—C12—C15	109.73 (10)	H25A—C25—H25B	109.5
C14—C12—C15	108.47 (10)	C22—C25—H25C	109.5
C13—C12—C11	109.36 (10)	H25A—C25—H25C	109.5
C14—C12—C11	110.56 (9)	H25B—C25—H25C	109.5

C6—C1—C2—C3	0.90 (16)	C6—C1—C11—C12	−104.02 (12)
C11—C1—C2—C3	−178.74 (10)	C2—C1—C11—C12	75.62 (13)
C1—C2—C3—C4	−0.63 (16)	C1—C11—C12—C13	56.49 (13)
C1—C2—C3—C21	177.21 (10)	C1—C11—C12—C14	−62.02 (13)
C2—C3—C4—C5	−0.23 (16)	C1—C11—C12—C15	177.63 (9)
C21—C3—C4—C5	−178.02 (10)	C2—C3—C21—C22	88.93 (12)
C3—C4—C5—C6	0.80 (17)	C4—C3—C21—C22	−93.29 (12)
C4—C5—C6—C1	−0.52 (17)	C3—C21—C22—C24	−170.87 (9)
C2—C1—C6—C5	−0.32 (17)	C3—C21—C22—C23	−53.79 (13)
C11—C1—C6—C5	179.32 (10)	C3—C21—C22—C25	68.93 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···N24ⁱ	0.99	2.49	3.4028 (17)	153

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₄
M_r	262.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	11.6475 (10), 13.3751 (13), 9.4691 (9)
β (°)	99.020 (7)
V (Å³)	1456.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.47 × 0.24 × 0.22

Data collection
Diffractometer	Stoe IPDS-II two-circle diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8679, 2725, 2410
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.04
No. of reflections	2725
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.16

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11A···N24ⁱ	0.99	2.49	3.4028 (17)	153

Symmetry code: (i) −x+1, −y+1, −z+1.

References

Arnaud-Neu, F., Böhmer, V., Dozol, J.-F., Grüttner, C., Jakobi, R. A., Kraft, D., Mauprivez, O., Rouquette, H., Schwing-Weill, M.-J., Simon, N. & Vogt, W. (1996). J. Chem. Soc. Perkin Trans. 2, pp. 1175–1182. Google Scholar
Barboso, S., Garcia Carrera, A., Matthews, S. E., Arnaud-Neu, F., Böhmer, V., Dozol, J.-F., Rouquette, H. & Schwing-Weill, M.-J. (1999). J. Chem. Soc. Perkin Trans. 2, pp. 719–723. CrossRef Google Scholar
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Danila, C., Böhmer, V. & Bolte, M. (2005b). Org. Biomol. Chem. 3, 3508–3513. Web of Science CSD CrossRef PubMed CAS Google Scholar
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