2-{4-[Bis(4-bromo-phen-yl)amino]-benzyl-idene}malono-nitrile.

In the crystal structure of the title compound, C22H13Br2N3, the two bromo-phenyl rings are rotated out of the plane of the central benzyl-idene ring by 68.7 (1) and 69.3 (1)°. Both cyano substituents are located nearly in the plane of the benzylidene ring, with the mean plane of the methylmalononitrile group being inclined to this ring by 5.8 (1)°. In the crystal, the mol-ecules are linked by weak C-H⋯N hydrogen bonds into layers parallel to the bc plane.

Related literature

For general background to aryl­amines such as tri­phenyl­amine as versatile optical materials, see: Ning et al. (2007 ▶); Noh et al. (2010 ▶). For related luminescent and electron-donating materials, see: Yao & Belfield (2005 ▶); Patra et al. (2007 ▶); Zhang et al. (2012 ▶). For the synthesis of the title compound, see: Chiang et al. (2005 ▶).

Experimental

Crystal data

C22H13Br2N3

M = 479.17

Monoclinic,

a = 14.6846 (6) Å

b = 10.3997 (4) Å

c = 13.1961 (4) Å

β = 103.501 (4)°

V = 1959.56 (12) Å3

Z = 4

Mo Kα radiation

μ = 4.15 mm−1

T = 298 K

0.30 × 0.20 × 0.20 mm

Data collection

Oxford Diffraction CrysAlis CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.369, T max = 0.491

9075 measured reflections

3843 independent reflections

2702 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.094

S = 1.02

3843 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.57 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) ItcLa, I. DOI: 10.1107/S1600536814013816/nc2326sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013816/nc2326Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814013816/nc2326Isup3.cml

CCDC reference: 1008127

Additional supporting information: crystallographic information; 3D view; checkCIF report

C22H13Br2N3	F(000) = 944
Mr = 479.17	Dx = 1.624 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2681 reflections
a = 14.6846 (6) Å	θ = 2.9–29.3°
b = 10.3997 (4) Å	µ = 4.15 mm−1
c = 13.1961 (4) Å	T = 298 K
β = 103.501 (4)°	Needle-like, yellow
V = 1959.56 (12) Å3	0.30 × 0.20 × 0.20 mm
Z = 4

Oxford Diffraction CrysAlis CCD diffractometer	3843 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2702 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω scans	θmax = 26.0°, θmin = 3.2°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −18→18
Tmin = 0.369, Tmax = 0.491	k = −7→12
9075 measured reflections	l = −14→16

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0359P)2 + 1.3631P] where P = (Fo2 + 2Fc2)/3
3843 reflections	(Δ/σ)max = 0.003
244 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.57 e Å−3

Experimental. Absorption correction: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.5 (release 08–05-2007 CrysAlis171. NET) (compiled May 8 2007,13:10:02) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
N1	0.7072 (2)	0.7143 (3)	0.4629 (2)	0.0468 (7)
N2	1.0781 (3)	1.4223 (5)	0.6211 (3)	0.0959 (15)
N3	0.9718 (2)	1.2359 (4)	0.3307 (3)	0.0669 (10)
C1	1.0307 (3)	1.3420 (5)	0.5799 (3)	0.0624 (11)
C2	0.9707 (2)	1.2363 (4)	0.4169 (3)	0.0470 (9)
C3	0.9731 (3)	1.2405 (4)	0.5257 (3)	0.0451 (9)
C4	0.9304 (3)	1.1577 (4)	0.5774 (3)	0.0468 (9)
H4A	0.9400	1.1749	0.6483	0.056*
C5	0.8725 (2)	1.0472 (3)	0.5432 (2)	0.0414 (8)
C6	0.8430 (2)	0.9732 (4)	0.6183 (2)	0.0469 (9)
H6A	0.8602	0.9987	0.6877	0.056*
C7	0.7902 (3)	0.8654 (4)	0.5933 (2)	0.0458 (9)
H7A	0.7731	0.8181	0.6458	0.055*
C8	0.7612 (2)	0.8249 (3)	0.4900 (2)	0.0407 (8)
C9	0.7887 (3)	0.8989 (4)	0.4134 (2)	0.0473 (9)
H9A	0.7700	0.8746	0.3438	0.057*
C10	0.8428 (2)	1.0064 (4)	0.4398 (2)	0.0461 (9)
H10A	0.8602	1.0536	0.3875	0.055*
C11	0.7119 (2)	0.6094 (3)	0.5341 (2)	0.0413 (8)
C12	0.7968 (2)	0.5562 (4)	0.5836 (3)	0.0501 (9)
H12A	0.8522	0.5923	0.5742	0.060*
C13	0.8002 (2)	0.4497 (4)	0.6470 (3)	0.0480 (9)
H13A	0.8574	0.4137	0.6802	0.058*
C14	0.7180 (2)	0.3981 (3)	0.6603 (2)	0.0426 (8)
C15	0.6331 (2)	0.4516 (4)	0.6153 (3)	0.0496 (9)
H15A	0.5781	0.4168	0.6269	0.060*
Br1	0.43314 (3)	0.65644 (5)	0.04171 (3)	0.06879 (17)
C16	0.6305 (2)	0.5586 (4)	0.5520 (3)	0.0484 (9)
H16A	0.5733	0.5964	0.5214	0.058*
C17	0.6453 (2)	0.7022 (3)	0.3628 (2)	0.0400 (8)
C18	0.6473 (3)	0.5930 (4)	0.3033 (3)	0.0477 (9)
H18A	0.6907	0.5285	0.3279	0.057*
C19	0.5850 (3)	0.5793 (4)	0.2072 (3)	0.0502 (9)
H19A	0.5861	0.5056	0.1676	0.060*
C20	0.5219 (2)	0.6753 (3)	0.1711 (2)	0.0440 (9)
C21	0.5201 (3)	0.7855 (4)	0.2277 (3)	0.0491 (9)
H21A	0.4777	0.8507	0.2018	0.059*
C22	0.5820 (3)	0.7985 (4)	0.3238 (3)	0.0482 (9)
H22A	0.5810	0.8730	0.3625	0.058*
Br2	0.72147 (3)	0.24595 (4)	0.74116 (4)	0.07151 (17)

	U11	U22	U33	U12	U13	U23
N1	0.0552 (18)	0.0382 (18)	0.0415 (15)	−0.0087 (16)	0.0003 (13)	0.0082 (13)
N2	0.141 (4)	0.093 (3)	0.055 (2)	−0.065 (3)	0.026 (2)	−0.022 (2)
N3	0.073 (2)	0.080 (3)	0.047 (2)	−0.018 (2)	0.0127 (17)	−0.0022 (18)
C1	0.087 (3)	0.063 (3)	0.040 (2)	−0.022 (3)	0.021 (2)	−0.007 (2)
C2	0.049 (2)	0.047 (2)	0.044 (2)	−0.0095 (19)	0.0077 (16)	−0.0032 (17)
C3	0.057 (2)	0.040 (2)	0.0378 (18)	−0.0081 (19)	0.0088 (16)	−0.0075 (16)
C4	0.061 (2)	0.045 (2)	0.0330 (16)	−0.003 (2)	0.0094 (16)	−0.0063 (16)
C5	0.052 (2)	0.038 (2)	0.0326 (16)	−0.0026 (18)	0.0070 (15)	−0.0015 (15)
C6	0.063 (2)	0.044 (2)	0.0316 (16)	−0.004 (2)	0.0079 (16)	−0.0021 (16)
C7	0.061 (2)	0.045 (2)	0.0321 (16)	−0.004 (2)	0.0119 (16)	0.0054 (16)
C8	0.0444 (19)	0.036 (2)	0.0405 (17)	0.0017 (17)	0.0075 (15)	0.0037 (15)
C9	0.062 (2)	0.046 (2)	0.0310 (17)	−0.007 (2)	0.0053 (16)	−0.0011 (16)
C10	0.062 (2)	0.041 (2)	0.0337 (16)	−0.008 (2)	0.0066 (16)	0.0035 (15)
C11	0.051 (2)	0.0346 (19)	0.0367 (17)	−0.0033 (18)	0.0079 (15)	0.0022 (15)
C12	0.040 (2)	0.053 (3)	0.057 (2)	−0.0042 (19)	0.0122 (17)	0.0134 (19)
C13	0.043 (2)	0.046 (2)	0.054 (2)	0.0045 (19)	0.0104 (17)	0.0130 (18)
C14	0.052 (2)	0.035 (2)	0.0400 (18)	−0.0036 (18)	0.0094 (16)	0.0011 (15)
C15	0.044 (2)	0.049 (2)	0.057 (2)	−0.012 (2)	0.0133 (17)	0.0034 (19)
Br1	0.0867 (3)	0.0633 (3)	0.0449 (2)	0.0030 (3)	−0.00761 (19)	−0.0020 (2)
C16	0.041 (2)	0.051 (2)	0.050 (2)	0.0016 (19)	0.0056 (16)	0.0080 (18)
C17	0.046 (2)	0.0343 (18)	0.0387 (17)	−0.0067 (18)	0.0072 (15)	0.0031 (15)
C18	0.056 (2)	0.035 (2)	0.049 (2)	0.0065 (19)	0.0071 (17)	0.0022 (17)
C19	0.069 (2)	0.038 (2)	0.0426 (19)	0.001 (2)	0.0118 (18)	−0.0046 (17)
C20	0.052 (2)	0.041 (2)	0.0370 (17)	−0.0025 (19)	0.0066 (15)	0.0047 (16)
C21	0.055 (2)	0.040 (2)	0.049 (2)	0.0092 (19)	0.0045 (17)	0.0026 (17)
C22	0.059 (2)	0.036 (2)	0.0460 (19)	0.004 (2)	0.0064 (17)	−0.0016 (17)
Br2	0.0765 (3)	0.0511 (3)	0.0828 (3)	−0.0111 (2)	0.0102 (2)	0.0252 (2)

N1—C8	1.395 (4)	C11—C12	1.381 (5)
N1—C17	1.424 (4)	C12—C13	1.382 (5)
N1—C11	1.431 (4)	C12—H12A	0.9300
N2—C1	1.140 (5)	C13—C14	1.369 (5)
N3—C2	1.142 (4)	C13—H13A	0.9300
C1—C3	1.436 (6)	C14—C15	1.368 (5)
C2—C3	1.428 (5)	C14—Br2	1.903 (3)
C3—C4	1.341 (5)	C15—C16	1.386 (5)
C4—C5	1.438 (5)	C15—H15A	0.9300
C4—H4A	0.9300	Br1—C20	1.900 (3)
C5—C10	1.399 (4)	C16—H16A	0.9300
C5—C6	1.401 (5)	C17—C22	1.382 (5)
C6—C7	1.359 (5)	C17—C18	1.384 (5)
C6—H6A	0.9300	C18—C19	1.387 (5)
C7—C8	1.396 (4)	C18—H18A	0.9300
C7—H7A	0.9300	C19—C20	1.370 (5)
C8—C9	1.403 (5)	C19—H19A	0.9300
C9—C10	1.368 (5)	C20—C21	1.372 (5)
C9—H9A	0.9300	C21—C22	1.384 (5)
C10—H10A	0.9300	C21—H21A	0.9300
C11—C16	1.377 (5)	C22—H22A	0.9300
C8—N1—C17	120.8 (3)	C11—C12—H12A	119.7
C8—N1—C11	121.5 (3)	C13—C12—H12A	119.7
C17—N1—C11	117.6 (3)	C14—C13—C12	118.8 (3)
N2—C1—C3	178.0 (5)	C14—C13—H13A	120.6
N3—C2—C3	177.4 (4)	C12—C13—H13A	120.6
C4—C3—C2	126.0 (3)	C15—C14—C13	121.8 (3)
C4—C3—C1	120.6 (3)	C15—C14—Br2	118.9 (3)
C2—C3—C1	113.3 (3)	C13—C14—Br2	119.2 (3)
C3—C4—C5	131.7 (3)	C14—C15—C16	118.8 (3)
C3—C4—H4A	114.2	C14—C15—H15A	120.6
C5—C4—H4A	114.2	C16—C15—H15A	120.6
C10—C5—C6	116.4 (3)	C11—C16—C15	120.6 (3)
C10—C5—C4	125.2 (3)	C11—C16—H16A	119.7
C6—C5—C4	118.4 (3)	C15—C16—H16A	119.7
C7—C6—C5	122.4 (3)	C22—C17—C18	119.0 (3)
C7—C6—H6A	118.8	C22—C17—N1	120.7 (3)
C5—C6—H6A	118.8	C18—C17—N1	120.3 (3)
C6—C7—C8	120.8 (3)	C17—C18—C19	120.4 (3)
C6—C7—H7A	119.6	C17—C18—H18A	119.8
C8—C7—H7A	119.6	C19—C18—H18A	119.8
N1—C8—C7	121.6 (3)	C20—C19—C18	119.5 (3)
N1—C8—C9	120.6 (3)	C20—C19—H19A	120.3
C7—C8—C9	117.7 (3)	C18—C19—H19A	120.3
C10—C9—C8	120.8 (3)	C19—C20—C21	121.1 (3)
C10—C9—H9A	119.6	C19—C20—Br1	120.3 (3)
C8—C9—H9A	119.6	C21—C20—Br1	118.6 (3)
C9—C10—C5	121.8 (3)	C20—C21—C22	119.2 (3)
C9—C10—H10A	119.1	C20—C21—H21A	120.4
C5—C10—H10A	119.1	C22—C21—H21A	120.4
C16—C11—C12	119.2 (3)	C17—C22—C21	120.8 (3)
C16—C11—N1	119.7 (3)	C17—C22—H22A	119.6
C12—C11—N1	121.1 (3)	C21—C22—H22A	119.6
C11—C12—C13	120.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···N3i	0.93	2.52	3.438 (5)	169
C6—H6A···N2ii	0.93	2.60	3.404 (5)	145

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯N3i	0.93	2.52	3.438 (5)	169
C6—H6A⋯N2ii	0.93	2.60	3.404 (5)	145

Symmetry codes: (i) ; (ii) .