4-Bromo-N-(3,4-methyl­enedioxy­benz­yl)­aniline

In the title compound, C₁₄H₁₂BrNO₂, the mol­ecules are linked by one C—H...Br hydrogen bond, so forming a C(13) chain running parallel to the [010] direction, and these chains are linked by further C—H...π and C—H...Br hydrogen bonds, resulting in a three-dimensional network structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.045
• wR factor = 0.106
• Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.265     0.346
            Tmin and Tmax expected:      0.179     0.260
            RR =      1.114
            Please check that your absorption correction is appropriate.
PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large .......       1.11
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.75
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1     ...          ?
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  O2      ..       3.21 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H8A    ..  BR1     ..       3.02 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H8B    ..  BR1     ..       3.08 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H11    ..  BR1     ..       3.09 Ang.

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.751
            Tmax scaled      0.260 Tmin scaled      0.199
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               2133
           Count of symmetry unique reflns         1220
           Completeness (_total/calc)            174.84%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       913
           Fraction of Friedel pairs measured     0.748
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   9 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

We have reported recently the crystyl structure of an aniline derives (Yang et al., 2007). As part of our study of the aniline derives, we report here the crystal structures of (I) (Fig.1).

The title compound(I), crystallizes in the orthorhombic space group Pca2₁ with Z = 4. In (I), the dihedral angle between the two benzene rings are 59.8 (1)°. Geometric parameters of (I) are normal (Allen et al., 1987) and selected geometric parameters are listed in the Table 1. The aniline N1—C9 bonds length is 1.391 (7) Å, this value is near with the aniline C—N bonds of the analogs reported (C—N = 1.396 Å, Silversides et al., C—N = 1.396 (5) Å, Yyang et al. 2007), but slightly shorter than the aniline C—N bonds of the analog reported (C—N = 1.414 Å, Koşar et al., 2004), this is probably due to the weakly inductive negative effect of the bromine atom on the aryl residue.

In the crystal structure of (I), the molecules are linked by one C—H···Br hydrogen bond into a simple C(13) chain (Bernstein et al., 1995) running parallel to the [010] direction. The atom C8 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via H8a, to the atom Br1 in the molecule at (x, -1 + y, z). These chains are linked by further C—H···π and C—H···Br hydrogen bonds, resulting in a three-dimensional network structure (Table 2 and Fig. 2).

Related literature

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Koşar et al. (2004); Silversides et al. (2006); Yang et al. (2007).

S2. Experimental

The mixture containing piperonaldehyde (1.5 g, 10 mmol) and 4-bromoaniline (1.72 g, 10 mmol) was refluxed for about 6 h in ethanol, then borohydride sodium(1.52 g, 40 mmol) was added and refluxed continuely for about 2 h, then acetone (20 ml) and water (40 ml) were added in turn, and the reaction mixture was cooled and the products were filtered off, washed with ethanol and dried. Colourless crystals of (I) suitatble for X-ray structure analysis were obtained by recrystallizing the crude product from ethanol (m.p.370–372 K).

S3. Refinement

All H atoms were located in difference Fourier maps. H atoms bonded to C and N atoms were treated as riding atoms, with C—H distances of 0.93 Å (aryl), 0.97 Å (methylene), N—H distances of 0.86 Å (amino), and with U_iso(H) = 1.2U_eq(C,N) (aryl, methylene, amino).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. A molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of part of the crystal structure of (I), showing the formation of a C(13) chain. For clarity, the H atoms not involved in the motif have been omitted. Dashed lines indicate hydrogen bonds. [Symmetry codes: (*) x, -1 + y, z; (#) x, 1 + y, z].

4-Bromo-N-(3,4-methylenedioxybenzyl)aniline

Crystal data

C14H12BrNO2	Dx = 1.631 Mg m^−3
Mr = 306.16	Melting point: 370 K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1828 reflections
a = 14.6264 (13) Å	θ = 2.8–25.8°
b = 14.2650 (12) Å	µ = 3.29 mm^−1
c = 5.9752 (8) Å	T = 298 K
V = 1246.7 (2) Å^3	Block, yellow
Z = 4	0.55 × 0.48 × 0.41 mm
F(000) = 616

Data collection

Siemens SMART 1000 CCD area-detector diffractometer	2133 independent reflections
Radiation source: fine-focus sealed tube	1641 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→17
Tmin = 0.265, Tmax = 0.346	k = −15→16
4925 measured reflections	l = −7→7

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0507P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
2133 reflections	Δρmax = 0.35 e Å^−3
163 parameters	Δρmin = −0.47 e Å^−3
1 restraint	Absolute structure: Flack (1983), 917 Freidel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.028 (18)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.6106 (3)	0.7514 (4)	0.8425 (10)	0.0380 (12)
H1	0.5825	0.7105	0.9227	0.046*
O1	0.6680 (3)	0.3832 (3)	0.8088 (8)	0.0518 (12)
O2	0.6013 (3)	0.3398 (3)	0.4741 (9)	0.0499 (12)
Br1	0.62189 (4)	1.15367 (4)	1.17625 (16)	0.0473 (2)
C1	0.6536 (4)	0.7235 (4)	0.6345 (13)	0.0416 (17)
H1a	0.7190	0.7340	0.6446	0.050*
H1b	0.6301	0.7617	0.5132	0.050*
C2	0.6358 (4)	0.6212 (4)	0.5839 (10)	0.0328 (14)
C3	0.6636 (3)	0.5539 (4)	0.7388 (9)	0.0334 (15)
H3	0.6907	0.5704	0.8741	0.040*
C4	0.6491 (3)	0.4622 (4)	0.6815 (15)	0.0334 (11)
C5	0.6106 (4)	0.4358 (4)	0.4820 (11)	0.0328 (14)
C6	0.5841 (4)	0.5002 (4)	0.3254 (11)	0.0365 (15)
H6	0.5588	0.4826	0.1889	0.044*
C7	0.5974 (4)	0.5944 (4)	0.3832 (10)	0.0361 (14)
H7	0.5797	0.6406	0.2823	0.043*
C8	0.6530 (4)	0.3075 (4)	0.6599 (17)	0.0570 (18)
H8a	0.6201	0.2578	0.7360	0.068*
H8b	0.7111	0.2826	0.6090	0.068*
C9	0.6144 (3)	0.8443 (4)	0.9130 (11)	0.0318 (13)
C14	0.5678 (4)	0.8713 (4)	1.1078 (9)	0.0368 (16)
H14	0.5339	0.8269	1.1860	0.044*
C13	0.5708 (3)	0.9618 (3)	1.1860 (13)	0.0348 (12)
H13	0.5391	0.9786	1.3147	0.042*
C12	0.6215 (4)	1.0273 (4)	1.0709 (10)	0.0335 (14)
C11	0.6678 (4)	1.0037 (4)	0.8828 (11)	0.0363 (15)
H11	0.7012	1.0492	0.8069	0.044*
C10	0.6662 (4)	0.9125 (4)	0.8017 (11)	0.0375 (14)
H10	0.6992	0.8967	0.6742	0.045*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.054 (3)	0.016 (2)	0.045 (3)	−0.007 (2)	0.007 (2)	0.000 (2)
O1	0.075 (3)	0.028 (2)	0.052 (3)	0.004 (2)	−0.019 (2)	0.005 (2)
O2	0.067 (3)	0.025 (3)	0.058 (3)	−0.001 (2)	−0.009 (2)	−0.007 (2)
Br1	0.0532 (3)	0.0253 (3)	0.0635 (4)	−0.0009 (3)	0.0084 (5)	−0.0109 (4)
C1	0.060 (3)	0.026 (3)	0.039 (5)	−0.008 (3)	0.010 (3)	−0.002 (3)
C2	0.037 (3)	0.026 (3)	0.036 (4)	0.003 (3)	0.006 (2)	−0.001 (3)
C3	0.037 (3)	0.035 (4)	0.028 (4)	−0.001 (3)	−0.004 (2)	−0.003 (3)
C4	0.038 (2)	0.029 (3)	0.034 (3)	0.000 (2)	−0.004 (4)	0.004 (4)
C5	0.039 (3)	0.022 (3)	0.038 (4)	0.001 (3)	0.002 (3)	−0.004 (3)
C6	0.044 (3)	0.036 (4)	0.030 (4)	−0.001 (3)	−0.009 (3)	−0.005 (3)
C7	0.048 (3)	0.028 (3)	0.033 (4)	0.004 (3)	−0.005 (3)	0.007 (3)
C8	0.078 (4)	0.028 (3)	0.065 (5)	0.005 (3)	−0.016 (5)	0.002 (5)
C9	0.030 (3)	0.025 (3)	0.040 (4)	0.002 (3)	−0.002 (2)	0.001 (3)
C14	0.037 (3)	0.033 (3)	0.040 (4)	−0.005 (3)	0.010 (2)	0.004 (3)
C13	0.037 (2)	0.032 (3)	0.035 (3)	0.001 (2)	0.002 (4)	−0.011 (4)
C12	0.030 (3)	0.024 (3)	0.047 (4)	0.000 (3)	−0.002 (3)	−0.003 (3)
C11	0.037 (3)	0.022 (3)	0.050 (4)	−0.005 (2)	0.013 (3)	−0.001 (3)
C10	0.041 (3)	0.029 (4)	0.042 (4)	0.001 (3)	0.009 (3)	−0.002 (3)

Geometric parameters (Å, º)

N1—C9	1.391 (7)	C5—C6	1.368 (8)
N1—C1	1.450 (9)	C6—C7	1.400 (7)
N1—H1	0.8600	C6—H6	0.9300
O1—C4	1.387 (8)	C7—H7	0.9300
O1—C8	1.417 (9)	C8—H8a	0.9700
O2—C5	1.377 (6)	C8—H8b	0.9700
O2—C8	1.420 (10)	C9—C10	1.401 (8)
Br1—C12	1.910 (6)	C9—C14	1.404 (8)
C1—C2	1.512 (8)	C14—C13	1.373 (7)
C1—H1a	0.9700	C14—H14	0.9300
C1—H1b	0.9700	C13—C12	1.377 (8)
C2—C7	1.379 (8)	C13—H13	0.9300
C2—C3	1.395 (7)	C12—C11	1.355 (8)
C3—C4	1.368 (7)	C11—C10	1.389 (7)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.372 (10)	C10—H10	0.9300
C9—N1—C1	120.3 (5)	C2—C7—H7	118.7
C9—N1—H1	119.9	C6—C7—H7	118.7
C1—N1—H1	119.9	O1—C8—O2	109.0 (5)
C4—O1—C8	104.1 (6)	O1—C8—H8a	109.9
C5—O2—C8	104.1 (5)	O2—C8—H8a	109.9
N1—C1—C2	111.2 (5)	O1—C8—H8b	109.9
N1—C1—H1a	109.4	O2—C8—H8b	109.9
C2—C1—H1a	109.4	H8a—C8—H8b	108.3
N1—C1—H1b	109.4	N1—C9—C10	122.6 (6)
C2—C1—H1b	109.4	N1—C9—C14	119.6 (5)
H1a—C1—H1b	108.0	C10—C9—C14	117.7 (5)
C7—C2—C3	120.3 (6)	C13—C14—C9	121.7 (5)
C7—C2—C1	120.8 (6)	C13—C14—H14	119.2
C3—C2—C1	118.8 (6)	C9—C14—H14	119.2
C4—C3—C2	116.5 (6)	C14—C13—C12	119.0 (6)
C4—C3—H3	121.7	C14—C13—H13	120.5
C2—C3—H3	121.7	C12—C13—H13	120.5
C3—C4—C5	123.0 (6)	C11—C12—C13	121.0 (5)
C3—C4—O1	127.4 (7)	C11—C12—Br1	120.4 (4)
C5—C4—O1	109.6 (5)	C13—C12—Br1	118.5 (4)
C6—C5—C4	121.8 (5)	C12—C11—C10	120.9 (6)
C6—C5—O2	128.1 (6)	C12—C11—H11	119.6
C4—C5—O2	110.1 (5)	C10—C11—H11	119.6
C5—C6—C7	115.9 (6)	C11—C10—C9	119.7 (6)
C5—C6—H6	122.1	C11—C10—H10	120.2
C7—C6—H6	122.1	C9—C10—H10	120.2
C2—C7—C6	122.5 (6)
C9—N1—C1—C2	−176.4 (5)	C1—C2—C7—C6	176.7 (5)
N1—C1—C2—C7	125.0 (6)	C5—C6—C7—C2	0.8 (8)
N1—C1—C2—C3	−58.5 (7)	C4—O1—C8—O2	−16.7 (7)
C7—C2—C3—C4	−1.1 (8)	C5—O2—C8—O1	17.4 (7)
C1—C2—C3—C4	−177.6 (5)	C1—N1—C9—C10	−6.2 (8)
C2—C3—C4—C5	0.9 (8)	C1—N1—C9—C14	176.2 (6)
C2—C3—C4—O1	−177.9 (5)	N1—C9—C14—C13	178.9 (5)
C8—O1—C4—C3	−171.6 (6)	C10—C9—C14—C13	1.2 (8)
C8—O1—C4—C5	9.5 (6)	C9—C14—C13—C12	−0.5 (8)
C3—C4—C5—C6	0.2 (9)	C14—C13—C12—C11	0.2 (9)
O1—C4—C5—C6	179.2 (5)	C14—C13—C12—Br1	178.0 (4)
C3—C4—C5—O2	−177.8 (5)	O2^i—Br1—C12—C11	−165.5 (5)
O1—C4—C5—O2	1.3 (7)	O2^i—Br1—C12—C13	16.6 (10)
C8—O2—C5—C6	170.9 (6)	C13—C12—C11—C10	−0.6 (9)
C8—O2—C5—C4	−11.4 (7)	Br1—C12—C11—C10	−178.4 (4)
C4—C5—C6—C7	−1.0 (9)	C12—C11—C10—C9	1.3 (9)
O2—C5—C6—C7	176.5 (5)	N1—C9—C10—C11	−179.2 (5)
C3—C2—C7—C6	0.3 (9)	C14—C9—C10—C11	−1.6 (8)

Symmetry code: (i) x, y+1, z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8a···Br1^ii	0.97	3.02	3.813 (9)	140
C8—H8b···Br1^iii	0.97	3.08	3.958 (6)	151
C11—H11···Br1^iv	0.93	3.09	3.944 (6)	154
C6—H6···Cg1^v	0.93	2.83	3.53 (2)	133
C13—H13···Cg2^vi	0.93	2.81	3.62 (2)	147

Symmetry codes: (ii) x, y−1, z; (iii) −x+3/2, y−1, z−1/2; (iv) −x+3/2, y, z−1/2; (v) −x+1, −y+1, z−1/2; (vi) −x+1, −y+2, z+1/2.