2,6-Dibromo-4-butyl­anilinium chloride

In the crystal structure of the title salt, C₁₀H₁₄Br₂N⁺·Cl⁻, the organic cations and chloride anions are linked into one-dimensional chains parallel to the a axis by N—H...Cl and N—H...Br hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.064
• wR factor = 0.159
• Data-to-parameter ratio = 23.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.23 Ratio
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.11
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         12
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br1    ..  Cl1     ..       3.35 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          5
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              Cl
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         14

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          7
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety         N1

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

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

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S1. Comment

In recent years there has been a rapidly increasing interest in the construction of various kinds of supramolecular systems for understanding molecular self-assembly principles and for designing molecular recognition. A supramolecular system generally refers to an assembly of molecules which are not covalently connected but assembled by other weak intermolecular interactions, such as hydrogen bonds (Lehn, 1995; Scheiner, 1997). We report here the crystal structure of the title compound, 2,6-dibromo-4-butylanilinium chloride.

In the title compound (Fig.1), the butyl group is approximately orthogonal to the benzene plane, as indicated by the torsion angles C1—C6—C7—C8 and C5—C6—C7—C8 of 76.2 (11) and -102.7 (10)°, respectively. The Br1, Br2 and N1 substituents are displaced by 0.0842 (8), 0.1142 (8) and -0.005 (5) Å, respectively, with respect to the benzene ring. Bond lengths and angles lie within normal ranges. In the crystal structure, the organic cations and Cl^- anions are linked by N—H···Cl and N—H···Br hydrogen bonds (Table 1) to form one-dimensional chains along the a axis (Fig. 2).

Related literature

For general background to supramolecular self-assembly chemisty, see: Lehn Lehn (1995); Scheiner (1997).

S2. Experimental

The title compound was purchased from ALFA AESAR. The compound (3 mmol) was dissolved in ethanol (20 ml) and the solution allowed to evaporate to obtain colourless block-shaped crystals of the title compound suitable for X-ray analysis.

S3. Refinement

All H atoms were fixed geometrically and treated as riding, with C–H = 0.93-0.97 Å, N–H = 0.89 Å, and with U_iso(H) = 1.2 U_iso(C) or 1.5 U_iso(C, N) for methyl and protonated amine H atoms. Restraints (SIMU and DELU) were applied to the U_ij parameters of atoms C9 and C10.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Partial crystal packing of the title compound showing a chain formed along the a axis. H atoms not involved in hydrogen bonding (dashed lines) are omitted for clarity.

2,6-Dibromo-4-butylanilinium chloride

Crystal data

C10H14Br2N^+·Cl^−	Z = 2
Mr = 343.49	F(000) = 336
Triclinic, P1	Dx = 1.758 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.9785 (10) Å	Cell parameters from 2959 reflections
b = 8.7844 (18) Å	θ = 3.5–27.5°
c = 14.898 (3) Å	µ = 6.42 mm^−1
α = 86.29 (3)°	T = 298 K
β = 87.58 (3)°	Block, colourless
γ = 87.17 (3)°	0.10 × 0.03 × 0.03 mm
V = 648.9 (2) Å^3

Data collection

Rigaku Mercury2 diffractometer	2959 independent reflections
Radiation source: fine-focus sealed tube	1843 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.073
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.5°
CCD profile fitting scans	h = −6→6
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
Tmin = 0.910, Tmax = 1.000	l = −19→19
6685 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.159	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0602P)^2 + 0.1405P] where P = (Fo^2 + 2Fc^2)/3
2959 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.74 e Å^−3
7 restraints	Δρmin = −0.59 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.72826 (13)	0.30511 (8)	0.02752 (5)	0.0481 (3)
Br2	−0.07834 (15)	0.10595 (9)	0.28643 (5)	0.0591 (3)
C6	0.3280 (15)	0.5078 (8)	0.2416 (5)	0.0510 (18)
C3	0.3104 (12)	0.2297 (6)	0.1577 (4)	0.0380 (15)
C5	0.4948 (15)	0.4763 (7)	0.1683 (5)	0.0533 (19)
H5A	0.6159	0.5483	0.1463	0.064*
C2	0.1509 (13)	0.2581 (7)	0.2341 (5)	0.0399 (15)
N1	0.2929 (10)	0.0916 (5)	0.1091 (4)	0.0414 (13)
H1B	0.4105	0.0939	0.0624	0.062*
H1C	0.1273	0.0870	0.0895	0.062*
H1D	0.3304	0.0099	0.1457	0.062*
C4	0.4871 (13)	0.3411 (7)	0.1268 (4)	0.0426 (16)
C1	0.1564 (14)	0.3928 (8)	0.2748 (5)	0.0503 (18)
H1A	0.0447	0.4087	0.3253	0.060*
Cl1	0.2000 (3)	0.13452 (17)	−0.10326 (12)	0.0454 (4)
C7	0.332 (2)	0.6574 (9)	0.2856 (6)	0.074 (2)
H7A	0.4159	0.7317	0.2438	0.088*
H7B	0.1476	0.6943	0.2976	0.088*
C8	0.475 (2)	0.6474 (10)	0.3703 (8)	0.100 (3)
H8A	0.6534	0.6011	0.3588	0.120*
H8B	0.3813	0.5790	0.4131	0.120*
C9	0.507 (3)	0.7949 (12)	0.4139 (8)	0.121 (3)
H9A	0.5983	0.8641	0.3707	0.145*
H9B	0.3291	0.8403	0.4266	0.145*
C10	0.656 (3)	0.7844 (12)	0.4977 (8)	0.124 (3)
H10A	0.7705	0.8690	0.4979	0.185*
H10B	0.7628	0.6905	0.5015	0.185*
H10C	0.5302	0.7869	0.5484	0.185*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0415 (4)	0.0531 (4)	0.0507 (5)	−0.0095 (3)	−0.0033 (3)	−0.0037 (3)
Br2	0.0639 (5)	0.0619 (5)	0.0529 (6)	−0.0181 (4)	0.0049 (4)	−0.0073 (4)
C6	0.065 (5)	0.044 (4)	0.045 (5)	−0.003 (4)	−0.011 (4)	−0.009 (3)
C3	0.042 (3)	0.030 (3)	0.044 (4)	−0.003 (3)	−0.012 (3)	−0.008 (3)
C5	0.064 (5)	0.034 (4)	0.063 (5)	−0.008 (3)	−0.019 (4)	0.002 (3)
C2	0.047 (4)	0.034 (3)	0.039 (4)	−0.004 (3)	−0.003 (3)	−0.002 (3)
N1	0.039 (3)	0.033 (3)	0.053 (4)	−0.007 (2)	−0.002 (3)	−0.010 (2)
C4	0.046 (4)	0.044 (4)	0.038 (4)	0.008 (3)	−0.012 (3)	0.001 (3)
C1	0.052 (4)	0.057 (4)	0.042 (4)	−0.001 (4)	0.003 (4)	−0.013 (3)
Cl1	0.0441 (9)	0.0400 (8)	0.0535 (11)	−0.0059 (7)	−0.0057 (8)	−0.0093 (7)
C7	0.109 (7)	0.044 (4)	0.070 (6)	−0.012 (4)	0.000 (6)	−0.013 (4)
C8	0.129 (8)	0.065 (6)	0.112 (10)	0.000 (6)	−0.036 (7)	−0.039 (6)
C9	0.181 (9)	0.080 (5)	0.111 (7)	−0.013 (6)	−0.050 (6)	−0.043 (5)
C10	0.183 (9)	0.083 (5)	0.113 (7)	−0.011 (6)	−0.049 (6)	−0.041 (5)

Geometric parameters (Å, º)

Br1—C4	1.898 (7)	C1—H1A	0.9300
Br2—C2	1.907 (6)	C7—C8	1.473 (12)
C6—C5	1.377 (10)	C7—H7A	0.9700
C6—C1	1.407 (10)	C7—H7B	0.9700
C6—C7	1.507 (10)	C8—C9	1.504 (12)
C3—C2	1.389 (9)	C8—H8A	0.9700
C3—C4	1.391 (8)	C8—H8B	0.9700
C3—N1	1.461 (7)	C9—C10	1.474 (15)
C5—C4	1.378 (9)	C9—H9A	0.9700
C5—H5A	0.9300	C9—H9B	0.9700
C2—C1	1.365 (9)	C10—H10A	0.9600
N1—H1B	0.8900	C10—H10B	0.9600
N1—H1C	0.8900	C10—H10C	0.9600
N1—H1D	0.8900
C5—C6—C1	117.0 (6)	C8—C7—C6	113.8 (7)
C5—C6—C7	121.8 (7)	C8—C7—H7A	108.8
C1—C6—C7	121.2 (7)	C6—C7—H7A	108.8
C2—C3—C4	117.2 (5)	C8—C7—H7B	108.8
C2—C3—N1	122.6 (5)	C6—C7—H7B	108.8
C4—C3—N1	120.1 (6)	H7A—C7—H7B	107.7
C6—C5—C4	121.8 (7)	C7—C8—C9	116.7 (9)
C6—C5—H5A	119.1	C7—C8—H8A	108.1
C4—C5—H5A	119.1	C9—C8—H8A	108.1
C1—C2—C3	121.7 (6)	C7—C8—H8B	108.1
C1—C2—Br2	118.2 (5)	C9—C8—H8B	108.1
C3—C2—Br2	120.2 (4)	H8A—C8—H8B	107.3
C3—N1—H1B	109.5	C10—C9—C8	116.4 (10)
C3—N1—H1C	109.5	C10—C9—H9A	108.2
H1B—N1—H1C	109.5	C8—C9—H9A	108.2
C3—N1—H1D	109.5	C10—C9—H9B	108.2
H1B—N1—H1D	109.5	C8—C9—H9B	108.2
H1C—N1—H1D	109.5	H9A—C9—H9B	107.4
C5—C4—C3	121.1 (6)	C9—C10—H10A	109.5
C5—C4—Br1	119.1 (5)	C9—C10—H10B	109.5
C3—C4—Br1	119.8 (5)	H10A—C10—H10B	109.5
C2—C1—C6	121.1 (6)	C9—C10—H10C	109.5
C2—C1—H1A	119.4	H10A—C10—H10C	109.5
C6—C1—H1A	119.4	H10B—C10—H10C	109.5
C1—C6—C5—C4	2.6 (11)	C2—C3—C4—Br1	175.9 (5)
C7—C6—C5—C4	−178.4 (7)	N1—C3—C4—Br1	−5.7 (8)
C4—C3—C2—C1	3.2 (9)	C3—C2—C1—C6	−1.0 (10)
N1—C3—C2—C1	−175.1 (6)	Br2—C2—C1—C6	177.7 (5)
C4—C3—C2—Br2	−175.5 (4)	C5—C6—C1—C2	−1.9 (10)
N1—C3—C2—Br2	6.1 (8)	C7—C6—C1—C2	179.1 (7)
C6—C5—C4—C3	−0.4 (10)	C5—C6—C7—C8	−102.7 (10)
C6—C5—C4—Br1	−178.9 (5)	C1—C6—C7—C8	76.2 (11)
C2—C3—C4—C5	−2.5 (9)	C6—C7—C8—C9	175.0 (10)
N1—C3—C4—C5	175.9 (6)	C7—C8—C9—C10	−178.9 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl1^i	0.89	2.59	3.240 (5)	130
N1—H1D···Cl1^ii	0.89	2.68	3.136 (5)	113
N1—H1C···Br1^iii	0.89	2.82	3.517 (5)	135
N1—H1B···Br1	0.89	2.51	3.094 (5)	124
N1—H1B···Cl1	0.89	2.72	3.212 (6)	116

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