3,3′-Dichloro­biphenyl-4,4′-diaminium sulfate

Qian, H.-F.; Huang, W.

doi:10.1107/S1600536811027905

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2059

doi:10.1107/S1600536811027905

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3,3′-Dichlorobiphenyl-4,4′-diaminium sulfate

Hui-Fen Qian ^a ^* and Wei Huang ^b

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
^*Correspondence e-mail: qhf@njut.edu.cn

(Received 11 July 2011; accepted 12 July 2011; online 16 July 2011)

In the title compound, C₁₂H₁₂Cl₂N₂²⁺·SO₄²⁻, the two rings are not coplanar [dihedral angle = 48.7 (2)°]. In the crystal, multiple N—H⋯O hydrogen-bond interactions are found between the ammonium and sulfate groups.

Related literature

For related compounds, see: Chawdhury et al. (1968 ); Chu et al. (2007 ); Dobrzycki & Wozniak (2007 ); You et al. (2009 ).

Experimental

Crystal data

C₁₂H₁₂Cl₂N₂²⁺·SO₄²⁻
M_r = 351.20
Triclinic, $[P \overline 1]$
a = 6.5475 (11) Å
b = 7.9353 (13) Å
c = 13.363 (2) Å
α = 82.300 (2)°
β = 81.309 (3)°
γ = 88.765 (2)°
V = 680.12 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.65 mm⁻¹
T = 291 K
0.12 × 0.12 × 0.10 mm

Data collection

Bruker 1K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.926, T_max = 0.939
3484 measured reflections
2369 independent reflections
1825 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.091
S = 1.00
2369 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.89	1.78	2.668 (3)	173
N1—H1B⋯O2	0.89	2.10	2.874 (3)	144
N1—H1C⋯O4ⁱⁱ	0.89	1.90	2.775 (3)	167
N2—H2A⋯O4ⁱⁱⁱ	0.89	1.90	2.781 (3)	172
N2—H2B⋯O2^iv	0.89	1.99	2.865 (3)	166
N2—H2C⋯O3^v	0.89	2.06	2.938 (3)	168
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x+1, y, z; (iii) -x+1, -y, -z+1; (iv) x, y, z+1; (v) x+1, y, z+1.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811027905/ff2021sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027905/ff2021Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027905/ff2021Isup3.cml

checkCIF report

Comment top

There have been two single-crystal structural investigations on 4,4'-diamino-3,3'-dichlorobiphenyl, namely 4,4'-diamino-3,3'-dichlorobiphenyl (Chawdhury et al., 1968) and 4,4'-Diammonio-3,3'-dichlorobiphenyl dichloride (Dobrzycki & Wozniak, 2007). We have previously reported the single-crystal structures of 2-aminobenzimidazolium hydrogen sulfate (You et al., 2009) and (1R,3S)-1,2,2-trimethylcyclopentane-1,3-diammonium sulfate (Chu et al., 2007). In this work, we describe the single-crystal structure of a sulfate salt of 4,4'-diamino-3,3'-dichlorobiphenyl.

The atom-numbering scheme of the title salt is shown in Fig. 1. The two phenyl rings are not coplanar with a dihedral angle of 48.7 (2)°. In the crystal packing, multiple N—H···O hydrogen-bond interactions are found between the ammonio and sulfate groups.

Related literature top

For related compounds, see: Chawdhury et al. (1968); Chu et al. (2007); Dobrzycki & Wozniak (2007); You et al. (2009).

Experimental top

The treatment of 4,4'-diamino-3,3'-dichlorobiphenyl dissolved in methanol with an excess of sulfuric acid yields the title compound. Single crystals suitable for X-ray diffraction measurement were obtained after 5 days' slow evaporation of the mother liquid at room temperature in air. Anal. Calcd. For C₁₂H₁₂N₂Cl₂²⁺.SO₄^2-: C, 41.04; H, 3.44; N, 7.98%. Found: C, 41.22; H, 3.63; N, 7.79%.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. An ORTEP drawing of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

3,3'-Dichlorobiphenyl-4,4'-diaminium sulfate top

Crystal data top

C₁₂H₁₂Cl₂N₂²⁺·SO₄²⁻	Z = 2
M_r = 351.20	F(000) = 360
Triclinic, P1	D_x = 1.715 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5475 (11) Å	Cell parameters from 1332 reflections
b = 7.9353 (13) Å	θ = 2.8–27.6°
c = 13.363 (2) Å	µ = 0.65 mm⁻¹
α = 82.300 (2)°	T = 291 K
β = 81.309 (3)°	Block, colourless
γ = 88.765 (2)°	0.12 × 0.12 × 0.10 mm
V = 680.12 (19) Å³

Data collection top

Bruker 1K CCD area-detector diffractometer	2369 independent reflections
Radiation source: fine-focus sealed tube	1825 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −7→7
T_min = 0.926, T_max = 0.939	k = −8→9
3484 measured reflections	l = −8→15

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0394P)²] where P = (F_o² + 2F_c²)/3
2369 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₂H₁₂Cl₂N₂²⁺·SO₄²⁻	γ = 88.765 (2)°
M_r = 351.20	V = 680.12 (19) Å³
Triclinic, P1	Z = 2
a = 6.5475 (11) Å	Mo Kα radiation
b = 7.9353 (13) Å	µ = 0.65 mm⁻¹
c = 13.363 (2) Å	T = 291 K
α = 82.300 (2)°	0.12 × 0.12 × 0.10 mm
β = 81.309 (3)°

Data collection top

Bruker 1K CCD area-detector diffractometer	2369 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1825 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.939	R_int = 0.030
3484 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.00	Δρ_max = 0.25 e Å⁻³
2369 reflections	Δρ_min = −0.38 e Å⁻³
192 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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	0.7508 (4)	0.2990 (3)	0.4692 (2)	0.0268 (6)
C2	0.5748 (4)	0.2423 (3)	0.4365 (2)	0.0282 (6)
H2	0.4653	0.1965	0.4843	0.034*
C3	0.5626 (4)	0.2540 (3)	0.3332 (2)	0.0264 (6)
C4	0.7242 (4)	0.3252 (3)	0.2613 (2)	0.0236 (6)
C5	0.8970 (4)	0.3847 (4)	0.2935 (2)	0.0290 (7)
H5	1.0043	0.4346	0.2458	0.035*
C6	0.9099 (4)	0.3697 (4)	0.3965 (2)	0.0298 (7)
H6	1.0278	0.4079	0.4174	0.036*
C7	0.7701 (4)	0.2740 (3)	0.5796 (2)	0.0259 (6)
C8	0.9509 (4)	0.2014 (3)	0.6102 (2)	0.0291 (7)
H8	1.0581	0.1721	0.5616	0.035*
C9	0.9706 (4)	0.1731 (3)	0.7124 (2)	0.0252 (6)
C10	0.8127 (4)	0.2160 (3)	0.7859 (2)	0.0230 (6)
C11	0.6338 (4)	0.2909 (3)	0.7563 (2)	0.0273 (6)
H11	0.5279	0.3217	0.8051	0.033*
C12	0.6141 (4)	0.3193 (3)	0.6538 (2)	0.0277 (6)
H12	0.4943	0.3697	0.6342	0.033*
Cl1	0.35323 (11)	0.16699 (10)	0.29449 (6)	0.0399 (2)
Cl2	1.19670 (10)	0.08523 (9)	0.74738 (6)	0.0351 (2)
N1	0.7263 (3)	0.3316 (3)	0.15195 (16)	0.0266 (5)
H1A	0.7437	0.4386	0.1222	0.040*
H1B	0.6069	0.2923	0.1404	0.040*
H1C	0.8295	0.2678	0.1263	0.040*
N2	0.8311 (3)	0.1779 (3)	0.89363 (16)	0.0267 (5)
H2A	0.8553	0.0673	0.9087	0.040*
H2B	0.7141	0.2058	0.9310	0.040*
H2C	0.9351	0.2373	0.9071	0.040*
O1	0.2424 (3)	0.4428 (2)	0.08113 (15)	0.0381 (5)
O2	0.4527 (3)	0.2079 (2)	0.02918 (15)	0.0335 (5)
O3	0.2129 (3)	0.3412 (2)	−0.07783 (14)	0.0306 (5)
O4	0.0875 (3)	0.1693 (2)	0.07938 (15)	0.0311 (5)
S1	0.25232 (10)	0.29314 (8)	0.02901 (5)	0.02355 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0310 (15)	0.0270 (15)	0.0227 (15)	−0.0027 (12)	−0.0041 (13)	−0.0045 (12)
C2	0.0283 (15)	0.0300 (16)	0.0234 (15)	−0.0024 (12)	0.0028 (12)	0.0000 (13)
C3	0.0234 (14)	0.0286 (16)	0.0269 (16)	−0.0015 (12)	−0.0037 (12)	−0.0029 (13)
C4	0.0298 (15)	0.0206 (14)	0.0195 (14)	0.0013 (11)	−0.0039 (12)	0.0002 (11)
C5	0.0284 (15)	0.0311 (16)	0.0257 (16)	−0.0100 (12)	0.0008 (13)	−0.0011 (13)
C6	0.0311 (15)	0.0347 (17)	0.0239 (15)	−0.0073 (13)	−0.0038 (13)	−0.0047 (13)
C7	0.0301 (15)	0.0286 (15)	0.0193 (15)	−0.0046 (12)	−0.0033 (12)	−0.0040 (12)
C8	0.0264 (15)	0.0346 (17)	0.0249 (16)	−0.0005 (12)	0.0041 (13)	−0.0077 (13)
C9	0.0232 (14)	0.0220 (14)	0.0303 (16)	−0.0028 (11)	−0.0023 (12)	−0.0042 (12)
C10	0.0261 (14)	0.0231 (14)	0.0198 (14)	−0.0046 (11)	−0.0033 (12)	−0.0019 (12)
C11	0.0249 (14)	0.0334 (16)	0.0235 (15)	0.0029 (12)	−0.0010 (12)	−0.0069 (13)
C12	0.0270 (15)	0.0300 (16)	0.0258 (16)	0.0030 (12)	−0.0065 (13)	−0.0008 (13)
Cl1	0.0288 (4)	0.0558 (5)	0.0356 (5)	−0.0112 (3)	−0.0081 (3)	−0.0029 (4)
Cl2	0.0242 (4)	0.0399 (4)	0.0404 (5)	0.0043 (3)	−0.0044 (3)	−0.0040 (4)
N1	0.0275 (12)	0.0301 (13)	0.0220 (13)	−0.0012 (10)	−0.0030 (10)	−0.0027 (11)
N2	0.0269 (12)	0.0304 (13)	0.0233 (13)	0.0014 (10)	−0.0039 (10)	−0.0057 (11)
O1	0.0500 (13)	0.0323 (12)	0.0339 (12)	−0.0032 (10)	−0.0032 (10)	−0.0142 (10)
O2	0.0250 (10)	0.0389 (12)	0.0351 (12)	0.0058 (9)	−0.0044 (9)	−0.0010 (10)
O3	0.0355 (11)	0.0356 (12)	0.0209 (10)	0.0000 (9)	−0.0091 (9)	0.0008 (9)
O4	0.0269 (10)	0.0288 (11)	0.0346 (12)	−0.0033 (8)	0.0008 (9)	0.0013 (9)
S1	0.0221 (4)	0.0265 (4)	0.0211 (4)	−0.0020 (3)	−0.0017 (3)	−0.0015 (3)

Geometric parameters (Å, º) top

C1—C6	1.385 (4)	C9—Cl2	1.724 (3)
C1—C2	1.396 (4)	C10—C11	1.389 (3)
C1—C7	1.486 (4)	C10—N2	1.454 (3)
C2—C3	1.386 (4)	C11—C12	1.383 (4)
C2—H2	0.9300	C11—H11	0.9300
C3—C4	1.391 (4)	C12—H12	0.9300
C3—Cl1	1.725 (3)	N1—H1A	0.8900
C4—C5	1.383 (4)	N1—H1B	0.8900
C4—N1	1.453 (3)	N1—H1C	0.8900
C5—C6	1.381 (4)	N2—H2A	0.8900
C5—H5	0.9300	N2—H2B	0.8900
C6—H6	0.9300	N2—H2C	0.8900
C7—C12	1.389 (4)	O1—S1	1.4506 (19)
C7—C8	1.398 (4)	O2—S1	1.4636 (18)
C8—C9	1.379 (4)	O3—S1	1.4871 (19)
C8—H8	0.9300	O4—S1	1.4939 (19)
C9—C10	1.384 (4)

C6—C1—C2	118.6 (3)	C9—C10—C11	119.7 (2)
C6—C1—C7	121.2 (2)	C9—C10—N2	120.2 (2)
C2—C1—C7	120.1 (3)	C11—C10—N2	120.1 (2)
C3—C2—C1	120.3 (3)	C12—C11—C10	119.6 (2)
C3—C2—H2	119.8	C12—C11—H11	120.2
C1—C2—H2	119.8	C10—C11—H11	120.2
C2—C3—C4	120.2 (2)	C11—C12—C7	121.2 (2)
C2—C3—Cl1	119.3 (2)	C11—C12—H12	119.4
C4—C3—Cl1	120.3 (2)	C7—C12—H12	119.4
C5—C4—C3	119.6 (2)	C4—N1—H1A	109.5
C5—C4—N1	117.4 (2)	C4—N1—H1B	109.5
C3—C4—N1	122.8 (2)	H1A—N1—H1B	109.5
C6—C5—C4	119.8 (3)	C4—N1—H1C	109.5
C6—C5—H5	120.1	H1A—N1—H1C	109.5
C4—C5—H5	120.1	H1B—N1—H1C	109.5
C5—C6—C1	121.4 (3)	C10—N2—H2A	109.5
C5—C6—H6	119.3	C10—N2—H2B	109.5
C1—C6—H6	119.3	H2A—N2—H2B	109.5
C12—C7—C8	118.6 (2)	C10—N2—H2C	109.5
C12—C7—C1	122.3 (2)	H2A—N2—H2C	109.5
C8—C7—C1	119.1 (2)	H2B—N2—H2C	109.5
C9—C8—C7	120.2 (2)	O1—S1—O2	111.47 (11)
C9—C8—H8	119.9	O1—S1—O3	109.96 (12)
C7—C8—H8	119.9	O2—S1—O3	109.85 (11)
C8—C9—C10	120.7 (2)	O1—S1—O4	110.49 (12)
C8—C9—Cl2	118.9 (2)	O2—S1—O4	108.41 (11)
C10—C9—Cl2	120.3 (2)	O3—S1—O4	106.53 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	1.78	2.668 (3)	173
N1—H1B···O2	0.89	2.10	2.874 (3)	144
N1—H1C···O4ⁱⁱ	0.89	1.90	2.775 (3)	167
N2—H2A···O4ⁱⁱⁱ	0.89	1.90	2.781 (3)	172
N2—H2B···O2^iv	0.89	1.99	2.865 (3)	166
N2—H2C···O3^v	0.89	2.06	2.938 (3)	168

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂Cl₂N₂²⁺·SO₄²⁻
M_r	351.20
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	6.5475 (11), 7.9353 (13), 13.363 (2)
α, β, γ (°)	82.300 (2), 81.309 (3), 88.765 (2)
V (Å³)	680.12 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.65
Crystal size (mm)	0.12 × 0.12 × 0.10

Data collection
Diffractometer	Bruker 1K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.926, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	3484, 2369, 1825
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.091, 1.00
No. of reflections	2369
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.38

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	1.78	2.668 (3)	173
N1—H1B···O2	0.89	2.10	2.874 (3)	144
N1—H1C···O4ⁱⁱ	0.89	1.90	2.775 (3)	167
N2—H2A···O4ⁱⁱⁱ	0.89	1.90	2.781 (3)	172
N2—H2B···O2^iv	0.89	1.99	2.865 (3)	166
N2—H2C···O3^v	0.89	2.06	2.938 (3)	168

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

Acknowledgements

We acknowledge the National Natural Science Foundation of China (No. 20871065) and the Jiangsu Province Department of Science and Technology (No. BK2009226) for financial aid.

References

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