3,3'-Dichloro-biphenyl-4,4'-diaminium sulfate.

In the title compound, C(12)H(12)Cl(2)N(2) (2+)·SO(4) (2-), the two rings are not coplanar [dihedral angle = 48.7 (2)°]. In the crystal, multiple N-H⋯O hydrogen-bond inter-actions 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

C12H12Cl2N2 2+·SO4 2−

M = 351.20

Triclinic,

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[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.091

S = 1.00

2369 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.38 e Å−3

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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811027905/ff2021sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536811027905/ff2021Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H12Cl2N22+·SO42−	Z = 2
Mr = 351.20	F(000) = 360
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0394P)2] where P = (Fo2 + 2Fc2)/3
2369 reflections	(Δ/σ)max < 0.001
192 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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···O2iv	0.89	1.99	2.865 (3)	166
N2—H2C···O3v	0.89	2.06	2.938 (3)	168

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⋯O2iv	0.89	1.99	2.865 (3)	166
N2—H2C⋯O3v	0.89	2.06	2.938 (3)	168

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .