Hydrazine-1,2-diium bis-(3-carb-oxy-4-hy-droxy-benzene-sulfonate) tetra-hydrate.

Reaction of 5-sulfosalicylic acid with hydrazine hydrate at pH = 1 results in the formation of the title hydrated salt, 0.5N(2)H(6) (2+)·C(7)H(5)O(6)S(-)·2H(2)O. The hydrazinium dications lie on centres of inversion. They are located between 3-carb-oxy-4-hy-droxy-benzene-sulfonate anions, forming inter-molecular N-H⋯O hydrogen bonds with sulfonate ions and water mol-ecules of crystallisation. Further intra- and inter-molecular O-H⋯O hydrogen bonds are observed in the crystal structure.

Related literature

For general background on hydrogen bonding in proton-transfer compounds of 3-carb­oxy-4-hy­droxy­benzene­sulfonate anions with Lewis bases, see: Smith et al. (2004 ▶, 2005 ▶). For recent related structures containing the 3-carb­oxy-4-hy­droxy­benzene­sulfonate anion, see: Wang, Yang et al. (2008 ▶); Wang, Yao et al. (2008 ▶); Smith & Wermuth (2009 ▶); Hemamalini & Fun (2010 ▶); Yin et al. (2010 ▶). For related structures containing the N2H6 2+ hydrazinium dication, see: Starosta & Leciejewicz (2008 ▶); Klapotke et al. (1996 ▶).

Experimental

Crystal data

0.5N2H6 2+·C7H5O6S−·2H2O

M = 270.25

Triclinic,

a = 7.0620 (5) Å

b = 7.2069 (4) Å

c = 11.5995 (8) Å

α = 78.460 (3)°

β = 75.806 (3)°

γ = 77.379 (3)°

V = 551.77 (6) Å3

Z = 2

Mo Kα radiation

μ = 0.33 mm−1

T = 296 K

0.50 × 0.40 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.823, T max = 0.882

9320 measured reflections

2711 independent reflections

2582 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.107

S = 1.12

2711 reflections

187 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.52 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Bruno et al., 2002 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014231/zq2096sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014231/zq2096Isup2.hkl

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

0.5N2H62+·C7H5O6S−·2H2O	Z = 2
Mr = 270.25	F(000) = 282
Triclinic, P1	Dx = 1.627 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.0620 (5) Å	Cell parameters from 6221 reflections
b = 7.2069 (4) Å	θ = 2.5–26.2°
c = 11.5995 (8) Å	µ = 0.33 mm−1
α = 78.460 (3)°	T = 296 K
β = 75.806 (3)°	Block, colourless
γ = 77.379 (3)°	0.50 × 0.40 × 0.30 mm
V = 551.77 (6) Å3

Bruker Kappa APEXII CCD area-detector diffractometer	2711 independent reflections
Radiation source: fine-focus sealed tube	2582 reflections with I > 2σ(I)
graphite	Rint = 0.057
ω and φ scans	θmax = 28.2°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −9→9
Tmin = 0.823, Tmax = 0.882	k = −9→9
9320 measured reflections	l = −13→15

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107	w = 1/[σ2(Fo2) + (0.0527P)2 + 0.1344P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max < 0.001
2711 reflections	Δρmax = 0.41 e Å−3
187 parameters	Δρmin = −0.52 e Å−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 1.12 (4)

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	0.28715 (19)	1.12543 (18)	0.37831 (12)	0.0277 (3)
H7	0.2576	1.2577	0.3783	0.033*
C2	0.36576 (19)	1.05458 (18)	0.27144 (12)	0.0268 (3)
C3	0.4096 (2)	0.8553 (2)	0.27042 (15)	0.0373 (3)
H1	0.4618	0.8079	0.1981	0.045*
C4	0.3755 (3)	0.7304 (2)	0.37640 (16)	0.0434 (4)
H3	0.4049	0.5983	0.3756	0.052*
C5	0.2966 (2)	0.8008 (2)	0.48587 (14)	0.0364 (3)
C6	0.2515 (2)	1.00021 (19)	0.48664 (13)	0.0290 (3)
C7	0.1686 (2)	1.0757 (2)	0.60113 (13)	0.0323 (3)
N1	0.01665 (18)	−0.00608 (18)	0.93729 (10)	0.0272 (3)
O1	0.59710 (15)	1.13796 (16)	0.06468 (10)	0.0369 (3)
O7	−0.03247 (17)	0.36335 (14)	0.80737 (10)	0.0340 (3)
O2	0.40796 (15)	1.40062 (14)	0.17028 (9)	0.0333 (3)
O8	0.19337 (19)	0.5388 (2)	0.88950 (13)	0.0505 (3)
O3	0.24335 (15)	1.22941 (15)	0.07799 (10)	0.0356 (3)
O4	0.1284 (2)	1.26416 (17)	0.58929 (11)	0.0445 (3)
O5	0.1392 (2)	0.97087 (18)	0.69881 (10)	0.0454 (3)
O6	0.2667 (2)	0.67267 (18)	0.58729 (12)	0.0568 (4)
H6	0.2187	0.7301	0.6450	0.085*
S1	0.40819 (4)	1.21604 (4)	0.13623 (3)	0.02543 (16)
H7A	−0.144 (2)	0.430 (3)	0.8122 (19)	0.046 (5)*
H7B	0.043 (3)	0.425 (3)	0.825 (2)	0.062 (7)*
H4	0.086 (4)	1.300 (4)	0.653 (2)	0.058 (7)*
H8B	0.312 (3)	0.559 (4)	0.858 (2)	0.069 (7)*
H8A	0.208 (4)	0.446 (3)	0.949 (2)	0.091 (10)*
H1A	−0.060 (3)	−0.070 (3)	0.9285 (17)	0.035 (5)*
H1B	−0.008 (3)	0.118 (3)	0.8930 (19)	0.045 (5)*
H1C	0.144 (3)	−0.067 (3)	0.9181 (19)	0.047 (5)*

	U11	U22	U33	U12	U13	U23
C1	0.0271 (6)	0.0250 (6)	0.0312 (6)	−0.0017 (5)	−0.0065 (5)	−0.0078 (5)
C2	0.0240 (6)	0.0262 (6)	0.0300 (6)	−0.0008 (4)	−0.0065 (5)	−0.0067 (5)
C3	0.0428 (8)	0.0286 (7)	0.0387 (8)	0.0024 (6)	−0.0068 (6)	−0.0130 (6)
C4	0.0567 (10)	0.0237 (6)	0.0467 (9)	0.0024 (6)	−0.0108 (8)	−0.0092 (6)
C5	0.0438 (8)	0.0273 (7)	0.0374 (7)	−0.0021 (6)	−0.0134 (6)	−0.0018 (6)
C6	0.0289 (6)	0.0291 (6)	0.0303 (6)	−0.0027 (5)	−0.0090 (5)	−0.0069 (5)
C7	0.0331 (7)	0.0350 (7)	0.0300 (7)	−0.0061 (5)	−0.0079 (5)	−0.0063 (5)
N1	0.0263 (6)	0.0313 (6)	0.0243 (6)	−0.0042 (4)	−0.0055 (4)	−0.0061 (4)
O1	0.0251 (5)	0.0461 (6)	0.0361 (5)	−0.0001 (4)	0.0002 (4)	−0.0140 (5)
O7	0.0362 (6)	0.0295 (5)	0.0361 (5)	−0.0013 (4)	−0.0069 (4)	−0.0105 (4)
O2	0.0336 (5)	0.0292 (5)	0.0376 (5)	−0.0074 (4)	−0.0033 (4)	−0.0094 (4)
O8	0.0391 (7)	0.0573 (8)	0.0577 (8)	−0.0184 (6)	−0.0190 (6)	0.0066 (6)
O3	0.0306 (5)	0.0376 (5)	0.0417 (6)	−0.0068 (4)	−0.0152 (4)	−0.0031 (4)
O4	0.0646 (8)	0.0348 (6)	0.0307 (6)	−0.0039 (5)	−0.0029 (5)	−0.0115 (4)
O5	0.0622 (8)	0.0433 (6)	0.0285 (5)	−0.0086 (5)	−0.0079 (5)	−0.0034 (5)
O6	0.0906 (11)	0.0314 (6)	0.0418 (7)	−0.0058 (6)	−0.0132 (7)	0.0033 (5)
S1	0.0201 (2)	0.0276 (2)	0.0285 (2)	−0.00186 (12)	−0.00404 (13)	−0.00819 (13)

C1—C2	1.3775 (19)	N1—N1i	1.433 (2)
C1—C6	1.3954 (19)	N1—H1A	0.82 (2)
C1—H7	0.9300	N1—H1B	0.94 (2)
C2—C3	1.4030 (18)	N1—H1C	0.91 (2)
C2—S1	1.7594 (14)	O1—S1	1.4495 (10)
C3—C4	1.374 (2)	O7—H7A	0.826 (15)
C3—H1	0.9300	O7—H7B	0.847 (15)
C4—C5	1.403 (2)	O2—S1	1.4610 (10)
C4—H3	0.9300	O8—H8B	0.859 (16)
C5—O6	1.3453 (19)	O8—H8A	0.874 (17)
C5—C6	1.404 (2)	O3—S1	1.4599 (10)
C6—C7	1.473 (2)	O4—H4	0.79 (3)
C7—O5	1.2282 (18)	O6—H6	0.8200
C7—O4	1.3115 (19)
C2—C1—C6	120.48 (12)	O5—C7—C6	122.77 (14)
C2—C1—H7	119.8	O4—C7—C6	114.08 (13)
C6—C1—H7	119.8	N1i—N1—H1A	108.5 (13)
C1—C2—C3	120.22 (13)	N1i—N1—H1B	109.8 (13)
C1—C2—S1	119.44 (10)	H1A—N1—H1B	109.2 (19)
C3—C2—S1	120.34 (11)	N1i—N1—H1C	104.8 (14)
C4—C3—C2	119.94 (14)	H1A—N1—H1C	110.6 (18)
C4—C3—H1	120.0	H1B—N1—H1C	113.7 (18)
C2—C3—H1	120.0	H7A—O7—H7B	108.4 (18)
C3—C4—C5	120.36 (13)	H8B—O8—H8A	104 (2)
C3—C4—H3	119.8	C7—O4—H4	111.4 (18)
C5—C4—H3	119.8	C5—O6—H6	109.5
O6—C5—C4	118.15 (13)	O1—S1—O3	112.19 (7)
O6—C5—C6	122.23 (14)	O1—S1—O2	112.97 (6)
C4—C5—C6	119.63 (14)	O3—S1—O2	110.87 (6)
C1—C6—C5	119.37 (13)	O1—S1—C2	107.30 (6)
C1—C6—C7	120.56 (12)	O3—S1—C2	106.83 (6)
C5—C6—C7	120.07 (13)	O2—S1—C2	106.24 (6)
O5—C7—O4	123.15 (14)
C6—C1—C2—C3	0.4 (2)	C4—C5—C6—C7	180.00 (15)
C6—C1—C2—S1	179.78 (10)	C1—C6—C7—O5	−178.27 (14)
C1—C2—C3—C4	−0.5 (2)	C5—C6—C7—O5	1.3 (2)
S1—C2—C3—C4	−179.82 (13)	C1—C6—C7—O4	2.0 (2)
C2—C3—C4—C5	0.1 (3)	C5—C6—C7—O4	−178.35 (14)
C3—C4—C5—O6	−179.70 (16)	C1—C2—S1—O1	139.04 (11)
C3—C4—C5—C6	0.3 (3)	C3—C2—S1—O1	−41.61 (14)
C2—C1—C6—C5	0.0 (2)	C1—C2—S1—O3	−100.46 (12)
C2—C1—C6—C7	179.62 (12)	C3—C2—S1—O3	78.89 (13)
O6—C5—C6—C1	179.65 (14)	C1—C2—S1—O2	17.95 (13)
C4—C5—C6—C1	−0.4 (2)	C3—C2—S1—O2	−162.70 (12)
O6—C5—C6—C7	0.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6···O5	0.82	1.88	2.6074 (18)	146.
O7—H7A···O2ii	0.83 (2)	1.98 (2)	2.8036 (15)	177 (2)
O7—H7B···O8	0.85 (2)	1.84 (2)	2.6754 (17)	171 (2)
O4—H4···O7iii	0.79 (3)	1.89 (3)	2.6758 (16)	174 (3)
O8—H8B···O2iv	0.86 (2)	2.00 (2)	2.8384 (16)	165 (2)
O8—H8A···O3v	0.87 (2)	1.95 (2)	2.8213 (17)	177 (3)
N1—H1A···O3vi	0.82 (2)	1.93 (2)	2.7493 (17)	175.2 (19)
N1—H1B···O7	0.94 (2)	1.84 (2)	2.7798 (16)	174.5 (19)
N1—H1C···O1vii	0.91 (2)	1.84 (2)	2.6813 (16)	154 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6⋯O5	0.82	1.88	2.6074 (18)	146
O7—H7A⋯O2i	0.83 (2)	1.98 (2)	2.8036 (15)	177 (2)
O7—H7B⋯O8	0.85 (2)	1.84 (2)	2.6754 (17)	171 (2)
O4—H4⋯O7ii	0.79 (3)	1.89 (3)	2.6758 (16)	174 (3)
O8—H8B⋯O2iii	0.86 (2)	2.00 (2)	2.8384 (16)	165 (2)
O8—H8A⋯O3iv	0.87 (2)	1.95 (2)	2.8213 (17)	177 (3)
N1—H1A⋯O3v	0.82 (2)	1.93 (2)	2.7493 (17)	175.2 (19)
N1—H1B⋯O7	0.94 (2)	1.84 (2)	2.7798 (16)	174.5 (19)
N1—H1C⋯O1vi	0.91 (2)	1.84 (2)	2.6813 (16)	154 (2)

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