3,4,5-Trihy-droxy-benzohydrazidium perchlorate-3,4,5-trihy-droxy-benzohydrazide-water (1/1/1).

The crystal studied of the title compound, C(7)H(9)N(2)O(4) (+)·ClO(4) (-)·C(7)H(8)N(2)O(4)·H(2)O, was found to be a racemic twin with a 0.72 (18):0.28 (18) domain ratio. The hydrazidium group is close to planar, with an r.m.s deviation of 0.105 Å; the hydrazide group deviates more from planarity, with an r.m.s deviation of 0.174 Å. In the crystal, the hydrazidium cation, hydrazide mol-ecule, perchlorate anions and water mol-ecules are linked through O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds into a three-dimensional supra-molecular network. In addition, the benzene rings of the hydrazidium and hydrazide units are connected via π-π inter-actions into infinite chains along the c axis; the centroid-centroid distances are 3.486 (3) and 3.559 (3) Å.

Related literature

For the crystal structure of trimeth­oxy­benzohydrazidium chloride, see: Saeed et al. (2008 ▶) and of 3,4,5–trimeth­oxy­benzohydrazide hemihydrate, see: Zareef et al. (2006 ▶).

Experimental

Crystal data

C7H9N2O4 +·ClO4 −·C7H8N2O4·H2O

M = 486.78

Orthorhombic,

a = 20.1213 (7) Å

b = 12.9178 (4) Å

c = 7.0122 (2) Å

V = 1822.63 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 100 K

0.15 × 0.04 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.957, T max = 0.991

14383 measured reflections

3393 independent reflections

2653 reflections with I > 2σ(I)

R int = 0.092

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.109

S = 1.03

3393 reflections

335 parameters

22 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.53 e Å−3

Absolute structure: Flack (1983 ▶), 1545 Friedel pairs

Flack parameter: 0.28 (11)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811030595/lx2194sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811030595/lx2194Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811030595/lx2194Isup3.cml

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

C7H9N2O4+·ClO4−·C7H8N2O4·H2O	F(000) = 1008
Mr = 486.78	Dx = 1.774 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1227 reflections
a = 20.1213 (7) Å	θ = 3.2–27.0°
b = 12.9178 (4) Å	µ = 0.30 mm−1
c = 7.0122 (2) Å	T = 100 K
V = 1822.63 (10) Å3	Needle, colorless
Z = 4	0.15 × 0.04 × 0.03 mm

Bruker APEXII CCD diffractometer	3393 independent reflections
Radiation source: fine-focus sealed tube	2653 reflections with I > 2σ(I)
graphite	Rint = 0.092
φ and ω scans	θmax = 25.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→24
Tmin = 0.957, Tmax = 0.991	k = −15→15
14383 measured reflections	l = −8→8

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.109	w = 1/[σ2(Fo2) + (0.0535P)2] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
3393 reflections	Δρmax = 0.39 e Å−3
335 parameters	Δρmin = −0.53 e Å−3
22 restraints	Absolute structure: Flack (1983), 1545 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.28 (11)

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
O1	0.47204 (14)	0.7004 (2)	0.1226 (4)	0.0100 (7)
O2	0.74400 (13)	0.8918 (2)	0.1487 (5)	0.0141 (7)
H2O	0.722 (2)	0.945 (2)	0.133 (8)	0.021*
O3	0.78618 (15)	0.7058 (2)	0.2858 (4)	0.0107 (7)
H3O	0.795 (2)	0.652 (2)	0.343 (6)	0.016*
O4	0.70017 (14)	0.5426 (2)	0.3081 (4)	0.0121 (7)
H4O	0.6714 (18)	0.496 (3)	0.301 (7)	0.018*
N1	0.42795 (17)	0.8931 (3)	0.1273 (5)	0.0095 (8)
H1A	0.4015 (19)	0.856 (3)	0.054 (5)	0.011*
H1B	0.416 (2)	0.880 (3)	0.247 (3)	0.011*
N2	0.49692 (17)	0.8702 (3)	0.1213 (6)	0.0119 (9)
H2N	0.5225 (18)	0.921 (2)	0.155 (7)	0.014*
C1	0.5142 (2)	0.7687 (3)	0.1322 (6)	0.0104 (9)
C2	0.58680 (19)	0.7498 (3)	0.1540 (7)	0.0075 (8)
C3	0.6324 (2)	0.8282 (3)	0.1261 (6)	0.0107 (9)
H3	0.6182	0.8929	0.0760	0.013*
C4	0.6987 (2)	0.8133 (3)	0.1707 (6)	0.0089 (9)
C5	0.7199 (2)	0.7175 (3)	0.2372 (6)	0.0097 (9)
C6	0.6750 (2)	0.6371 (3)	0.2535 (6)	0.0097 (9)
C7	0.6085 (2)	0.6524 (3)	0.2159 (6)	0.0101 (9)
H7	0.5776	0.5974	0.2317	0.012*
O5	0.46214 (14)	0.4747 (2)	0.3255 (4)	0.0143 (7)
O6	0.23020 (14)	0.1848 (2)	0.2092 (4)	0.0150 (8)
H6O	0.2019 (19)	0.218 (3)	0.268 (6)	0.022*
O7	0.32391 (15)	0.0490 (2)	0.1104 (5)	0.0153 (7)
H7O	0.2861 (14)	0.045 (4)	0.162 (7)	0.023*
O8	0.44941 (15)	0.1051 (2)	0.0634 (5)	0.0140 (7)
H8O	0.4886 (12)	0.125 (3)	0.071 (7)	0.021*
N3	0.3796 (2)	0.6259 (3)	0.3853 (5)	0.0119 (8)
H3A	0.3444 (16)	0.666 (3)	0.360 (6)	0.014*
H3B	0.4158 (16)	0.643 (4)	0.314 (6)	0.014*
H3C	0.394 (2)	0.631 (4)	0.509 (3)	0.014*
N4	0.35607 (18)	0.5261 (3)	0.3343 (5)	0.0119 (8)
H4N	0.3207 (15)	0.531 (4)	0.264 (6)	0.014*
C8	0.4038 (2)	0.4525 (3)	0.2963 (6)	0.0111 (10)
C9	0.3795 (2)	0.3506 (3)	0.2357 (6)	0.0114 (9)
C10	0.3123 (2)	0.3228 (3)	0.2482 (6)	0.0095 (9)
H10	0.2800	0.3717	0.2883	0.011*
C11	0.2938 (2)	0.2221 (3)	0.2007 (6)	0.0104 (10)
C12	0.3409 (2)	0.1510 (3)	0.1452 (7)	0.0110 (9)
C13	0.4064 (2)	0.1793 (3)	0.1252 (6)	0.0119 (9)
C14	0.4260 (2)	0.2797 (3)	0.1712 (6)	0.0122 (10)
H14	0.4713	0.2994	0.1583	0.015*
O9	0.59168 (16)	0.4012 (2)	0.2777 (5)	0.0151 (8)
H9A	0.596 (3)	0.344 (2)	0.334 (7)	0.023*
H9B	0.5591 (17)	0.432 (3)	0.325 (7)	0.023*
Cl1	0.61543 (5)	0.11830 (8)	0.15644 (16)	0.0126 (2)
O10	0.67545 (14)	0.0734 (2)	0.0667 (4)	0.0114 (7)
O11	0.57866 (15)	0.1783 (2)	0.0090 (4)	0.0131 (7)
O12	0.63558 (14)	0.1903 (2)	0.3124 (4)	0.0103 (7)
O13	0.57257 (14)	0.0391 (2)	0.2378 (4)	0.0116 (7)

	U11	U22	U33	U12	U13	U23
O1	0.0097 (15)	0.0054 (14)	0.0148 (16)	−0.0020 (12)	−0.0002 (14)	0.0012 (13)
O2	0.0099 (15)	0.0100 (14)	0.0225 (16)	−0.0009 (13)	−0.0038 (17)	0.0047 (16)
O3	0.0085 (16)	0.0089 (15)	0.0147 (17)	−0.0007 (13)	−0.0049 (14)	0.0025 (13)
O4	0.0091 (16)	0.0054 (15)	0.0220 (16)	−0.0008 (12)	−0.0041 (14)	0.0013 (14)
N1	0.0069 (17)	0.0144 (18)	0.007 (2)	−0.0003 (15)	−0.0011 (16)	−0.0039 (17)
N2	0.0061 (18)	0.0097 (18)	0.020 (2)	0.0008 (15)	−0.0016 (17)	−0.0005 (17)
C1	0.017 (2)	0.009 (2)	0.005 (2)	0.0016 (18)	0.003 (2)	0.0009 (19)
C2	0.0069 (19)	0.0091 (19)	0.0063 (18)	0.0001 (16)	−0.001 (2)	−0.004 (2)
C3	0.016 (2)	0.010 (2)	0.007 (2)	0.0042 (17)	−0.002 (2)	−0.0006 (19)
C4	0.007 (2)	0.008 (2)	0.011 (2)	−0.0006 (17)	0.002 (2)	−0.0016 (19)
C5	0.008 (2)	0.014 (2)	0.007 (2)	−0.0008 (18)	0.0025 (19)	−0.0014 (19)
C6	0.018 (2)	0.0026 (19)	0.008 (2)	0.0024 (18)	−0.0033 (19)	0.0021 (17)
C7	0.016 (2)	0.0049 (18)	0.009 (2)	−0.0022 (18)	−0.0016 (19)	−0.0014 (17)
O5	0.0089 (17)	0.0131 (15)	0.0209 (18)	0.0001 (13)	0.0026 (14)	0.0016 (14)
O6	0.0079 (17)	0.0131 (16)	0.024 (2)	0.0022 (13)	0.0060 (14)	−0.0018 (14)
O7	0.0101 (16)	0.0121 (15)	0.024 (2)	0.0006 (13)	0.0031 (15)	−0.0022 (14)
O8	0.0095 (16)	0.0114 (16)	0.0211 (17)	0.0021 (13)	−0.0007 (14)	−0.0036 (14)
N3	0.011 (2)	0.011 (2)	0.014 (2)	0.0029 (18)	−0.0010 (18)	−0.0016 (18)
N4	0.0106 (19)	0.0060 (17)	0.019 (2)	0.0033 (16)	−0.0024 (17)	−0.0059 (17)
C8	0.012 (2)	0.018 (2)	0.003 (2)	0.0012 (19)	−0.0009 (18)	0.0013 (19)
C9	0.017 (3)	0.0084 (19)	0.0084 (19)	0.0011 (19)	−0.003 (2)	0.0002 (17)
C10	0.014 (2)	0.005 (2)	0.009 (2)	0.0044 (18)	0.003 (2)	0.0011 (18)
C11	0.009 (2)	0.016 (2)	0.006 (2)	0.0005 (19)	0.0024 (17)	0.0025 (18)
C12	0.014 (2)	0.0065 (19)	0.013 (2)	0.0022 (17)	−0.005 (2)	−0.001 (2)
C13	0.013 (2)	0.012 (2)	0.011 (2)	0.0060 (18)	−0.0003 (19)	−0.005 (2)
C14	0.013 (2)	0.016 (2)	0.008 (2)	−0.0017 (18)	0.000 (2)	0.001 (2)
O9	0.0136 (18)	0.0108 (17)	0.0209 (19)	0.0038 (14)	0.0024 (15)	0.0002 (14)
Cl1	0.0136 (5)	0.0122 (5)	0.0120 (5)	−0.0006 (5)	0.0010 (5)	0.0001 (5)
O10	0.0094 (16)	0.0089 (15)	0.0158 (15)	0.0011 (13)	0.0038 (14)	0.0029 (13)
O11	0.0144 (17)	0.0134 (16)	0.0114 (15)	0.0056 (14)	−0.0025 (14)	0.0017 (13)
O12	0.0122 (16)	0.0094 (15)	0.0095 (15)	−0.0040 (13)	0.0011 (13)	−0.0020 (13)
O13	0.0110 (16)	0.0074 (14)	0.0164 (16)	−0.0070 (13)	0.0039 (14)	−0.0035 (13)

O1—C1	1.227 (5)	O7—H7O	0.843 (19)
O2—C4	1.372 (5)	O8—C13	1.362 (5)
O2—H2O	0.826 (19)	O8—H8O	0.830 (19)
O3—C5	1.384 (5)	N3—N4	1.420 (5)
O3—H3O	0.82 (2)	N3—H3A	0.892 (19)
O4—C6	1.376 (5)	N3—H3B	0.911 (19)
O4—H4O	0.839 (19)	N3—H3C	0.919 (19)
N1—N2	1.420 (5)	N4—C8	1.377 (6)
N1—H1A	0.880 (19)	N4—H4N	0.867 (19)
N1—H1B	0.891 (19)	C8—C9	1.467 (6)
N2—C1	1.358 (5)	C9—C14	1.385 (6)
N2—H2N	0.863 (19)	C9—C10	1.402 (6)
C1—C2	1.488 (6)	C10—C11	1.393 (6)
C2—C3	1.381 (6)	C10—H10	0.9500
C2—C7	1.401 (6)	C11—C12	1.376 (6)
C3—C4	1.384 (6)	C12—C13	1.375 (6)
C3—H3	0.9500	C13—C14	1.393 (6)
C4—C5	1.389 (6)	C14—H14	0.9500
C5—C6	1.382 (6)	O9—H9A	0.85 (2)
C6—C7	1.379 (6)	O9—H9B	0.83 (2)
C7—H7	0.9500	Cl1—O13	1.455 (3)
O5—C8	1.226 (5)	Cl1—O10	1.480 (3)
O6—C11	1.368 (5)	Cl1—O11	1.489 (3)
O6—H6O	0.82 (2)	Cl1—O12	1.492 (3)
O7—C12	1.382 (5)
C4—O2—H2O	105 (3)	H3A—N3—H3B	113 (4)
C5—O3—H3O	115 (3)	N4—N3—H3C	114 (3)
C6—O4—H4O	112 (3)	H3A—N3—H3C	113 (4)
N2—N1—H1A	117 (3)	H3B—N3—H3C	104 (4)
N2—N1—H1B	104 (3)	C8—N4—N3	116.3 (4)
H1A—N1—H1B	107 (4)	C8—N4—H4N	121 (3)
C1—N2—N1	116.8 (3)	N3—N4—H4N	110 (3)
C1—N2—H2N	124 (3)	O5—C8—N4	118.3 (4)
N1—N2—H2N	115 (3)	O5—C8—C9	125.2 (4)
O1—C1—N2	120.9 (4)	N4—C8—C9	116.3 (4)
O1—C1—C2	124.5 (3)	C14—C9—C10	120.1 (4)
N2—C1—C2	114.6 (4)	C14—C9—C8	117.6 (4)
C3—C2—C7	119.8 (4)	C10—C9—C8	122.2 (4)
C3—C2—C1	121.2 (4)	C11—C10—C9	118.9 (4)
C7—C2—C1	119.0 (4)	C11—C10—H10	120.6
C2—C3—C4	120.4 (4)	C9—C10—H10	120.6
C2—C3—H3	119.8	O6—C11—C12	114.9 (4)
C4—C3—H3	119.8	O6—C11—C10	124.6 (4)
O2—C4—C3	120.8 (4)	C12—C11—C10	120.4 (4)
O2—C4—C5	119.5 (4)	C13—C12—C11	120.7 (4)
C3—C4—C5	119.8 (4)	C13—C12—O7	118.2 (4)
C6—C5—O3	121.8 (4)	C11—C12—O7	121.1 (4)
C6—C5—C4	119.8 (4)	O8—C13—C12	117.0 (4)
O3—C5—C4	118.4 (4)	O8—C13—C14	123.2 (4)
O4—C6—C7	122.5 (4)	C12—C13—C14	119.7 (4)
O4—C6—C5	116.7 (4)	C9—C14—C13	120.0 (4)
C7—C6—C5	120.8 (4)	C9—C14—H14	120.0
C6—C7—C2	119.3 (4)	C13—C14—H14	120.0
C6—C7—H7	120.3	H9A—O9—H9B	108 (5)
C2—C7—H7	120.3	O13—Cl1—O10	112.02 (17)
C11—O6—H6O	119 (3)	O13—Cl1—O11	110.14 (18)
C12—O7—H7O	102 (3)	O10—Cl1—O11	108.30 (18)
C13—O8—H8O	111 (3)	O13—Cl1—O12	108.18 (18)
N4—N3—H3A	102 (3)	O10—Cl1—O12	109.52 (18)
N4—N3—H3B	110 (3)	O11—Cl1—O12	108.63 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O12i	0.88 (2)	1.95 (3)	2.769 (5)	155 (4)
N1—H1B···O11ii	0.89 (2)	1.99 (3)	2.835 (5)	159 (4)
N2—H2N···O13iii	0.86 (2)	1.92 (2)	2.783 (4)	175 (4)
O2—H2O···O10iii	0.83 (2)	1.96 (2)	2.782 (4)	173 (5)
N3—H3A···O3iv	0.89 (2)	2.10 (2)	2.958 (5)	161 (4)
N3—H3B···O1	0.91 (2)	1.90 (2)	2.788 (5)	163 (4)
N3—H3C···O9ii	0.92 (2)	1.95 (2)	2.833 (5)	160 (4)
O3—H3O···O4	0.82 (2)	2.39 (5)	2.732 (4)	106 (4)
O3—H3O···O10v	0.82 (2)	1.96 (3)	2.720 (4)	153 (4)
N4—H4N···O2iv	0.87 (2)	2.01 (3)	2.811 (5)	154 (4)
O4—H4O···O9	0.84 (2)	2.02 (2)	2.854 (4)	171 (5)
O6—H6O···O12vi	0.82 (2)	1.81 (3)	2.598 (4)	160 (5)
O7—H7O···O6	0.84 (2)	2.15 (4)	2.667 (4)	119 (4)
O7—H7O···O4vi	0.84 (2)	2.31 (3)	3.085 (4)	154 (4)
O8—H8O···O11	0.83 (2)	1.99 (2)	2.794 (4)	164 (5)
O8—H8O···O13	0.83 (2)	2.34 (4)	2.892 (4)	125 (4)
O9—H9A···O12	0.85 (2)	2.14 (3)	2.875 (4)	145 (5)
O9—H9A···O1ii	0.85 (2)	2.51 (5)	3.036 (4)	121 (4)
O9—H9B···O5	0.83 (2)	2.03 (3)	2.794 (4)	152 (5)
C3—H3···O13iii	0.95	2.39	3.079 (5)	129.
C7—H7···O9	0.95	2.57	3.291 (5)	133.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O12i	0.88 (2)	1.95 (3)	2.769 (5)	155 (4)
N1—H1B⋯O11ii	0.89 (2)	1.99 (3)	2.835 (5)	159 (4)
N2—H2N⋯O13iii	0.86 (2)	1.92 (2)	2.783 (4)	175 (4)
O2—H2O⋯O10iii	0.83 (2)	1.96 (2)	2.782 (4)	173 (5)
N3—H3A⋯O3iv	0.89 (2)	2.10 (2)	2.958 (5)	161 (4)
N3—H3B⋯O1	0.91 (2)	1.90 (2)	2.788 (5)	163 (4)
N3—H3C⋯O9ii	0.92 (2)	1.95 (2)	2.833 (5)	160 (4)
O3—H3O⋯O4	0.82 (2)	2.39 (5)	2.732 (4)	106 (4)
O3—H3O⋯O10v	0.82 (2)	1.96 (3)	2.720 (4)	153 (4)
N4—H4N⋯O2iv	0.87 (2)	2.01 (3)	2.811 (5)	154 (4)
O4—H4O⋯O9	0.84 (2)	2.02 (2)	2.854 (4)	171 (5)
O6—H6O⋯O12vi	0.82 (2)	1.81 (3)	2.598 (4)	160 (5)
O7—H7O⋯O6	0.84 (2)	2.15 (4)	2.667 (4)	119 (4)
O7—H7O⋯O4vi	0.84 (2)	2.31 (3)	3.085 (4)	154 (4)
O8—H8O⋯O11	0.83 (2)	1.99 (2)	2.794 (4)	164 (5)
O8—H8O⋯O13	0.83 (2)	2.34 (4)	2.892 (4)	125 (4)
O9—H9A⋯O12	0.85 (2)	2.14 (3)	2.875 (4)	145 (5)
O9—H9A⋯O1ii	0.85 (2)	2.51 (5)	3.036 (4)	121 (4)
O9—H9B⋯O5	0.83 (2)	2.03 (3)	2.794 (4)	152 (5)
C3—H3⋯O13iii	0.95	2.39	3.079 (5)	129
C7—H7⋯O9	0.95	2.57	3.291 (5)	133

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