(E)-1-(4-Nitro-phen-yl)-2-(4-{[(E)-2-(4-nitro-phen-yl)hydrazinyl-idene]meth-yl}benzyl-idene)hydrazine dihydrate.

The 30 non-H atoms in title dihydrazine compound, C(20)H(16)N(6)O(4)·2H(2)O, are close to coplanar, the r.m.s. deviation for these atoms being 0.096 Å. The conformation about each of the C=N bonds is E, and the mol-ecule has non-crystallographic 2/m symmetry. The presence of O-H⋯O and N-H⋯O hydrogen bonding leads to a three-dimensional network in the crystal structure. A highly disordered solvent mol-ecule is present within a mol-ecular cavity defined by the organic and water mol-ecules. Its contribution to the electron density was removed from the observed data in the final cycles of refinement and the formula, molecular weight and density are given without taking into account the contribution of the solvent molecule.

Related literature

For background to the structural chemistry of hydrazones, see: Baddeley et al. (2009 ▶); Ferguson et al. (2005 ▶); Glidewell et al. (2006 ▶); Low et al. (2006 ▶); Wardell et al. (2005 ▶, 2006 ▶). For the synthesis, see: Bengelsdorf (1958 ▶).

Experimental

Crystal data

C20H16N6O4·2H2O

M = 440.42

Triclinic,

a = 7.7549 (4) Å

b = 9.3245 (7) Å

c = 15.3374 (11) Å

α = 100.749 (3)°

β = 90.533 (4)°

γ = 103.131 (5)°

V = 1059.56 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 120 K

0.38 × 0.22 × 0.07 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T min = 0.770, T max = 1.000

16566 measured reflections

3688 independent reflections

2638 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.177

S = 1.09

3688 reflections

301 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.30 e Å−3

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and PLATON (Spek, 2009 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053963/hg2618sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053963/hg2618Isup2.hkl

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

C20H16N6O4·2H2O	Z = 2
Mr = 440.42	F(000) = 460
Triclinic, P1	Dx = 1.380 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7549 (4) Å	Cell parameters from 4364 reflections
b = 9.3245 (7) Å	θ = 2.9–27.5°
c = 15.3374 (11) Å	µ = 0.11 mm−1
α = 100.749 (3)°	T = 120 K
β = 90.533 (4)°	Block, dark-red
γ = 103.131 (5)°	0.38 × 0.22 × 0.07 mm
V = 1059.56 (12) Å3

Nonius KappaCCD area-detector diffractometer	3688 independent reflections
Radiation source: Enraf–Nonius FR591 rotating anode	2638 reflections with I > 2σ(I)
10 cm confocal mirrors	Rint = 0.039
Detector resolution: 9.091 pixels mm-1	θmax = 25.0°, θmin = 3.0°
φ and ω scans	h = −9→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2007)	k = −11→11
Tmin = 0.770, Tmax = 1.000	l = −18→18
16566 measured reflections

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0852P)2 + 0.5693P] where P = (Fo2 + 2Fc2)/3
3688 reflections	(Δ/σ)max < 0.001
301 parameters	Δρmax = 0.45 e Å−3
6 restraints	Δρmin = −0.30 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	−0.2175 (2)	−0.6067 (2)	1.41897 (13)	0.0387 (5)
O2	−0.3174 (3)	−0.6708 (2)	1.28198 (14)	0.0421 (5)
O3	1.1204 (2)	0.9370 (2)	0.69699 (13)	0.0388 (5)
O4	0.9881 (2)	0.8999 (2)	0.56744 (12)	0.0340 (5)
N1	−0.2205 (3)	−0.5823 (2)	1.34244 (16)	0.0314 (5)
N2	0.2344 (3)	−0.0749 (2)	1.26201 (14)	0.0285 (5)
H2N	0.3112	−0.0149	1.3030	0.034*
N3	0.2300 (3)	−0.0459 (2)	1.17772 (14)	0.0279 (5)
N4	0.5188 (3)	0.3449 (2)	0.80714 (13)	0.0268 (5)
N5	0.5234 (3)	0.3707 (2)	0.72248 (13)	0.0272 (5)
H5N	0.4508	0.3089	0.6803	0.033*
N6	1.0012 (3)	0.8658 (2)	0.64104 (14)	0.0281 (5)
C1	−0.1068 (3)	−0.4476 (3)	1.32299 (17)	0.0264 (6)
C2	0.0140 (3)	−0.3527 (3)	1.38838 (18)	0.0298 (6)
H2	0.0190	−0.3740	1.4464	0.036*
C3	0.1262 (3)	−0.2277 (3)	1.36776 (17)	0.0275 (6)
H3	0.2084	−0.1618	1.4119	0.033*
C4	0.1193 (3)	−0.1974 (3)	1.28162 (16)	0.0250 (6)
C5	−0.0061 (3)	−0.2935 (3)	1.21764 (18)	0.0312 (6)
H5	−0.0141	−0.2721	1.1597	0.037*
C6	−0.1168 (4)	−0.4174 (3)	1.23830 (19)	0.0330 (6)
H6	−0.2005	−0.4829	1.1946	0.040*
C7	0.3492 (3)	0.0666 (3)	1.16298 (17)	0.0285 (6)
H7	0.4329	0.1230	1.2094	0.034*
C8	0.3571 (3)	0.1086 (3)	1.07560 (17)	0.0270 (6)
C9	0.4848 (4)	0.2336 (3)	1.06298 (18)	0.0371 (7)
H9	0.5628	0.2913	1.1114	0.044*
C10	0.4993 (4)	0.2748 (3)	0.98095 (18)	0.0365 (7)
H10	0.5857	0.3617	0.9740	0.044*
C11	0.3902 (3)	0.1917 (3)	0.90894 (17)	0.0267 (6)
C12	0.2590 (4)	0.0692 (3)	0.92239 (19)	0.0399 (7)
H12	0.1792	0.0129	0.8743	0.048*
C13	0.2436 (4)	0.0288 (3)	1.00415 (19)	0.0400 (7)
H13	0.1535	−0.0554	1.0117	0.048*
C14	0.4076 (3)	0.2275 (3)	0.82018 (17)	0.0274 (6)
H14	0.3356	0.1628	0.7716	0.033*
C15	0.6399 (3)	0.4935 (3)	0.70347 (16)	0.0246 (6)
C16	0.7616 (3)	0.5904 (3)	0.76914 (16)	0.0259 (6)
H16	0.7625	0.5721	0.8280	0.031*
C17	0.8788 (3)	0.7112 (3)	0.74798 (17)	0.0267 (6)
H17	0.9626	0.7757	0.7920	0.032*
C18	0.8752 (3)	0.7394 (3)	0.66236 (17)	0.0251 (6)
C19	0.7543 (3)	0.6461 (3)	0.59689 (17)	0.0275 (6)
H19	0.7515	0.6670	0.5387	0.033*
C20	0.6385 (3)	0.5231 (3)	0.61741 (17)	0.0274 (6)
H20	0.5569	0.4577	0.5727	0.033*
O1W	0.3412 (2)	0.1327 (2)	0.56735 (12)	0.0346 (5)
H1W	0.2326 (16)	0.095 (3)	0.565 (2)	0.052*
H2W	0.386 (4)	0.141 (4)	0.5191 (12)	0.052*
O2W	0.4975 (2)	0.9015 (2)	0.59601 (13)	0.0349 (5)
H3W	0.434 (3)	0.961 (3)	0.590 (2)	0.052*
H4W	0.429 (3)	0.826 (2)	0.609 (2)	0.052*

	U11	U22	U33	U12	U13	U23
O1	0.0431 (11)	0.0390 (12)	0.0363 (12)	0.0049 (9)	0.0133 (9)	0.0185 (9)
O2	0.0404 (11)	0.0315 (11)	0.0495 (13)	−0.0048 (9)	−0.0040 (10)	0.0116 (10)
O3	0.0373 (11)	0.0373 (11)	0.0372 (12)	−0.0057 (9)	−0.0012 (9)	0.0132 (9)
O4	0.0418 (11)	0.0321 (11)	0.0311 (11)	0.0050 (8)	0.0072 (8)	0.0175 (8)
N1	0.0298 (12)	0.0267 (12)	0.0424 (15)	0.0093 (10)	0.0104 (10)	0.0146 (11)
N2	0.0320 (12)	0.0277 (12)	0.0272 (12)	0.0028 (9)	0.0048 (9)	0.0136 (9)
N3	0.0344 (12)	0.0279 (12)	0.0247 (12)	0.0085 (10)	0.0076 (9)	0.0115 (9)
N4	0.0301 (12)	0.0279 (12)	0.0259 (12)	0.0073 (9)	0.0064 (9)	0.0129 (9)
N5	0.0301 (12)	0.0277 (12)	0.0227 (12)	0.0000 (9)	0.0038 (9)	0.0106 (9)
N6	0.0319 (12)	0.0258 (12)	0.0296 (13)	0.0075 (10)	0.0078 (10)	0.0115 (10)
C1	0.0244 (13)	0.0230 (13)	0.0345 (15)	0.0062 (11)	0.0077 (11)	0.0110 (11)
C2	0.0325 (14)	0.0327 (15)	0.0309 (15)	0.0132 (12)	0.0116 (11)	0.0155 (12)
C3	0.0282 (14)	0.0284 (14)	0.0279 (14)	0.0059 (11)	0.0065 (11)	0.0108 (11)
C4	0.0262 (13)	0.0246 (13)	0.0278 (14)	0.0089 (10)	0.0078 (10)	0.0095 (11)
C5	0.0352 (15)	0.0308 (15)	0.0302 (15)	0.0045 (12)	0.0016 (12)	0.0161 (12)
C6	0.0336 (15)	0.0291 (15)	0.0368 (16)	0.0054 (12)	−0.0007 (12)	0.0102 (12)
C7	0.0289 (14)	0.0270 (14)	0.0300 (15)	0.0029 (11)	0.0040 (11)	0.0111 (11)
C8	0.0278 (14)	0.0264 (14)	0.0296 (14)	0.0070 (11)	0.0068 (11)	0.0115 (11)
C9	0.0369 (15)	0.0376 (16)	0.0303 (16)	−0.0083 (12)	−0.0002 (12)	0.0116 (12)
C10	0.0377 (16)	0.0336 (15)	0.0336 (16)	−0.0077 (12)	0.0036 (12)	0.0146 (13)
C11	0.0275 (13)	0.0264 (14)	0.0299 (15)	0.0074 (11)	0.0068 (11)	0.0132 (11)
C12	0.0414 (16)	0.0389 (17)	0.0334 (16)	−0.0101 (13)	−0.0032 (12)	0.0157 (13)
C13	0.0405 (16)	0.0368 (16)	0.0383 (17)	−0.0111 (13)	0.0025 (13)	0.0206 (13)
C14	0.0300 (14)	0.0240 (14)	0.0284 (14)	0.0030 (11)	0.0031 (11)	0.0095 (11)
C15	0.0257 (13)	0.0219 (13)	0.0287 (14)	0.0074 (10)	0.0074 (10)	0.0088 (11)
C16	0.0298 (14)	0.0286 (14)	0.0220 (13)	0.0084 (11)	0.0061 (10)	0.0097 (11)
C17	0.0283 (14)	0.0256 (14)	0.0264 (14)	0.0049 (11)	0.0033 (10)	0.0073 (11)
C18	0.0248 (13)	0.0227 (13)	0.0312 (15)	0.0066 (10)	0.0080 (11)	0.0121 (11)
C19	0.0327 (14)	0.0280 (14)	0.0259 (14)	0.0085 (11)	0.0073 (11)	0.0131 (11)
C20	0.0295 (14)	0.0263 (14)	0.0264 (14)	0.0035 (11)	0.0028 (11)	0.0090 (11)
O1W	0.0327 (11)	0.0375 (11)	0.0319 (11)	0.0007 (9)	0.0043 (8)	0.0118 (9)
O2W	0.0358 (11)	0.0304 (11)	0.0409 (12)	0.0022 (8)	0.0049 (9)	0.0192 (9)

O1—N1	1.238 (3)	C8—C13	1.382 (4)
O2—N1	1.235 (3)	C8—C9	1.393 (4)
O3—N6	1.235 (3)	C9—C10	1.381 (4)
O4—N6	1.237 (3)	C9—H9	0.9500
N1—C1	1.444 (3)	C10—C11	1.379 (4)
N2—C4	1.364 (3)	C10—H10	0.9500
N2—N3	1.371 (3)	C11—C12	1.395 (4)
N2—H2N	0.8796	C11—C14	1.461 (3)
N3—C7	1.288 (3)	C12—C13	1.374 (4)
N4—C14	1.280 (3)	C12—H12	0.9500
N4—N5	1.364 (3)	C13—H13	0.9500
N5—C15	1.368 (3)	C14—H14	0.9500
N5—H5N	0.8799	C15—C20	1.398 (3)
N6—C18	1.442 (3)	C15—C16	1.406 (4)
C1—C6	1.384 (4)	C16—C17	1.370 (3)
C1—C2	1.393 (4)	C16—H16	0.9500
C2—C3	1.377 (3)	C17—C18	1.388 (3)
C2—H2	0.9500	C17—H17	0.9500
C3—C4	1.405 (3)	C18—C19	1.389 (4)
C3—H3	0.9500	C19—C20	1.376 (3)
C4—C5	1.404 (4)	C19—H19	0.9500
C5—C6	1.365 (4)	C20—H20	0.9500
C5—H5	0.9500	O1W—H1W	0.833 (10)
C6—H6	0.9500	O1W—H2W	0.831 (10)
C7—C8	1.463 (3)	O2W—H3W	0.839 (10)
C7—H7	0.9500	O2W—H4W	0.836 (10)
O2—N1—O1	121.7 (2)	C10—C9—C8	120.9 (3)
O2—N1—C1	119.1 (2)	C10—C9—H9	119.6
O1—N1—C1	119.3 (2)	C8—C9—H9	119.6
C4—N2—N3	119.5 (2)	C9—C10—C11	120.9 (2)
C4—N2—H2N	120.4	C9—C10—H10	119.5
N3—N2—H2N	120.1	C11—C10—H10	119.5
C7—N3—N2	115.9 (2)	C10—C11—C12	118.1 (2)
C14—N4—N5	116.7 (2)	C10—C11—C14	122.4 (2)
N4—N5—C15	119.9 (2)	C12—C11—C14	119.5 (2)
N4—N5—H5N	119.9	C13—C12—C11	121.0 (3)
C15—N5—H5N	120.2	C13—C12—H12	119.5
O3—N6—O4	121.8 (2)	C11—C12—H12	119.5
O3—N6—C18	118.8 (2)	C12—C13—C8	121.0 (2)
O4—N6—C18	119.5 (2)	C12—C13—H13	119.5
C6—C1—C2	121.1 (2)	C8—C13—H13	119.5
C6—C1—N1	119.0 (2)	N4—C14—C11	120.8 (2)
C2—C1—N1	119.9 (2)	N4—C14—H14	119.6
C3—C2—C1	119.2 (2)	C11—C14—H14	119.6
C3—C2—H2	120.4	N5—C15—C20	119.6 (2)
C1—C2—H2	120.4	N5—C15—C16	121.0 (2)
C2—C3—C4	120.2 (2)	C20—C15—C16	119.4 (2)
C2—C3—H3	119.9	C17—C16—C15	119.8 (2)
C4—C3—H3	119.9	C17—C16—H16	120.1
N2—C4—C3	119.3 (2)	C15—C16—H16	120.1
N2—C4—C5	121.4 (2)	C16—C17—C18	120.1 (2)
C3—C4—C5	119.3 (2)	C16—C17—H17	120.0
C6—C5—C4	120.3 (2)	C18—C17—H17	120.0
C6—C5—H5	119.9	C17—C18—C19	120.9 (2)
C4—C5—H5	119.9	C17—C18—N6	119.3 (2)
C5—C6—C1	119.9 (3)	C19—C18—N6	119.8 (2)
C5—C6—H6	120.0	C20—C19—C18	119.2 (2)
C1—C6—H6	120.0	C20—C19—H19	120.4
N3—C7—C8	120.8 (2)	C18—C19—H19	120.4
N3—C7—H7	119.6	C19—C20—C15	120.6 (2)
C8—C7—H7	119.6	C19—C20—H20	119.7
C13—C8—C9	118.1 (2)	C15—C20—H20	119.7
C13—C8—C7	122.8 (2)	H1W—O1W—H2W	117 (3)
C9—C8—C7	119.1 (2)	H3W—O2W—H4W	106 (3)
C4—N2—N3—C7	−176.2 (2)	C9—C10—C11—C14	−176.8 (2)
C14—N4—N5—C15	−179.5 (2)	C10—C11—C12—C13	−2.6 (4)
O2—N1—C1—C6	3.6 (3)	C14—C11—C12—C13	177.3 (3)
O1—N1—C1—C6	−177.0 (2)	C11—C12—C13—C8	0.3 (5)
O2—N1—C1—C2	−174.6 (2)	C9—C8—C13—C12	1.6 (4)
O1—N1—C1—C2	4.8 (3)	C7—C8—C13—C12	−177.9 (3)
C6—C1—C2—C3	−0.6 (4)	N5—N4—C14—C11	−178.8 (2)
N1—C1—C2—C3	177.6 (2)	C10—C11—C14—N4	−4.7 (4)
C1—C2—C3—C4	−0.5 (4)	C12—C11—C14—N4	175.3 (2)
N3—N2—C4—C3	179.1 (2)	N4—N5—C15—C20	−177.1 (2)
N3—N2—C4—C5	−1.1 (3)	N4—N5—C15—C16	3.0 (3)
C2—C3—C4—N2	−178.5 (2)	N5—C15—C16—C17	178.9 (2)
C2—C3—C4—C5	1.7 (4)	C20—C15—C16—C17	−0.9 (4)
N2—C4—C5—C6	178.3 (2)	C15—C16—C17—C18	1.2 (4)
C3—C4—C5—C6	−1.9 (4)	C16—C17—C18—C19	−0.3 (4)
C4—C5—C6—C1	0.8 (4)	C16—C17—C18—N6	−179.1 (2)
C2—C1—C6—C5	0.5 (4)	O3—N6—C18—C17	7.1 (3)
N1—C1—C6—C5	−177.7 (2)	O4—N6—C18—C17	−173.2 (2)
N2—N3—C7—C8	−179.8 (2)	O3—N6—C18—C19	−171.7 (2)
N3—C7—C8—C13	−2.3 (4)	O4—N6—C18—C19	7.9 (3)
N3—C7—C8—C9	178.2 (2)	C17—C18—C19—C20	−0.9 (4)
C13—C8—C9—C10	−1.1 (4)	N6—C18—C19—C20	177.9 (2)
C7—C8—C9—C10	178.4 (2)	C18—C19—C20—C15	1.2 (4)
C8—C9—C10—C11	−1.3 (4)	N5—C15—C20—C19	179.9 (2)
C9—C10—C11—C12	3.1 (4)	C16—C15—C20—C19	−0.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1w···O4i	0.833 (17)	2.32 (2)	3.084 (2)	153 (2)
O1W—H2w···O2wii	0.83 (2)	2.01 (2)	2.808 (3)	163 (3)
N5—H5n···O1w	0.88	2.17	3.021 (3)	163
O2W—H3w···O1wiii	0.84 (3)	1.98 (3)	2.800 (3)	165 (3)
O2W—H4w···O1iv	0.84 (2)	2.28 (2)	3.061 (3)	156 (3)
O2W—H4w···O2iv	0.84 (2)	2.45 (2)	3.204 (3)	150 (3)
N2—H2n···O2wv	0.88	2.09	2.959 (3)	172
C7—H7···O2vi	0.95	2.48	3.374 (3)	157
C14—H14···O3i	0.95	2.45	3.338 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1w⋯O4i	0.83 (2)	2.32 (2)	3.084 (2)	153 (2)
O1W—H2w⋯O2wii	0.83 (2)	2.01 (2)	2.808 (3)	163 (3)
N5—H5n⋯O1w	0.88	2.17	3.021 (3)	163
O2W—H3w⋯O1wiii	0.84 (3)	1.98 (3)	2.800 (3)	165 (3)
O2W—H4w⋯O1iv	0.84 (2)	2.28 (2)	3.061 (3)	156 (3)
O2W—H4w⋯O2iv	0.84 (2)	2.45 (2)	3.204 (3)	150 (3)
N2—H2n⋯O2wv	0.88	2.09	2.959 (3)	172
C7—H7⋯O2vi	0.95	2.48	3.374 (3)	157
C14—H14⋯O3i	0.95	2.45	3.338 (3)	156

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