(E)-Ethyl N′-(3-hy­droxy­benzyl­idene)hydrazinecarboxyl­ate dihydrate

Hu, X.-C.; Zhang, J.; Yang, D.-Y.; Lv, L.-P.

doi:10.1107/S1600536811025104

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1884

doi:10.1107/S1600536811025104

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(E)-Ethyl N′-(3-hydroxybenzylidene)hydrazinecarboxylate dihydrate

Xian-Chao Hu,^a,^b ^* Jie Zhang,^a Da-Yong Yang ^c and Lu-Ping Lv ^d

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, ^bResearch Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, ^cHangzhou Fist Chemical Co. Ltd, Xiaoshan, Hangzhou 310007, People's Republic of China, and ^dLinjiang College, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 23 June 2011; accepted 26 June 2011; online 2 July 2011)

The asymmetric unit of the title compound, C₁₀H₁₂N₂O₃·2H₂O, contains two organic molecules with similar conformations and four water molecules. Each organic molecule is close to planar (r.m.s. deviations = 0.035 and 0.108 Å) and adopts a trans conformation with respect to its C=N bond. In the crystal, the components are linked into a three-dimensional network by N—H⋯O, O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds, some of which are bifurcated. An R₂²(8) loop occurs between adjacent organic molecules.

Related literature

For general background to benzaldehydehydrazone derivatives, see: Parashar et al. (1988 ); Hadjoudis et al. (1987 ); Borg et al. (1999 ). For a related structure, see: Shang et al. (2007 ).

Experimental

Crystal data

C₁₀H₁₂N₂O₃·2H₂O
M_r = 244.25
Monoclinic, P 2₁ /c
a = 12.8074 (10) Å
b = 21.9101 (18) Å
c = 8.9048 (7) Å
β = 96.490 (3)°
V = 2482.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 223 K
0.20 × 0.19 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.977, T_max = 0.989
22432 measured reflections
4819 independent reflections
3377 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.126
S = 0.95
4819 reflections
341 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O6ⁱ	0.86	2.29	3.0968 (18)	157
N4—H4N⋯O3	0.86	2.24	3.0849 (18)	167
O6—H6⋯O4W	0.82	1.90	2.675 (2)	157
C3—H3⋯O5	0.93	2.51	3.422 (2)	168
O1W—H1A⋯O2Wⁱⁱ	0.84 (3)	2.04 (3)	2.874 (3)	178 (3)
O1W—H1B⋯O2Wⁱⁱⁱ	0.91 (3)	1.99 (3)	2.906 (2)	177 (3)
O2W—H2A⋯O4	0.91 (3)	2.02 (3)	2.899 (2)	163 (2)
O2W—H2B⋯O1^iv	0.85 (3)	2.25 (3)	2.9268 (19)	136 (2)
O2W—H2B⋯N1^iv	0.85 (3)	2.41 (3)	3.165 (2)	148 (2)
O3W—H3A⋯O4ⁱⁱⁱ	0.89 (3)	2.27 (3)	2.9417 (19)	132 (2)
O3W—H3A⋯N3ⁱⁱⁱ	0.89 (3)	2.38 (3)	3.200 (2)	153 (3)
O3W—H3B⋯O1	0.90 (3)	2.10 (3)	2.991 (2)	171 (3)
O4W—H4B⋯O3W^v	0.98 (6)	1.84 (6)	2.819 (3)	173 (5)
O4W—H4A⋯O3W^iv	0.81 (3)	2.15 (3)	2.955 (2)	169 (3)
Symmetry codes: (i) x-1, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[x+1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025104/hb5929sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025104/hb5929Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025104/hb5929Isup3.cml

checkCIF report

Comment top

Benzaldehydehydrazone derivatives have received considerable attentions for a long time due to their pharmacological activity (Parashar et al., 1988) and their photochromic properties(Hadjoudis et al., 1987). Meanwhile, it's an important intermidiate of 1,3,4-oxadiazoles, which have been reported to be versatile compounds with many properties (Borg et al., 1999). As a further investigation of this type of derivatives, we report herein the crystal structure of the title compound.

The title compound, C₁₀H₁₂N₂O₃ .2H₂O, crystallizes with two very similar independent molecules in the asymmetric unit. Each independent molecule adopts a trans configuration with respect to the C═N bond. The N1/N2/O1/O2/C7-C10 and N3/N4/O4/O5/C17-C20 planes form dihedral angles of 2.56 (10)° and 8.02 (8)°, respectively, with the C1—C6 and C1—C16 planes. The bond lengths and angles of the main molecule agree with those observed for (E)-Methyl N'-(4-hydroxybenzylidene)hydrazinecarboxylate (Shang et al., 2007).

In the crystal, molecules are linked into three-dimensional network by N—H···O,O—H···O,C—H···O and O—H···N hydrogen bonds (Table 1, Fig.2).

Related literature top

For general background to benzaldehydehydrazone derivatives, see: Parashar et al. (1988); Hadjoudis et al. (1987); Borg et al. (1999). For a related structure, see: Shang et al. (2007).

Experimental top

3-hydroxybenzaldehyde (1.22g, 0.01mol) and ethyl hydrazinecarboxylate(1.04g, 0.01mol) were dissolved in stirred methanol (30ml) and left for 3h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 88% yield. Colourless blocks of (I) were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 438-441 K).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of (I), showing 40% probability displacement ellipsoids and the atomic numbering.
	Fig. 2. Crystal packing of the title compound, viewed approximately down the a axis. Dashed lines indicate hydrogen bonds. H atoms not intervening in H-bonding were eliminated for clarity.

(E)-Ethyl N'-(3-hydroxybenzylidene)hydrazinecarboxylate dihydrate top

Crystal data top

C₁₀H₁₂N₂O₃·2H₂O	F(000) = 1040
M_r = 244.25	D_x = 1.307 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4819 reflections
a = 12.8074 (10) Å	θ = 1.6–25.0°
b = 21.9101 (18) Å	µ = 0.11 mm⁻¹
c = 8.9048 (7) Å	T = 223 K
β = 96.490 (3)°	Block, colourless
V = 2482.8 (3) Å³	0.20 × 0.19 × 0.18 mm
Z = 8

Data collection top

Bruker SMART CCD diffractometer	4819 independent reflections
Radiation source: fine-focus sealed tube	3377 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −15→15
T_min = 0.977, T_max = 0.989	k = −26→27
22432 measured reflections	l = −10→10

Refinement top

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.126	w = 1/[σ²(F_o²) + (0.0615P)² + 0.604P] where P = (F_o² + 2F_c²)/3
S = 0.95	(Δ/σ)_max < 0.001
4819 reflections	Δρ_max = 0.16 e Å⁻³
341 parameters	Δρ_min = −0.14 e Å⁻³
0 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: 0.0022 (6)

Crystal data top

C₁₀H₁₂N₂O₃·2H₂O	V = 2482.8 (3) Å³
M_r = 244.25	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.8074 (10) Å	µ = 0.11 mm⁻¹
b = 21.9101 (18) Å	T = 223 K
c = 8.9048 (7) Å	0.20 × 0.19 × 0.18 mm
β = 96.490 (3)°

Data collection top

Bruker SMART CCD diffractometer	4819 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	3377 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.989	R_int = 0.036
22432 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	Δρ_max = 0.16 e Å⁻³
4819 reflections	Δρ_min = −0.14 e Å⁻³
341 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C10	−0.09028 (17)	0.12370 (9)	1.3239 (3)	0.0742 (6)
H10A	−0.1020	0.0806	1.3319	0.111*
H10B	−0.1545	0.1434	1.2842	0.111*
H10C	−0.0670	0.1400	1.4221	0.111*
O1W	0.42004 (14)	0.30255 (7)	0.7045 (2)	0.0734 (5)
O2W	0.68695 (13)	0.73071 (8)	0.58510 (19)	0.0723 (4)
O3W	0.14922 (13)	0.05421 (8)	1.0133 (2)	0.0770 (5)
O4W	0.98022 (17)	0.48067 (8)	0.3000 (2)	0.0847 (5)
H2A	0.694 (2)	0.6903 (13)	0.607 (3)	0.100 (9)*
H1A	0.387 (2)	0.2930 (13)	0.621 (4)	0.112 (12)*
H1B	0.386 (2)	0.2811 (13)	0.772 (3)	0.114 (10)*
H2B	0.745 (2)	0.7398 (11)	0.554 (3)	0.096 (9)*
H3A	0.213 (3)	0.0450 (13)	0.989 (3)	0.125 (11)*
H4A	0.938 (3)	0.5007 (15)	0.341 (3)	0.122 (12)*
H3B	0.150 (2)	0.0953 (15)	1.023 (3)	0.133 (12)*
H4B	1.041 (5)	0.472 (3)	0.374 (6)	0.28 (3)*
C1	0.28335 (13)	0.39669 (8)	0.9118 (2)	0.0477 (4)
H1	0.2871	0.3558	0.8849	0.057*
C2	0.34613 (13)	0.43925 (8)	0.8508 (2)	0.0507 (4)
C3	0.33908 (16)	0.49999 (8)	0.8888 (3)	0.0667 (6)
H3	0.3813	0.5287	0.8480	0.080*
C4	0.26972 (18)	0.51811 (9)	0.9868 (3)	0.0793 (7)
H4	0.2646	0.5592	1.0112	0.095*
C5	0.20760 (16)	0.47581 (8)	1.0491 (3)	0.0670 (6)
H5	0.1608	0.4884	1.1155	0.080*
C6	0.21479 (13)	0.41483 (7)	1.0130 (2)	0.0480 (4)
C7	0.14945 (14)	0.37163 (8)	1.0848 (2)	0.0536 (5)
H7	0.1046	0.3868	1.1511	0.064*
C8	0.07698 (13)	0.22053 (8)	1.1273 (2)	0.0506 (4)
C9	−0.00809 (14)	0.13484 (8)	1.2203 (2)	0.0547 (5)
H9A	0.0575	0.1155	1.2595	0.066*
H9B	−0.0303	0.1183	1.1207	0.066*
C11	0.77878 (13)	0.39363 (8)	0.4056 (2)	0.0483 (4)
H11	0.7901	0.4350	0.3906	0.058*
C12	0.83693 (13)	0.35064 (8)	0.3377 (2)	0.0513 (4)
C13	0.81986 (16)	0.28929 (9)	0.3588 (3)	0.0669 (6)
H13	0.8588	0.2605	0.3125	0.080*
C14	0.74537 (18)	0.27088 (9)	0.4480 (3)	0.0791 (7)
H14	0.7341	0.2295	0.4623	0.095*
C15	0.68699 (16)	0.31331 (8)	0.5169 (3)	0.0669 (6)
H15	0.6365	0.3004	0.5773	0.080*
C16	0.70352 (13)	0.37501 (8)	0.4961 (2)	0.0483 (4)
C17	0.64060 (14)	0.41813 (8)	0.5720 (2)	0.0529 (5)
H17	0.5858	0.4029	0.6212	0.063*
C18	0.59999 (13)	0.56870 (8)	0.6705 (2)	0.0478 (4)
C19	0.52938 (14)	0.65317 (8)	0.7918 (2)	0.0552 (5)
H19A	0.5111	0.6780	0.7025	0.066*
H19B	0.5992	0.6646	0.8366	0.066*
C20	0.45141 (16)	0.66243 (9)	0.9025 (3)	0.0696 (6)
H20A	0.4511	0.7046	0.9317	0.104*
H20B	0.4704	0.6376	0.9902	0.104*
H20C	0.3827	0.6510	0.8567	0.104*
N1	0.15055 (11)	0.31441 (6)	1.06170 (17)	0.0508 (4)
N2	0.08175 (12)	0.28158 (7)	1.13816 (19)	0.0604 (4)
H2	0.0413	0.3004	1.1936	0.073*
N3	0.65632 (10)	0.47535 (6)	0.57456 (16)	0.0480 (4)
N4	0.58747 (11)	0.50831 (6)	0.65046 (18)	0.0543 (4)
H4N	0.5359	0.4901	0.6854	0.065*
O1	0.12881 (11)	0.18908 (6)	1.05295 (17)	0.0687 (4)
O2	0.00520 (9)	0.20017 (5)	1.21202 (15)	0.0578 (4)
O3	0.41697 (10)	0.42375 (6)	0.75455 (16)	0.0694 (4)
H3C	0.4154	0.3867	0.7409	0.104*
O4	0.66657 (10)	0.59992 (5)	0.62166 (16)	0.0600 (4)
O5	0.52645 (9)	0.58923 (5)	0.75261 (16)	0.0579 (4)
O6	0.91245 (10)	0.36631 (6)	0.24827 (17)	0.0721 (4)
H6	0.9188	0.4035	0.2474	0.086 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C10	0.0782 (14)	0.0505 (12)	0.1003 (17)	−0.0111 (10)	0.0373 (13)	0.0089 (11)
O1W	0.0912 (11)	0.0552 (9)	0.0780 (12)	0.0013 (8)	0.0280 (11)	−0.0056 (8)
O2W	0.0765 (10)	0.0610 (10)	0.0868 (11)	−0.0007 (8)	0.0417 (9)	0.0052 (8)
O3W	0.0635 (9)	0.0624 (10)	0.1118 (13)	−0.0038 (7)	0.0396 (9)	−0.0021 (9)
O4W	0.0879 (12)	0.0599 (10)	0.1142 (15)	−0.0092 (8)	0.0454 (12)	−0.0058 (9)
C1	0.0481 (9)	0.0356 (9)	0.0620 (11)	−0.0014 (7)	0.0182 (8)	−0.0010 (8)
C2	0.0505 (10)	0.0451 (10)	0.0601 (11)	−0.0003 (8)	0.0220 (8)	0.0027 (8)
C3	0.0721 (13)	0.0414 (11)	0.0938 (16)	−0.0056 (9)	0.0409 (12)	0.0067 (10)
C4	0.0957 (16)	0.0370 (10)	0.1155 (19)	−0.0006 (10)	0.0575 (15)	−0.0041 (11)
C5	0.0732 (13)	0.0435 (11)	0.0930 (16)	0.0030 (9)	0.0476 (12)	−0.0037 (10)
C6	0.0463 (9)	0.0396 (9)	0.0608 (11)	−0.0005 (7)	0.0179 (8)	0.0021 (8)
C7	0.0520 (10)	0.0439 (10)	0.0702 (13)	0.0006 (8)	0.0301 (9)	−0.0017 (9)
C8	0.0487 (10)	0.0424 (10)	0.0641 (12)	−0.0002 (8)	0.0208 (9)	0.0022 (8)
C9	0.0596 (11)	0.0377 (9)	0.0693 (13)	−0.0040 (8)	0.0179 (9)	0.0027 (8)
C11	0.0500 (9)	0.0389 (9)	0.0586 (11)	−0.0006 (7)	0.0171 (8)	−0.0023 (8)
C12	0.0490 (9)	0.0453 (10)	0.0632 (11)	0.0006 (8)	0.0215 (8)	−0.0053 (8)
C13	0.0677 (12)	0.0437 (11)	0.0959 (16)	0.0051 (9)	0.0386 (11)	−0.0112 (10)
C14	0.0901 (15)	0.0365 (10)	0.120 (2)	0.0013 (10)	0.0539 (14)	−0.0020 (11)
C15	0.0716 (12)	0.0425 (11)	0.0944 (16)	−0.0034 (9)	0.0437 (12)	−0.0001 (10)
C16	0.0463 (9)	0.0421 (9)	0.0590 (11)	0.0023 (7)	0.0174 (8)	−0.0028 (8)
C17	0.0490 (10)	0.0458 (11)	0.0680 (12)	−0.0006 (8)	0.0253 (9)	−0.0024 (9)
C18	0.0459 (9)	0.0449 (10)	0.0550 (11)	0.0017 (7)	0.0156 (8)	−0.0055 (8)
C19	0.0565 (10)	0.0356 (9)	0.0757 (13)	0.0021 (8)	0.0175 (9)	−0.0074 (9)
C20	0.0687 (12)	0.0515 (12)	0.0933 (16)	0.0045 (10)	0.0290 (12)	−0.0180 (11)
N1	0.0482 (8)	0.0416 (8)	0.0667 (10)	−0.0036 (6)	0.0247 (7)	0.0024 (7)
N2	0.0621 (9)	0.0418 (9)	0.0857 (12)	−0.0043 (7)	0.0448 (9)	−0.0020 (8)
N3	0.0462 (8)	0.0434 (8)	0.0573 (9)	0.0035 (6)	0.0190 (7)	−0.0056 (7)
N4	0.0508 (8)	0.0408 (8)	0.0766 (11)	−0.0019 (6)	0.0308 (8)	−0.0107 (7)
O1	0.0744 (9)	0.0447 (7)	0.0956 (11)	−0.0005 (6)	0.0471 (8)	−0.0044 (7)
O2	0.0606 (7)	0.0382 (6)	0.0807 (9)	−0.0043 (5)	0.0344 (7)	0.0017 (6)
O3	0.0766 (9)	0.0517 (8)	0.0894 (10)	−0.0078 (6)	0.0513 (8)	−0.0038 (7)
O4	0.0623 (8)	0.0471 (7)	0.0762 (9)	−0.0043 (6)	0.0321 (7)	−0.0032 (6)
O5	0.0558 (7)	0.0389 (7)	0.0846 (9)	−0.0018 (5)	0.0320 (7)	−0.0125 (6)
O6	0.0766 (9)	0.0526 (9)	0.0970 (11)	−0.0015 (7)	0.0529 (8)	−0.0098 (7)

Geometric parameters (Å, º) top

C10—C9	1.496 (2)	C9—H9B	0.9700
C10—H10A	0.9600	C11—C12	1.382 (2)
C10—H10B	0.9600	C11—C16	1.386 (2)
C10—H10C	0.9600	C11—H11	0.9300
O1W—H1A	0.84 (3)	C12—O6	1.365 (2)
O1W—H1B	0.91 (3)	C12—C13	1.378 (3)
O2W—H2A	0.91 (3)	C13—C14	1.370 (3)
O2W—H2B	0.85 (3)	C13—H13	0.9300
O3W—H3A	0.89 (3)	C14—C15	1.380 (3)
O3W—H3B	0.90 (3)	C14—H14	0.9300
O4W—H4A	0.81 (3)	C15—C16	1.384 (2)
O4W—H4B	0.98 (6)	C15—H15	0.9300
C1—C2	1.382 (2)	C16—C17	1.456 (2)
C1—C6	1.386 (2)	C17—N3	1.270 (2)
C1—H1	0.9300	C17—H17	0.9300
C2—O3	1.359 (2)	C18—O4	1.212 (2)
C2—C3	1.379 (3)	C18—O5	1.3339 (19)
C3—C4	1.372 (3)	C18—N4	1.342 (2)
C3—H3	0.9300	C19—O5	1.443 (2)
C4—C5	1.378 (3)	C19—C20	1.494 (2)
C4—H4	0.9300	C19—H19A	0.9700
C5—C6	1.380 (2)	C19—H19B	0.9700
C5—H5	0.9300	C20—H20A	0.9600
C6—C7	1.458 (2)	C20—H20B	0.9600
C7—N1	1.271 (2)	C20—H20C	0.9600
C7—H7	0.9300	N1—N2	1.3759 (18)
C8—O1	1.206 (2)	N2—H2	0.8600
C8—O2	1.3303 (19)	N3—N4	1.3750 (18)
C8—N2	1.342 (2)	N4—H4N	0.8600
C9—O2	1.444 (2)	O3—H3C	0.8200
C9—H9A	0.9700	O6—H6	0.8200

C9—C10—H10A	109.5	O6—C12—C11	122.46 (16)
C9—C10—H10B	109.5	C13—C12—C11	120.25 (16)
H10A—C10—H10B	109.5	C14—C13—C12	119.85 (17)
C9—C10—H10C	109.5	C14—C13—H13	120.1
H10A—C10—H10C	109.5	C12—C13—H13	120.1
H10B—C10—H10C	109.5	C13—C14—C15	120.52 (18)
H1A—O1W—H1B	103 (3)	C13—C14—H14	119.7
H2A—O2W—H2B	103 (2)	C15—C14—H14	119.7
H3A—O3W—H3B	104 (3)	C14—C15—C16	119.99 (17)
H4A—O4W—H4B	109 (4)	C14—C15—H15	120.0
C2—C1—C6	120.13 (16)	C16—C15—H15	120.0
C2—C1—H1	119.9	C11—C16—C15	119.49 (15)
C6—C1—H1	119.9	C11—C16—C17	122.43 (15)
O3—C2—C3	117.57 (15)	C15—C16—C17	118.08 (15)
O3—C2—C1	122.59 (15)	N3—C17—C16	123.66 (15)
C3—C2—C1	119.83 (16)	N3—C17—H17	118.2
C4—C3—C2	120.04 (17)	C16—C17—H17	118.2
C4—C3—H3	120.0	O4—C18—O5	125.14 (16)
C2—C3—H3	120.0	O4—C18—N4	125.94 (15)
C3—C4—C5	120.39 (18)	O5—C18—N4	108.92 (14)
C3—C4—H4	119.8	O5—C19—C20	106.88 (14)
C5—C4—H4	119.8	O5—C19—H19A	110.3
C4—C5—C6	120.05 (17)	C20—C19—H19A	110.3
C4—C5—H5	120.0	O5—C19—H19B	110.3
C6—C5—H5	120.0	C20—C19—H19B	110.3
C5—C6—C1	119.53 (15)	H19A—C19—H19B	108.6
C5—C6—C7	118.03 (15)	C19—C20—H20A	109.5
C1—C6—C7	122.43 (15)	C19—C20—H20B	109.5
N1—C7—C6	123.50 (15)	H20A—C20—H20B	109.5
N1—C7—H7	118.3	C19—C20—H20C	109.5
C6—C7—H7	118.3	H20A—C20—H20C	109.5
O1—C8—O2	125.35 (16)	H20B—C20—H20C	109.5
O1—C8—N2	125.86 (16)	C7—N1—N2	114.59 (14)
O2—C8—N2	108.80 (14)	C8—N2—N1	120.80 (14)
O2—C9—C10	106.76 (14)	C8—N2—H2	119.6
O2—C9—H9A	110.4	N1—N2—H2	119.6
C10—C9—H9A	110.4	C17—N3—N4	114.73 (14)
O2—C9—H9B	110.4	C18—N4—N3	120.63 (14)
C10—C9—H9B	110.4	C18—N4—H4N	119.7
H9A—C9—H9B	108.6	N3—N4—H4N	119.7
C12—C11—C16	119.90 (16)	C8—O2—C9	117.01 (13)
C12—C11—H11	120.0	C2—O3—H3C	109.5
C16—C11—H11	120.0	C18—O5—C19	117.34 (13)
O6—C12—C13	117.29 (15)	C12—O6—H6	109.5

C6—C1—C2—O3	177.98 (18)	C12—C11—C16—C17	179.33 (18)
C6—C1—C2—C3	−1.1 (3)	C14—C15—C16—C11	0.1 (3)
O3—C2—C3—C4	−179.3 (2)	C14—C15—C16—C17	−179.6 (2)
C1—C2—C3—C4	−0.1 (3)	C11—C16—C17—N3	−7.5 (3)
C2—C3—C4—C5	0.7 (4)	C15—C16—C17—N3	172.2 (2)
C3—C4—C5—C6	−0.1 (4)	C6—C7—N1—N2	−178.90 (17)
C4—C5—C6—C1	−1.2 (3)	O1—C8—N2—N1	−0.5 (3)
C4—C5—C6—C7	178.4 (2)	O2—C8—N2—N1	179.68 (16)
C2—C1—C6—C5	1.8 (3)	C7—N1—N2—C8	−178.09 (19)
C2—C1—C6—C7	−177.82 (18)	C16—C17—N3—N4	179.20 (17)
C5—C6—C7—N1	−179.1 (2)	O4—C18—N4—N3	3.2 (3)
C1—C6—C7—N1	0.6 (3)	O5—C18—N4—N3	−177.24 (15)
C16—C11—C12—O6	−179.59 (17)	C17—N3—N4—C18	175.34 (18)
C16—C11—C12—C13	0.5 (3)	O1—C8—O2—C9	2.9 (3)
O6—C12—C13—C14	179.7 (2)	N2—C8—O2—C9	−177.33 (16)
C11—C12—C13—C14	−0.4 (3)	C10—C9—O2—C8	178.68 (17)
C12—C13—C14—C15	0.1 (4)	O4—C18—O5—C19	−2.9 (3)
C13—C14—C15—C16	0.0 (4)	N4—C18—O5—C19	177.54 (16)
C12—C11—C16—C15	−0.4 (3)	C20—C19—O5—C18	−171.15 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O6ⁱ	0.86	2.29	3.0968 (18)	157
N4—H4N···O3	0.86	2.24	3.0849 (18)	167
O6—H6···O4W	0.82	1.90	2.675 (2)	157
C3—H3···O5	0.93	2.51	3.422 (2)	168
O1W—H1A···O2Wⁱⁱ	0.84 (3)	2.04 (3)	2.874 (3)	178 (3)
O1W—H1B···O2Wⁱⁱⁱ	0.91 (3)	1.99 (3)	2.906 (2)	177 (3)
O2W—H2A···O4	0.91 (3)	2.02 (3)	2.899 (2)	163 (2)
O2W—H2B···O1^iv	0.85 (3)	2.25 (3)	2.9268 (19)	136 (2)
O2W—H2B···N1^iv	0.85 (3)	2.41 (3)	3.165 (2)	148 (2)
O3W—H3A···O4ⁱⁱⁱ	0.89 (3)	2.27 (3)	2.9417 (19)	132 (2)
O3W—H3A···N3ⁱⁱⁱ	0.89 (3)	2.38 (3)	3.200 (2)	153 (3)
O3W—H3B···O1	0.90 (3)	2.10 (3)	2.991 (2)	171 (3)
O4W—H4B···O3W^v	0.98 (6)	1.84 (6)	2.819 (3)	173 (5)
O4W—H4A···O3W^iv	0.81 (3)	2.15 (3)	2.955 (2)	169 (3)

Symmetry codes: (i) x−1, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, y+1/2, −z+3/2; (v) x+1, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂O₃·2H₂O
M_r	244.25
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	12.8074 (10), 21.9101 (18), 8.9048 (7)
β (°)	96.490 (3)
V (Å³)	2482.8 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.20 × 0.19 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.977, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	22432, 4819, 3377
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.126, 0.95
No. of reflections	4819
No. of parameters	341
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.14

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O6ⁱ	0.86	2.29	3.0968 (18)	157
N4—H4N···O3	0.86	2.24	3.0849 (18)	167
O6—H6···O4W	0.82	1.90	2.675 (2)	157
C3—H3···O5	0.93	2.51	3.422 (2)	168
O1W—H1A···O2Wⁱⁱ	0.84 (3)	2.04 (3)	2.874 (3)	178 (3)
O1W—H1B···O2Wⁱⁱⁱ	0.91 (3)	1.99 (3)	2.906 (2)	177 (3)
O2W—H2A···O4	0.91 (3)	2.02 (3)	2.899 (2)	163 (2)
O2W—H2B···O1^iv	0.85 (3)	2.25 (3)	2.9268 (19)	136 (2)
O2W—H2B···N1^iv	0.85 (3)	2.41 (3)	3.165 (2)	148 (2)
O3W—H3A···O4ⁱⁱⁱ	0.89 (3)	2.27 (3)	2.9417 (19)	132 (2)
O3W—H3A···N3ⁱⁱⁱ	0.89 (3)	2.38 (3)	3.200 (2)	153 (3)
O3W—H3B···O1	0.90 (3)	2.10 (3)	2.991 (2)	171 (3)
O4W—H4B···O3W^v	0.98 (6)	1.84 (6)	2.819 (3)	173 (5)
O4W—H4A···O3W^iv	0.81 (3)	2.15 (3)	2.955 (2)	169 (3)

Symmetry codes: (i) x−1, y, z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y−1/2, −z+3/2; (iv) −x+1, y+1/2, −z+3/2; (v) x+1, −y+1/2, z−1/2.

Acknowledgements

The authors thank Hangzhou Vocational and Technical College, China, for financial support.

References

Borg, S., Vollinga, R. C., Labarre, M., Payza, K., Terenius, L. & Luthman, K. (1999). J. Med. Chem. 42, 4331–4342. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2002). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, J. (1987). Tetrahedron, 43, 1345–1360. CrossRef CAS Web of Science Google Scholar
Parashar, R. K., Sharma, R. C., Kumar, A. & Mohanm, G. (1988). Inorg. Chim Acta, 151, 201–208. CrossRef CAS Web of Science Google Scholar
Shang, Z.-H., Zhang, H.-L. & Ding, Y. (2007). Acta Cryst. E63, o3394. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar