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

Li, W.-W.; Yu, T.-M.; Lv, L.-P.; Hu, X.-C.

doi:10.1107/S1600536811035689

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2584

https://doi.org/10.1107/S1600536811035689

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

Wei-Wei Li,^a Tie-Ming Yu,^a Lu-Ping Lv ^a and Xian-Chao Hu ^b,^c ^*

^aLinjiang College, Hangzhou Vocational and Technical College, Hangzhou 310018, People's Republic of China, ^bCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China, and ^cResearch Center of Analysis and Measurement, Zhejiang University of Technology, Hangzhou 310014, People's Republic of China
^*Correspondence e-mail: zgdhxc@126.com

(Received 31 August 2011; accepted 1 September 2011; online 14 September 2011)

The title compound, C₉H₁₀N₂O₃·2H₂O, crystallizes with two organic molecules and four water molecules in the asymmetric unit. Both organic molecules adopt a trans conformation with respect to the C=N bond and are close to planar [dihedral angles between the side chain and the aromatic ring = 9.34 (8) and 4.96 (8)°]. In the crystal, the components are linked into three-dimensional network by N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For 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

C₉H₁₀N₂O₃·2H₂O
M_r = 230.22
Monoclinic, P 2₁ /c
a = 11.7316 (16) Å
b = 20.785 (3) Å
c = 9.5259 (16) Å
β = 99.675 (3)°
V = 2289.7 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 223 K
0.18 × 0.17 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.977, T_max = 0.989
19583 measured reflections
4438 independent reflections
3346 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.117
S = 1.03
4438 reflections
326 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 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
O1W—H1B⋯O2W	0.85 (3)	2.02 (3)	2.859 (2)	169 (2)
O1W—H1A⋯O2Wⁱ	0.86 (3)	1.95 (3)	2.809 (3)	172 (3)
N2—H2⋯O6ⁱⁱ	0.86	2.07	2.9278 (17)	171
O2W—H2A⋯O4ⁱⁱⁱ	1.02 (3)	1.88 (3)	2.893 (2)	171 (3)
O2W—H2B⋯O1	0.81 (3)	2.23 (3)	2.9102 (18)	141 (3)
O2W—H2B⋯N1	0.81 (3)	2.59 (3)	3.322 (2)	149 (3)
O3W—H3A⋯O4^iv	0.88 (3)	2.15 (3)	2.877 (2)	139 (3)
O3W—H3B⋯O1^v	0.95 (3)	1.90 (3)	2.832 (2)	168 (3)
O3—H3W⋯O1W	0.82	1.93	2.6617 (19)	147
O4W—H4B⋯O3Wⁱⁱⁱ	0.87 (3)	2.00 (3)	2.864 (2)	172 (2)
O4W—H4A⋯O3W^vi	0.82 (4)	2.20 (4)	3.013 (3)	170 (3)
N4—H4N⋯O3^vii	0.86	2.10	2.9509 (18)	169
O6—H6⋯O4W	0.92 (3)	1.75 (3)	2.665 (2)	176 (2)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x, -y+1, -z+2; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) x, y, z-1; (vi) x, y, z+1; (vii) -x+1, -y+1, -z+1.

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: https://doi.org/10.1107/S1600536811035689/hb6397sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035689/hb6397Isup2.hkl

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, (I).

The title compound, C₉H₁₀N₂O₃ .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-C9 and N3/N4/O4/O5/C16-C18 planes form dihedral angles of 9.34 (8)° and 4.96 (8)°, respectively, with the C1—C6 and C10—C15 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 structure, Intramolecular O—H···N and O—H···O hydrogen bonds are observed in each independent molecule. molecules are linked into three-dimensional network by N—H···O and O—H···Ohydrogen bonds (Table 1, Fig.2).

Related literature top

For 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 methyl hydrazinecarboxylate(0.9g, 0.01mol) were dissolved in stirred methanol (30ml) and left for 2h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 90% yield. Colourless blocks of (I) were obtained by slow evaporation of a ethanol solution at room temperature (m.p. 418-421 K).

Structure description top

For 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).

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 30% probability displacement ellipsoids. Dashed lines represent hydrogen bonds.
	Fig. 2. Crystal packing of the title compound, viewed approximately down the c axis. Dashed lines indicate hydrogen bonds. H atoms not intervening in H-bonding were eliminated for clarity.

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

Crystal data top

C₉H₁₀N₂O₃·2H₂O	F(000) = 976
M_r = 230.22	D_x = 1.336 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4438 reflections
a = 11.7316 (16) Å	θ = 1.6–26.0°
b = 20.785 (3) Å	µ = 0.11 mm⁻¹
c = 9.5259 (16) Å	T = 223 K
β = 99.675 (3)°	Block, colourless
V = 2289.7 (6) Å³	0.18 × 0.17 × 0.15 mm
Z = 8

Data collection top

Bruker SMART CCD diffractometer	4438 independent reflections
Radiation source: fine-focus sealed tube	3346 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
φ and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −13→14
T_min = 0.977, T_max = 0.989	k = −24→25
19583 measured reflections	l = −11→11

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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0525P)² + 0.6042P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
4438 reflections	Δρ_max = 0.22 e Å⁻³
326 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0121 (13)

Crystal data top

C₉H₁₀N₂O₃·2H₂O	V = 2289.7 (6) Å³
M_r = 230.22	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.7316 (16) Å	µ = 0.11 mm⁻¹
b = 20.785 (3) Å	T = 223 K
c = 9.5259 (16) Å	0.18 × 0.17 × 0.15 mm
β = 99.675 (3)°

Data collection top

Bruker SMART CCD diffractometer	4438 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	3346 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.989	R_int = 0.023
19583 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.22 e Å⁻³
4438 reflections	Δρ_min = −0.14 e Å⁻³
326 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
C1	0.24171 (13)	0.62113 (8)	0.93235 (17)	0.0448 (4)
H1	0.2511	0.5777	0.9139	0.054*
C2	0.29711 (14)	0.66693 (8)	0.86354 (17)	0.0482 (4)
C3	0.28141 (16)	0.73158 (9)	0.8879 (2)	0.0573 (5)
H3	0.3184	0.7624	0.8410	0.069*
C4	0.21077 (18)	0.74998 (9)	0.9821 (2)	0.0646 (5)
H4	0.1997	0.7935	0.9981	0.078*
C5	0.15620 (16)	0.70477 (8)	1.0530 (2)	0.0572 (5)
H5	0.1088	0.7178	1.1168	0.069*
C6	0.17198 (13)	0.64001 (8)	1.02913 (17)	0.0445 (4)
C7	0.11467 (14)	0.59292 (8)	1.10740 (17)	0.0473 (4)
H7	0.0626	0.6075	1.1640	0.057*
C8	0.08718 (13)	0.43208 (8)	1.18676 (17)	0.0445 (4)
C9	0.02974 (17)	0.33892 (8)	1.2976 (2)	0.0630 (5)
H9A	−0.0218	0.3263	1.3609	0.095*
H9B	0.1077	0.3282	1.3394	0.095*
H9C	0.0093	0.3167	1.2086	0.095*
C10	0.24610 (13)	0.40621 (8)	0.55031 (17)	0.0480 (4)
H10	0.2391	0.3631	0.5735	0.058*
C11	0.17966 (14)	0.45186 (8)	0.60274 (19)	0.0522 (4)
C12	0.19031 (17)	0.51613 (9)	0.5701 (2)	0.0607 (5)
H12	0.1448	0.5469	0.6051	0.073*
C13	0.26877 (18)	0.53409 (9)	0.4855 (2)	0.0644 (5)
H13	0.2769	0.5774	0.4643	0.077*
C14	0.33570 (16)	0.48887 (9)	0.43165 (19)	0.0570 (5)
H14	0.3887	0.5016	0.3746	0.068*
C15	0.32374 (14)	0.42458 (8)	0.46271 (17)	0.0467 (4)
C16	0.39374 (15)	0.37710 (8)	0.40232 (19)	0.0539 (4)
H16	0.4485	0.3914	0.3493	0.065*
C17	0.44785 (15)	0.21513 (8)	0.36295 (19)	0.0533 (4)
C18	0.52822 (17)	0.12027 (9)	0.2861 (2)	0.0629 (5)
H18A	0.5858	0.1071	0.2314	0.094*
H18B	0.4541	0.1039	0.2426	0.094*
H18C	0.5475	0.1037	0.3812	0.094*
N1	0.13314 (11)	0.53299 (6)	1.10118 (14)	0.0444 (3)
N2	0.07182 (11)	0.49575 (6)	1.18140 (14)	0.0483 (3)
H2	0.0235	0.5134	1.2282	0.058*
N3	0.38247 (12)	0.31715 (7)	0.41971 (16)	0.0534 (4)
N4	0.45443 (13)	0.27907 (7)	0.35476 (18)	0.0629 (4)
H4N	0.5036	0.2965	0.3089	0.075*
O1	0.15029 (10)	0.40159 (6)	1.12288 (14)	0.0586 (3)
O2	0.02087 (10)	0.40691 (5)	1.27386 (13)	0.0539 (3)
O1W	0.45469 (16)	0.53255 (7)	0.82064 (18)	0.0679 (4)
O3	0.36825 (11)	0.65024 (6)	0.76926 (14)	0.0668 (4)
H3W	0.3707	0.6109	0.7630	0.100*
O2W	0.33906 (13)	0.44786 (8)	0.98696 (18)	0.0720 (4)
O4	0.38368 (12)	0.18520 (6)	0.42559 (17)	0.0732 (4)
O3W	0.19045 (16)	0.27222 (8)	0.05155 (19)	0.0845 (5)
O5	0.52396 (11)	0.18889 (6)	0.29060 (15)	0.0629 (4)
O4W	0.10070 (16)	0.31023 (8)	0.7479 (2)	0.0787 (5)
O6	0.10057 (13)	0.43537 (7)	0.68672 (17)	0.0761 (4)
H4A	0.132 (3)	0.2983 (17)	0.827 (4)	0.141 (15)*
H1A	0.518 (2)	0.5347 (13)	0.881 (3)	0.102 (10)*
H1B	0.413 (2)	0.5075 (13)	0.861 (3)	0.094 (8)*
H4B	0.135 (2)	0.2862 (13)	0.692 (3)	0.092 (8)*
H2B	0.279 (2)	0.4539 (13)	1.017 (3)	0.106 (9)*
H2A	0.347 (3)	0.4003 (17)	0.965 (3)	0.139 (11)*
H3A	0.263 (3)	0.2683 (15)	0.039 (3)	0.126 (11)*
H3B	0.187 (2)	0.3149 (15)	0.085 (3)	0.120 (10)*
H6	0.103 (2)	0.3920 (13)	0.705 (2)	0.094 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0445 (8)	0.0408 (9)	0.0520 (9)	0.0018 (7)	0.0162 (7)	0.0025 (7)
C2	0.0450 (9)	0.0510 (10)	0.0519 (9)	0.0020 (7)	0.0176 (7)	0.0062 (7)
C3	0.0626 (11)	0.0454 (10)	0.0690 (11)	−0.0062 (8)	0.0262 (9)	0.0070 (8)
C4	0.0798 (13)	0.0409 (10)	0.0801 (13)	−0.0042 (9)	0.0336 (11)	−0.0047 (9)
C5	0.0653 (11)	0.0479 (10)	0.0654 (11)	−0.0014 (8)	0.0313 (9)	−0.0075 (8)
C6	0.0411 (8)	0.0458 (9)	0.0485 (9)	−0.0020 (7)	0.0128 (7)	−0.0003 (7)
C7	0.0462 (9)	0.0467 (10)	0.0540 (9)	−0.0012 (7)	0.0225 (7)	−0.0019 (7)
C8	0.0418 (8)	0.0441 (9)	0.0501 (9)	−0.0038 (7)	0.0152 (7)	−0.0024 (7)
C9	0.0709 (12)	0.0434 (10)	0.0791 (13)	−0.0057 (8)	0.0253 (10)	0.0067 (9)
C10	0.0461 (9)	0.0441 (9)	0.0579 (10)	0.0014 (7)	0.0200 (8)	0.0006 (7)
C11	0.0489 (9)	0.0520 (10)	0.0607 (10)	0.0027 (7)	0.0236 (8)	−0.0013 (8)
C12	0.0687 (12)	0.0491 (11)	0.0712 (12)	0.0085 (9)	0.0317 (10)	−0.0057 (8)
C13	0.0806 (13)	0.0430 (10)	0.0763 (12)	0.0006 (9)	0.0326 (11)	0.0001 (9)
C14	0.0634 (11)	0.0507 (10)	0.0633 (11)	−0.0012 (8)	0.0292 (9)	0.0035 (8)
C15	0.0460 (9)	0.0470 (9)	0.0500 (9)	0.0023 (7)	0.0168 (7)	0.0001 (7)
C16	0.0557 (10)	0.0497 (11)	0.0637 (11)	0.0022 (8)	0.0316 (9)	0.0034 (8)
C17	0.0485 (9)	0.0490 (10)	0.0680 (11)	0.0027 (8)	0.0259 (8)	0.0024 (8)
C18	0.0634 (11)	0.0483 (11)	0.0799 (13)	0.0027 (8)	0.0203 (10)	−0.0109 (9)
N1	0.0421 (7)	0.0455 (8)	0.0493 (7)	−0.0037 (6)	0.0184 (6)	0.0001 (6)
N2	0.0490 (7)	0.0413 (8)	0.0618 (8)	−0.0004 (6)	0.0296 (7)	−0.0002 (6)
N3	0.0511 (8)	0.0493 (9)	0.0671 (9)	0.0047 (6)	0.0307 (7)	0.0012 (7)
N4	0.0639 (9)	0.0461 (9)	0.0916 (11)	0.0041 (7)	0.0501 (9)	0.0029 (8)
O1	0.0615 (7)	0.0477 (7)	0.0744 (8)	0.0030 (6)	0.0338 (6)	−0.0050 (6)
O2	0.0568 (7)	0.0418 (6)	0.0699 (8)	−0.0023 (5)	0.0302 (6)	0.0034 (5)
O1W	0.0705 (10)	0.0576 (9)	0.0822 (10)	0.0064 (7)	0.0321 (9)	0.0102 (7)
O3	0.0772 (9)	0.0521 (7)	0.0843 (9)	0.0051 (6)	0.0516 (7)	0.0114 (6)
O2W	0.0593 (8)	0.0651 (10)	0.1011 (11)	−0.0063 (7)	0.0406 (8)	−0.0012 (8)
O4	0.0724 (9)	0.0517 (8)	0.1089 (11)	−0.0003 (6)	0.0542 (8)	0.0060 (7)
O3W	0.0890 (11)	0.0631 (10)	0.1173 (13)	−0.0099 (8)	0.0631 (10)	−0.0202 (9)
O5	0.0653 (8)	0.0459 (7)	0.0876 (9)	0.0016 (6)	0.0423 (7)	−0.0042 (6)
O4W	0.0942 (12)	0.0573 (9)	0.0935 (12)	0.0052 (8)	0.0418 (11)	0.0071 (9)
O6	0.0803 (10)	0.0565 (9)	0.1084 (12)	0.0107 (7)	0.0646 (9)	0.0068 (8)

Geometric parameters (Å, º) top

C1—C2	1.379 (2)	C13—C14	1.378 (3)
C1—C6	1.388 (2)	C13—H13	0.9300
C1—H1	0.9300	C14—C15	1.381 (2)
C2—O3	1.3695 (19)	C14—H14	0.9300
C2—C3	1.381 (2)	C15—C16	1.462 (2)
C3—C4	1.374 (2)	C16—N3	1.267 (2)
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.376 (2)	C17—O4	1.209 (2)
C4—H4	0.9300	C17—O5	1.3329 (19)
C5—C6	1.383 (2)	C17—N4	1.334 (2)
C5—H5	0.9300	C18—O5	1.428 (2)
C6—C7	1.461 (2)	C18—H18A	0.9600
C7—N1	1.267 (2)	C18—H18B	0.9600
C7—H7	0.9300	C18—H18C	0.9600
C8—O1	1.2132 (18)	N1—N2	1.3731 (17)
C8—N2	1.335 (2)	N2—H2	0.8600
C8—O2	1.3357 (18)	N3—N4	1.3776 (18)
C9—O2	1.432 (2)	N4—H4N	0.8600
C9—H9A	0.9600	O1W—H1A	0.86 (3)
C9—H9B	0.9600	O1W—H1B	0.85 (3)
C9—H9C	0.9600	O3—H3W	0.8200
C10—C11	1.374 (2)	O2W—H2B	0.81 (3)
C10—C15	1.388 (2)	O2W—H2A	1.02 (3)
C10—H10	0.9300	O3W—H3A	0.88 (3)
C11—O6	1.367 (2)	O3W—H3B	0.95 (3)
C11—C12	1.382 (3)	O4W—H4A	0.82 (4)
C12—C13	1.373 (3)	O4W—H4B	0.87 (3)
C12—H12	0.9300	O6—H6	0.92 (3)

C2—C1—C6	119.88 (15)	C11—C12—H12	120.3
C2—C1—H1	120.1	C12—C13—C14	120.89 (17)
C6—C1—H1	120.1	C12—C13—H13	119.6
O3—C2—C1	121.65 (15)	C14—C13—H13	119.6
O3—C2—C3	118.03 (14)	C13—C14—C15	119.70 (16)
C1—C2—C3	120.31 (15)	C13—C14—H14	120.2
C4—C3—C2	119.52 (16)	C15—C14—H14	120.2
C4—C3—H3	120.2	C14—C15—C10	119.71 (15)
C2—C3—H3	120.2	C14—C15—C16	119.00 (15)
C3—C4—C5	120.79 (17)	C10—C15—C16	121.30 (15)
C3—C4—H4	119.6	N3—C16—C15	122.31 (15)
C5—C4—H4	119.6	N3—C16—H16	118.8
C4—C5—C6	119.84 (16)	C15—C16—H16	118.8
C4—C5—H5	120.1	O4—C17—O5	124.86 (17)
C6—C5—H5	120.1	O4—C17—N4	126.06 (16)
C5—C6—C1	119.63 (15)	O5—C17—N4	109.08 (14)
C5—C6—C7	118.84 (14)	O5—C18—H18A	109.5
C1—C6—C7	121.52 (15)	O5—C18—H18B	109.5
N1—C7—C6	122.52 (14)	H18A—C18—H18B	109.5
N1—C7—H7	118.7	O5—C18—H18C	109.5
C6—C7—H7	118.7	H18A—C18—H18C	109.5
O1—C8—N2	126.05 (14)	H18B—C18—H18C	109.5
O1—C8—O2	125.11 (15)	C7—N1—N2	114.72 (13)
N2—C8—O2	108.84 (13)	C8—N2—N1	119.99 (12)
O2—C9—H9A	109.5	C8—N2—H2	120.0
O2—C9—H9B	109.5	N1—N2—H2	120.0
H9A—C9—H9B	109.5	C16—N3—N4	114.91 (14)
O2—C9—H9C	109.5	C17—N4—N3	120.01 (14)
H9A—C9—H9C	109.5	C17—N4—H4N	120.0
H9B—C9—H9C	109.5	N3—N4—H4N	120.0
C11—C10—C15	119.87 (16)	C8—O2—C9	116.76 (13)
C11—C10—H10	120.1	H1A—O1W—H1B	103 (2)
C15—C10—H10	120.1	C2—O3—H3W	109.5
O6—C11—C10	121.45 (16)	H2B—O2W—H2A	109 (3)
O6—C11—C12	118.05 (15)	H3A—O3W—H3B	103 (3)
C10—C11—C12	120.50 (15)	C17—O5—C18	117.01 (14)
C13—C12—C11	119.32 (16)	H4A—O4W—H4B	102 (3)
C13—C12—H12	120.3	C11—O6—H6	110.8 (15)

C6—C1—C2—O3	178.82 (15)	C13—C14—C15—C10	−1.3 (3)
C6—C1—C2—C3	−1.5 (3)	C13—C14—C15—C16	178.77 (18)
O3—C2—C3—C4	−179.89 (17)	C11—C10—C15—C14	1.6 (3)
C1—C2—C3—C4	0.4 (3)	C11—C10—C15—C16	−178.51 (17)
C2—C3—C4—C5	0.5 (3)	C14—C15—C16—N3	−175.88 (18)
C3—C4—C5—C6	−0.3 (3)	C10—C15—C16—N3	4.2 (3)
C4—C5—C6—C1	−0.8 (3)	C6—C7—N1—N2	−179.94 (14)
C4—C5—C6—C7	179.01 (17)	O1—C8—N2—N1	−2.0 (3)
C2—C1—C6—C5	1.7 (2)	O2—C8—N2—N1	178.36 (13)
C2—C1—C6—C7	−178.10 (15)	C7—N1—N2—C8	−177.79 (15)
C5—C6—C7—N1	−173.42 (17)	C15—C16—N3—N4	179.48 (16)
C1—C6—C7—N1	6.4 (3)	O4—C17—N4—N3	−1.1 (3)
C15—C10—C11—O6	178.56 (17)	O5—C17—N4—N3	178.98 (15)
C15—C10—C11—C12	−0.7 (3)	C16—N3—N4—C17	−178.25 (18)
O6—C11—C12—C13	−179.77 (19)	O1—C8—O2—C9	2.9 (2)
C10—C11—C12—C13	−0.5 (3)	N2—C8—O2—C9	−177.42 (15)
C11—C12—C13—C14	0.8 (3)	O4—C17—O5—C18	0.8 (3)
C12—C13—C14—C15	0.1 (3)	N4—C17—O5—C18	−179.25 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1B···O2W	0.85 (3)	2.02 (3)	2.859 (2)	169 (2)
O1W—H1A···O2Wⁱ	0.86 (3)	1.95 (3)	2.809 (3)	172 (3)
N2—H2···O6ⁱⁱ	0.86	2.07	2.9278 (17)	171
O2W—H2A···O4ⁱⁱⁱ	1.02 (3)	1.88 (3)	2.893 (2)	171 (3)
O2W—H2B···O1	0.81 (3)	2.23 (3)	2.9102 (18)	141 (3)
O2W—H2B···N1	0.81 (3)	2.59 (3)	3.322 (2)	149 (3)
O3W—H3A···O4^iv	0.88 (3)	2.15 (3)	2.877 (2)	139 (3)
O3W—H3B···O1^v	0.95 (3)	1.90 (3)	2.832 (2)	168 (3)
O3—H3W···O1W	0.82	1.93	2.6617 (19)	147
O4W—H4B···O3Wⁱⁱⁱ	0.87 (3)	2.00 (3)	2.864 (2)	172 (2)
O4W—H4A···O3W^vi	0.82 (4)	2.20 (4)	3.013 (3)	170 (3)
N4—H4N···O3^vii	0.86	2.10	2.9509 (18)	169
O6—H6···O4W	0.92 (3)	1.75 (3)	2.665 (2)	176 (2)

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

Experimental details

Crystal data
Chemical formula	C₉H₁₀N₂O₃·2H₂O
M_r	230.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	11.7316 (16), 20.785 (3), 9.5259 (16)
β (°)	99.675 (3)
V (Å³)	2289.7 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.18 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART CCD
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	19583, 4438, 3346
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.117, 1.03
No. of reflections	4438
No. of parameters	326
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −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
O1W—H1B···O2W	0.85 (3)	2.02 (3)	2.859 (2)	169 (2)
O1W—H1A···O2Wⁱ	0.86 (3)	1.95 (3)	2.809 (3)	172 (3)
N2—H2···O6ⁱⁱ	0.86	2.07	2.9278 (17)	171.2
O2W—H2A···O4ⁱⁱⁱ	1.02 (3)	1.88 (3)	2.893 (2)	171 (3)
O2W—H2B···O1	0.81 (3)	2.23 (3)	2.9102 (18)	141 (3)
O2W—H2B···N1	0.81 (3)	2.59 (3)	3.322 (2)	149 (3)
O3W—H3A···O4^iv	0.88 (3)	2.15 (3)	2.877 (2)	139 (3)
O3W—H3B···O1^v	0.95 (3)	1.90 (3)	2.832 (2)	168 (3)
O3—H3W···O1W	0.82	1.93	2.6617 (19)	147.2
O4W—H4B···O3Wⁱⁱⁱ	0.87 (3)	2.00 (3)	2.864 (2)	172 (2)
O4W—H4A···O3W^vi	0.82 (4)	2.20 (4)	3.013 (3)	170 (3)
N4—H4N···O3^vii	0.86	2.10	2.9509 (18)	169.4
O6—H6···O4W	0.92 (3)	1.75 (3)	2.665 (2)	176 (2)

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

Acknowledgements

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

References

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