(E)-Methyl N′-[(1H-indol-3-yl)methyl­idene]hydrazinecarboxyl­ate 0.25-hydrate

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

doi:10.1107/S1600536811026249

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1956

doi:10.1107/S1600536811026249

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(E)-Methyl N′-[(1H-indol-3-yl)methylidene]hydrazinecarboxylate 0.25-hydrate

Lu-Ping Lv,^a Tie-Ming Yu,^a Wen-Bo Yu ^a and Xian-Chao Hu ^b ^*

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

(Received 17 June 2011; accepted 1 July 2011; online 9 July 2011)

The asymmetric unit of the title compound, C₁₁H₁₁N₃O₂·0.25H₂O, contains two independent organic molecules and a water molecule, which lies on a twofold rotation axis. The side chains of the two molecules have slightly different orientations, the C=N—N—C torsion angle being −163.03 (15)° in one and −177.52 (14)° in the other, with each adopting a trans configuration with respect to the C=N bond. In the crystal, molecules are linked into chains extending along b by N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds and in addition, four intermolecular C—H⋯π interactions are present.

Related literature

For general background to Schiff bases, see: Cimerman et al. (1997 ); Offe et al. (1952 ); Richardson et al. (1988 ). For related structures, see: Shang et al. (2007 ); Tamboura et al. (2009 ).

Experimental

Crystal data

C₁₁H₁₁N₃O₂·0.25H₂O
M_r = 886.93
Monoclinic, C 2/c
a = 27.842 (2) Å
b = 11.7574 (11) Å
c = 18.565 (2) Å
β = 130.558 (5)°
V = 4617.2 (8) Å³
Z = 16
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 223 K
0.21 × 0.17 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.977, T_max = 0.989
21333 measured reflections
4052 independent reflections
3083 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.124
S = 1.05
4052 reflections
298 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 and Cg5 are the centroids of the C16–C19/N4 and C12–C17 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.86	2.15	2.9426 (18)	154
O1W—H1WA⋯N2ⁱⁱ	0.93 (2)	2.19 (2)	3.0773 (17)	161 (2)
O1W—H1WA⋯O1ⁱⁱ	0.93 (2)	2.60 (2)	3.2217 (14)	125 (2)
N6—H6⋯O1W	0.86	2.17	3.0087 (17)	166
C7—H7⋯Cg4ⁱⁱⁱ	0.93	2.85	3.594 (3)	137
C9—H9⋯Cg5ⁱⁱⁱ	0.93	2.74	3.537 (3)	145
C22—H22A⋯Cg4^iv	0.96	2.92	3.555 (4)	125
C22—H22A⋯Cg5^iv	0.96	2.86	3.796 (3)	125
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x, y-1, -z+{\script{1\over 2}}]$ ; (iv) $[-x+{\script{1\over 2}}, y+{\script{3\over 2}}, -z+{\script{1\over 2}}]$ .

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/S1600536811026249/zs2120sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811026249/zs2120Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811026249/zs2120Isup3.cml

checkCIF report

Comment top

Schiff bases have attracted much attention due to their potential analytical applications (Cimerman et al., 1997). They are also important ligands, which have been reported to have mild bacteriostatic activity and are used as potential oral iron-chelating drugs for genetic disorders such as thalassemia (Offe et al., 1952; Richardson et al., 1988). Metal complexes based on Schiff bases have received considerable attention because they can be utilized as model compounds of active centres in various complexes (Tamboura et al., 2009). We report here the crystal structure of the title compound C₁₁H₁₁N₃O₂ . 0.25H₂O.

The title compound (Fig. 1) has two independent, but almost conformationally identical molecules in the asymmetric unit, together with a water molecule of solvation which lies on a twofold rotation axis. Each molecule adopts a trans configuration with respect to the C═ N bond. The N2/N3/O1/O2/C10/C11 and N5/N6/O3/O4/C21/C22 planes form dihedral angles of 20.39 (6)° and 16.57 (6)°, respectively, with the C1—C8/N1 and C12—C19/N4 planes. The dihedral angle between the two independent benzene rings is 64.06 (4)°. The bond lengths and angles are comparable to those observed for methyl N'-[(E)-4-methoxybenzylidene]hydrazinecarboxylate (Shang et al., 2007).

The molecules are linked into chains extending along the b axis by N—H···O, O—H···N and O—H···O hydrogen bonds (Table 1 and Fig. 2). In addition, four intermolecular C—H···π interactions are present.

Related literature top

For general background to Schiff bases, see: Cimerman et al. (1997); Offe et al. (1952); Richardson et al. (1988). For related structures, see: Shang et al. (2007); Tamboura et al. (2009).

Experimental top

1H-Indole-3-carbaldehyde (1.45 g, 0.01 mol) and methyl hydrazinecarboxylate (0.90g, 0.01 mol) were dissolved in stirred methanol (15 ml) and left for 3.5 h at room temperature. The resulting solid was filtered off and recrystallized from ethanol to give the title compound in 93% yield. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature (m.p. 465–467 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. The molecular conformation and atom numbering scheme for the two independent organic molecules and the water molecule of solvation in the asymmetric unit of the title compound. The water molecule lies on a twofold rotation axis and the hydrogen bond is shown as a dashed line. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal packing of the title compound in the unit cell. Hydrogen bonds are shown as dashed lines.

(E)-Methyl N'-[(1H-indol-3-yl)methylidene]hydrazinecarboxylate 0.25-hydrate top

Crystal data top

C₁₁H₁₁N₃O₂·0.25H₂O	F(000) = 1864
M_r = 886.93	D_x = 1.276 Mg m⁻³
Monoclinic, C2/c	Melting point = 465–467 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 27.842 (2) Å	Cell parameters from 4052 reflections
b = 11.7574 (11) Å	θ = 1.9–25.0°
c = 18.565 (2) Å	µ = 0.09 mm⁻¹
β = 130.558 (5)°	T = 223 K
V = 4617.2 (8) Å³	Block, colourless
Z = 16	0.21 × 0.17 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4052 independent reflections
Radiation source: fine-focus sealed tube	3083 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −33→33
T_min = 0.977, T_max = 0.989	k = −13→13
21333 measured reflections	l = −22→22

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0709P)² + 0.7592P] where P = (F_o² + 2F_c²)/3
4052 reflections	(Δ/σ)_max < 0.001
298 parameters	Δρ_max = 0.16 e Å⁻³
1 restraint	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₁H₁₁N₃O₂·0.25H₂O	V = 4617.2 (8) Å³
M_r = 886.93	Z = 16
Monoclinic, C2/c	Mo Kα radiation
a = 27.842 (2) Å	µ = 0.09 mm⁻¹
b = 11.7574 (11) Å	T = 223 K
c = 18.565 (2) Å	0.21 × 0.17 × 0.15 mm
β = 130.558 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4052 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	3083 reflections with I > 2σ(I)
T_min = 0.977, T_max = 0.989	R_int = 0.029
21333 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	1 restraint
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.16 e Å⁻³
4052 reflections	Δρ_min = −0.19 e Å⁻³
298 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	0.37219 (7)	0.37491 (12)	0.56024 (11)	0.0531 (4)
H1A	0.4010	0.3162	0.5814	0.064*
C2	0.30987 (8)	0.35174 (15)	0.51235 (14)	0.0696 (5)
H2	0.2965	0.2765	0.5014	0.083*
C3	0.26622 (9)	0.43864 (17)	0.47977 (16)	0.0820 (6)
H3	0.2242	0.4201	0.4476	0.098*
C4	0.28342 (9)	0.55074 (16)	0.49370 (16)	0.0789 (5)
H4	0.2539	0.6085	0.4715	0.095*
C5	0.34667 (8)	0.57480 (12)	0.54227 (13)	0.0584 (4)
C6	0.39200 (7)	0.48869 (12)	0.57692 (10)	0.0475 (3)
C7	0.43931 (9)	0.65934 (14)	0.61492 (13)	0.0665 (5)
H7	0.4696	0.7161	0.6391	0.080*
C8	0.45160 (7)	0.54508 (13)	0.62345 (11)	0.0522 (4)
C9	0.51368 (7)	0.50072 (14)	0.67094 (11)	0.0552 (4)
H9	0.5470	0.5521	0.7009	0.066*
C10	0.60747 (8)	0.27236 (15)	0.71437 (11)	0.0607 (4)
C11	0.69308 (11)	0.1737 (2)	0.7468 (2)	0.1228 (10)
H11A	0.7380	0.1807	0.7843	0.184*
H11B	0.6730	0.1700	0.6809	0.184*
H11C	0.6839	0.1056	0.7644	0.184*
C12	0.10157 (13)	0.8858 (2)	0.10052 (18)	0.0940 (8)
H12	0.0845	0.9202	0.0432	0.113*
C13	0.15456 (13)	0.9284 (2)	0.1845 (2)	0.0928 (7)
H13	0.1743	0.9920	0.1842	0.111*
C14	0.17960 (9)	0.87807 (16)	0.27089 (15)	0.0760 (5)
H14	0.2158	0.9085	0.3271	0.091*
C15	0.15154 (7)	0.78446 (14)	0.27389 (12)	0.0591 (4)
H15	0.1682	0.7524	0.3318	0.071*
C16	0.09771 (8)	0.73753 (14)	0.18920 (11)	0.0575 (4)
C17	0.07411 (10)	0.78978 (18)	0.10343 (13)	0.0741 (5)
C18	0.01498 (10)	0.6371 (2)	0.06843 (15)	0.0889 (7)
H18	−0.0161	0.5817	0.0330	0.107*
C19	0.05859 (8)	0.63973 (15)	0.16554 (12)	0.0629 (4)
C20	0.06170 (8)	0.56012 (14)	0.22699 (14)	0.0649 (5)
H20	0.0370	0.4947	0.2013	0.078*
C21	0.13167 (8)	0.50520 (12)	0.46021 (14)	0.0601 (4)
C22	0.16560 (12)	0.40801 (19)	0.59737 (16)	0.0963 (7)
H22A	0.1588	0.3377	0.6159	0.144*
H22B	0.1545	0.4705	0.6174	0.144*
H22C	0.2093	0.4140	0.6265	0.144*
N1	0.37741 (8)	0.67819 (11)	0.56674 (12)	0.0742 (4)
H1	0.3599	0.7439	0.5534	0.089*
N2	0.52637 (6)	0.39465 (11)	0.67489 (9)	0.0563 (3)
N3	0.58987 (6)	0.37255 (13)	0.72462 (10)	0.0686 (4)
H3N	0.6178	0.4232	0.7620	0.082*
N4	0.02321 (9)	0.7252 (2)	0.03134 (11)	0.0964 (6)
H4A	0.0003	0.7393	−0.0282	0.116*
N5	0.09752 (6)	0.57712 (10)	0.31589 (11)	0.0603 (4)
N6	0.09703 (7)	0.49139 (11)	0.36687 (11)	0.0670 (4)
H6	0.0749	0.4308	0.3390	0.080*
O1	0.57234 (6)	0.19418 (10)	0.66782 (9)	0.0769 (4)
O2	0.66952 (6)	0.27132 (13)	0.76297 (11)	0.0956 (5)
O1W	0.0000	0.30761 (12)	0.2500	0.0550 (4)
O3	0.16253 (6)	0.58794 (9)	0.50562 (9)	0.0702 (3)
O4	0.12715 (6)	0.41067 (10)	0.49677 (10)	0.0790 (4)
H1WA	−0.0053 (11)	0.2590 (17)	0.2837 (14)	0.110 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0528 (9)	0.0430 (8)	0.0676 (10)	0.0006 (6)	0.0410 (8)	0.0033 (7)
C2	0.0606 (11)	0.0536 (10)	0.0968 (13)	−0.0079 (8)	0.0522 (11)	−0.0047 (9)
C3	0.0542 (11)	0.0768 (13)	0.1139 (16)	−0.0024 (9)	0.0541 (12)	−0.0064 (11)
C4	0.0640 (12)	0.0660 (11)	0.1093 (15)	0.0177 (9)	0.0574 (12)	0.0080 (10)
C5	0.0641 (11)	0.0464 (8)	0.0772 (11)	0.0035 (7)	0.0515 (10)	0.0014 (7)
C6	0.0533 (9)	0.0443 (8)	0.0554 (9)	0.0002 (6)	0.0401 (8)	0.0017 (6)
C7	0.0784 (12)	0.0476 (9)	0.0950 (13)	−0.0127 (8)	0.0659 (11)	−0.0078 (8)
C8	0.0590 (10)	0.0474 (8)	0.0620 (10)	−0.0076 (7)	0.0446 (9)	−0.0042 (7)
C9	0.0545 (10)	0.0576 (10)	0.0632 (10)	−0.0147 (7)	0.0425 (9)	−0.0093 (7)
C10	0.0535 (10)	0.0675 (11)	0.0551 (9)	0.0027 (8)	0.0327 (8)	0.0019 (8)
C11	0.0888 (17)	0.129 (2)	0.133 (2)	0.0305 (15)	0.0641 (16)	−0.0249 (17)
C12	0.123 (2)	0.1079 (18)	0.0932 (16)	0.0552 (16)	0.0886 (17)	0.0451 (14)
C13	0.1119 (19)	0.0849 (15)	0.130 (2)	0.0228 (13)	0.1002 (19)	0.0324 (14)
C14	0.0701 (12)	0.0744 (12)	0.0918 (14)	0.0033 (9)	0.0564 (11)	0.0109 (10)
C15	0.0549 (10)	0.0629 (10)	0.0582 (9)	0.0075 (7)	0.0362 (8)	0.0080 (8)
C16	0.0570 (10)	0.0627 (10)	0.0539 (9)	0.0217 (8)	0.0365 (8)	0.0073 (7)
C17	0.0815 (13)	0.0883 (14)	0.0601 (11)	0.0357 (11)	0.0494 (11)	0.0148 (10)
C18	0.0670 (13)	0.1005 (17)	0.0687 (13)	0.0171 (11)	0.0306 (11)	−0.0243 (12)
C19	0.0501 (9)	0.0642 (11)	0.0613 (10)	0.0093 (8)	0.0304 (9)	−0.0114 (8)
C20	0.0497 (10)	0.0529 (9)	0.0816 (13)	−0.0011 (7)	0.0380 (10)	−0.0145 (9)
C21	0.0554 (10)	0.0384 (8)	0.0911 (13)	−0.0019 (7)	0.0497 (10)	−0.0021 (8)
C22	0.1127 (18)	0.0771 (14)	0.0996 (17)	−0.0153 (12)	0.0692 (16)	0.0080 (11)
N1	0.0903 (11)	0.0386 (7)	0.1144 (12)	0.0056 (7)	0.0758 (11)	0.0035 (7)
N2	0.0464 (8)	0.0592 (8)	0.0643 (8)	−0.0069 (6)	0.0364 (7)	−0.0063 (6)
N3	0.0460 (8)	0.0722 (9)	0.0825 (10)	−0.0108 (7)	0.0394 (8)	−0.0202 (8)
N4	0.0883 (13)	0.1306 (17)	0.0476 (9)	0.0431 (12)	0.0341 (10)	0.0016 (10)
N5	0.0542 (8)	0.0436 (7)	0.0782 (10)	−0.0021 (6)	0.0410 (8)	−0.0039 (6)
N6	0.0647 (9)	0.0428 (7)	0.0899 (11)	−0.0131 (6)	0.0486 (9)	−0.0071 (7)
O1	0.0685 (8)	0.0574 (7)	0.0732 (8)	0.0012 (6)	0.0321 (7)	0.0016 (6)
O2	0.0550 (8)	0.1026 (11)	0.1118 (11)	0.0021 (7)	0.0465 (8)	−0.0286 (9)
O1W	0.0567 (9)	0.0410 (8)	0.0685 (10)	0.000	0.0412 (8)	0.000
O3	0.0713 (8)	0.0426 (6)	0.0865 (9)	−0.0090 (5)	0.0468 (7)	−0.0039 (6)
O4	0.0910 (10)	0.0490 (7)	0.1064 (11)	−0.0161 (6)	0.0684 (9)	−0.0004 (6)

Geometric parameters (Å, º) top

C1—C2	1.367 (2)	C13—H13	0.9300
C1—C6	1.403 (2)	C14—C15	1.372 (2)
C1—H1A	0.9300	C14—H14	0.9300
C2—C3	1.390 (3)	C15—C16	1.399 (2)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.368 (3)	C16—C17	1.409 (2)
C3—H3	0.9300	C16—C19	1.442 (2)
C4—C5	1.389 (2)	C17—N4	1.382 (3)
C4—H4	0.9300	C18—N4	1.344 (3)
C5—N1	1.382 (2)	C18—C19	1.371 (3)
C5—C6	1.406 (2)	C18—H18	0.9300
C6—C8	1.441 (2)	C19—C20	1.434 (3)
C7—N1	1.347 (2)	C20—N5	1.272 (2)
C7—C8	1.370 (2)	C20—H20	0.9300
C7—H7	0.9300	C21—O3	1.2055 (18)
C8—C9	1.434 (2)	C21—N6	1.336 (2)
C9—N2	1.285 (2)	C21—O4	1.3502 (19)
C9—H9	0.9300	C22—O4	1.427 (2)
C10—O1	1.2038 (19)	C22—H22A	0.9600
C10—O2	1.331 (2)	C22—H22B	0.9600
C10—N3	1.336 (2)	C22—H22C	0.9600
C11—O2	1.447 (3)	N1—H1	0.8600
C11—H11A	0.9600	N2—N3	1.3868 (18)
C11—H11B	0.9600	N3—H3N	0.8600
C11—H11C	0.9600	N4—H4A	0.8600
C12—C13	1.367 (3)	N5—N6	1.3887 (19)
C12—C17	1.384 (3)	N6—H6	0.8600
C12—H12	0.9300	O1W—H1WA	0.928 (15)
C13—C14	1.398 (3)

C2—C1—C6	118.95 (14)	C13—C14—H14	119.5
C2—C1—H1A	120.5	C14—C15—C16	119.54 (16)
C6—C1—H1A	120.5	C14—C15—H15	120.2
C1—C2—C3	121.17 (16)	C16—C15—H15	120.2
C1—C2—H2	119.4	C15—C16—C17	118.01 (18)
C3—C2—H2	119.4	C15—C16—C19	134.57 (15)
C4—C3—C2	121.77 (17)	C17—C16—C19	107.38 (17)
C4—C3—H3	119.1	N4—C17—C12	130.9 (2)
C2—C3—H3	119.1	N4—C17—C16	106.6 (2)
C3—C4—C5	117.33 (16)	C12—C17—C16	122.4 (2)
C3—C4—H4	121.3	N4—C18—C19	110.9 (2)
C5—C4—H4	121.3	N4—C18—H18	124.6
N1—C5—C4	130.18 (15)	C19—C18—H18	124.6
N1—C5—C6	107.65 (14)	C18—C19—C20	125.10 (19)
C4—C5—C6	122.17 (15)	C18—C19—C16	105.46 (19)
C1—C6—C5	118.61 (14)	C20—C19—C16	129.43 (15)
C1—C6—C8	134.87 (14)	N5—C20—C19	121.37 (15)
C5—C6—C8	106.51 (13)	N5—C20—H20	119.3
N1—C7—C8	110.71 (14)	C19—C20—H20	119.3
N1—C7—H7	124.6	O3—C21—N6	126.17 (16)
C8—C7—H7	124.6	O3—C21—O4	124.73 (18)
C7—C8—C9	122.58 (14)	N6—C21—O4	109.10 (14)
C7—C8—C6	106.16 (14)	O4—C22—H22A	109.5
C9—C8—C6	131.26 (14)	O4—C22—H22B	109.5
N2—C9—C8	124.40 (14)	H22A—C22—H22B	109.5
N2—C9—H9	117.8	O4—C22—H22C	109.5
C8—C9—H9	117.8	H22A—C22—H22C	109.5
O1—C10—O2	124.77 (17)	H22B—C22—H22C	109.5
O1—C10—N3	124.98 (16)	C7—N1—C5	108.96 (13)
O2—C10—N3	110.25 (15)	C7—N1—H1	125.5
O2—C11—H11A	109.5	C5—N1—H1	125.5
O2—C11—H11B	109.5	C9—N2—N3	113.83 (13)
H11A—C11—H11B	109.5	C10—N3—N2	119.82 (14)
O2—C11—H11C	109.5	C10—N3—H3N	120.1
H11A—C11—H11C	109.5	N2—N3—H3N	120.1
H11B—C11—H11C	109.5	C18—N4—C17	109.66 (16)
C13—C12—C17	117.93 (19)	C18—N4—H4A	125.2
C13—C12—H12	121.0	C17—N4—H4A	125.2
C17—C12—H12	121.0	C20—N5—N6	115.05 (14)
C12—C13—C14	121.1 (2)	C21—N6—N5	118.48 (13)
C12—C13—H13	119.4	C21—N6—H6	120.8
C14—C13—H13	119.4	N5—N6—H6	120.8
C15—C14—C13	120.9 (2)	C10—O2—C11	115.48 (17)
C15—C14—H14	119.5	C21—O4—C22	116.13 (15)

C6—C1—C2—C3	0.4 (3)	C15—C16—C17—C12	−1.0 (2)
C1—C2—C3—C4	0.2 (3)	C19—C16—C17—C12	−179.00 (16)
C2—C3—C4—C5	−0.2 (3)	N4—C18—C19—C20	177.95 (16)
C3—C4—C5—N1	−179.76 (19)	N4—C18—C19—C16	−1.3 (2)
C3—C4—C5—C6	−0.5 (3)	C15—C16—C19—C18	−176.42 (17)
C2—C1—C6—C5	−1.0 (2)	C17—C16—C19—C18	1.06 (17)
C2—C1—C6—C8	179.73 (16)	C15—C16—C19—C20	4.4 (3)
N1—C5—C6—C1	−179.47 (14)	C17—C16—C19—C20	−178.17 (15)
C4—C5—C6—C1	1.1 (2)	C18—C19—C20—N5	−169.80 (16)
N1—C5—C6—C8	−0.04 (17)	C16—C19—C20—N5	9.3 (3)
C4—C5—C6—C8	−179.45 (17)	C8—C7—N1—C5	0.4 (2)
N1—C7—C8—C9	179.48 (14)	C4—C5—N1—C7	179.13 (19)
N1—C7—C8—C6	−0.42 (19)	C6—C5—N1—C7	−0.2 (2)
C1—C6—C8—C7	179.56 (17)	C8—C9—N2—N3	179.82 (14)
C5—C6—C8—C7	0.28 (17)	O1—C10—N3—N2	−4.1 (3)
C1—C6—C8—C9	−0.3 (3)	O2—C10—N3—N2	175.87 (15)
C5—C6—C8—C9	−179.62 (16)	C9—N2—N3—C10	−163.03 (15)
C7—C8—C9—N2	−175.11 (16)	C19—C18—N4—C17	1.1 (2)
C6—C8—C9—N2	4.8 (3)	C12—C17—N4—C18	178.02 (19)
C17—C12—C13—C14	−1.2 (3)	C16—C17—N4—C18	−0.4 (2)
C12—C13—C14—C15	−0.3 (3)	C19—C20—N5—N6	−178.25 (13)
C13—C14—C15—C16	1.1 (3)	O3—C21—N6—N5	2.6 (2)
C14—C15—C16—C17	−0.5 (2)	O4—C21—N6—N5	−177.00 (13)
C14—C15—C16—C19	176.80 (17)	C20—N5—N6—C21	−177.52 (14)
C13—C12—C17—N4	−176.32 (18)	O1—C10—O2—C11	8.4 (3)
C13—C12—C17—C16	1.8 (3)	N3—C10—O2—C11	−171.5 (2)
C15—C16—C17—N4	177.52 (13)	O3—C21—O4—C22	−4.5 (2)
C19—C16—C17—N4	−0.45 (17)	N6—C21—O4—C22	175.15 (16)

Hydrogen-bond geometry (Å, º) top

Cg4 and Cg5 are the centroids of the C16–C19/N4 and C12–C17 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	2.15	2.9426 (18)	154
O1W—H1WA···N2ⁱⁱ	0.93 (2)	2.19 (2)	3.0773 (17)	161 (2)
O1W—H1WA···O1ⁱⁱ	0.93 (2)	2.60 (2)	3.2217 (14)	125 (2)
N6—H6···O1W	0.86	2.17	3.0087 (17)	166
C7—H7···Cg4ⁱⁱⁱ	0.93	2.85	3.594 (3)	137
C9—H9···Cg5ⁱⁱⁱ	0.93	2.74	3.537 (3)	145
C22—H22A···Cg4^iv	0.96	2.92	3.555 (4)	125
C22—H22A···Cg5^iv	0.96	2.86	3.796 (3)	125

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁N₃O₂·0.25H₂O
M_r	886.93
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	223
a, b, c (Å)	27.842 (2), 11.7574 (11), 18.565 (2)
β (°)	130.558 (5)
V (Å³)	4617.2 (8)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.21 × 0.17 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector 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	21333, 4052, 3083
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.124, 1.05
No. of reflections	4052
No. of parameters	298
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.19

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

Hydrogen-bond geometry (Å, º) top

Cg4 and Cg5 are the centroids of the C16–C19/N4 and C12–C17 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	2.15	2.9426 (18)	153.7
O1W—H1WA···N2ⁱⁱ	0.928 (15)	2.187 (16)	3.0773 (17)	160.5 (19)
O1W—H1WA···O1ⁱⁱ	0.928 (15)	2.60 (2)	3.2217 (14)	124.5 (17)
N6—H6···O1W	0.86	2.17	3.0087 (17)	165.8
C7—H7···Cg4ⁱⁱⁱ	0.93	2.85	3.594 (3)	137
C9—H9···Cg5ⁱⁱⁱ	0.93	2.74	3.537 (3)	145
C22—H22A···Cg4^iv	0.96	2.92	3.555 (4)	125
C22—H22A···Cg5^iv	0.96	2.86	3.796 (3)	125

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

Acknowledgements

The authors thank the Science and Technology Project of Zhejiang Province (grant No. 2007 F70077) and Hangzhou Vocational and Technical College for financial support.

References

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Volume 67| Part 8| August 2011| Page o1956

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