(E)-N'-(4-Chloro­benzyl­idene)-, (E)-N'-(4-bromo­benzyl­idene)- and (E)-N'-[4-(diethyl­amino)­benzyl­idene]- derivatives of 4-hy­droxy­benzo­hydrazide

The 4-chloro- [C₁₄H₁₁ClN₂O₂, (I)], 4-bromo- [C₁₄H₁₀BrN₂O₂, (II)] and 4-diethyl­amino- [C₁₈H₂₁N₃O₂, (III)] derivatives of benzyl­idene-4-hy­droxy­benzo­hydrazide, all crystallize in the same space group (P2₁/c), (I) and (II) also being isomorphous. In all three compounds, the conformation about the C=N bond is E. The mol­ecules of (I) and (II) are relatively planar, with dihedral angles between the two benzene rings of 5.75 (12) and 9.81 (17)°, respectively. In (III), however, the same angle is 77.27 (9)°. In the crystal structures of (I) and (II), two-dimensional slab-like networks extending in the a and c directions are formed via N-H...O and O-H...O hydrogen bonds. The mol­ecules stack head-to-tail via [pi]-[pi] inter­actions involving the aromatic rings [centroid-centroid distance = 3.7622 (14) Å in (I) and 3.8021 (19) Å in (II)]. In (III), undulating two-dimensional networks extending in the b and c directions are formed via N-H...O and O-H...O hydrogen bonds. The mol­ecules stack head-to-head via [pi]-[pi] inter­actions involving inversion-related benzene rings [cen­troid-centroid distances = 3.6977 (12) and 3.8368 (11) Å].

S1. Comment

The condensation reaction of aromatic aldehydes with primary amines can be used to form a huge variety of Schiff bases. Such compounds have been intensely studied due to their ease of synthesis, versatile structures and wide applications (Sigman & Jacobsen, 1998; Akitsu & Einaga, 2006; Pradeep, 2005; Butcher et al., 2005). Furthermore, Schiff bases have also been employed as ligands for the complexation of metal ions (Kumar et al., 2009). The excellent antibacterial and antitumour properties of such compounds have attracted much interest over the years (Hodnett & Mooney, 1970; Bahner et al., 1968; Merchant & Chothia, 1970). Hydrazone compounds possess exceptional biological properties, especially for their potential pharmacological and antitumour properties (Kucukguzel et al., 2006; Khattab, 2005; Karthikeyan et al., 2006; Okabe et al., 1993) and for their antibacterial activities (Cukurovali et al., 2002), or their uses in technology and analytical chemistry (Kitaev, 1977). Recently, a number of hydrazone compounds have been prepared and structurally characterized (Abdul Alhadi et al., 2009; Mohd Lair et al., 2009; Cao & Lu, 2009; Qu & Cao, 2009). Hydrazone compounds have also been used as chelating ligands for the spectrophotometric and fluorimetric determination of trace metal ions (Katyal & Dutt, 1975; Galiano-Roth & Collum, 1988; Sugano et al., 2009).

Hydrazone derivatives can possess nonlinear optical (NLO) properties because of their large molecular nonlinearities and their remarkable propensity to form noncentrosymmetric crystal systems (Serbutoviez et al., 1995). The chemistry of 2-hydroxybenzohydrazide and its derivatives have been studied because of their multiple coordination environments (Chang, 2008; Huo et al., 2004). The presence of O and N atoms also means that various hydrogen-bonding motifs can be formed, which can lead to the formation of versatile supramolecular architectures in the crystal structures. 4-Hydroxybenzohydrazide has also been used to prepare a number of compounds which have been shown to possess a variety of biological activities, for example, antitumour (Patil et al., 2011; Bhole & Bhusari, 2011), antibacterial (Rajput, 2012) and antitubercular (Bhole et al., 2012).

In the present work, we report the synthesis and crystal structures of three new Schiff base compounds formed by the reaction of 4-hydroxybenzohydrazide with 4-chlorobenzaldehyde, 4-bromobenzaldehyde and 4-diethylaminobenzaldehyde, compounds (I), (II) and (III), respectively.

The molecular structure of (I) is illustrated in Fig. 1. The two benzene rings, A (C1–C6) and B (C9–C14), are almost coplanar, with a dihedral angle of 5.75 (12)°. The molecule has an E conformation about the C8═N2 bond. The mean plane of the N2—N1—C7═O1 segment [maximum deviation 0.003 (2) Å For which atom?] is inclined to rings A and B by 28.51 (15) and 22.77 (15)°, respectively, while the C7—N1—N2═C8 torsion angle is 166.6 (2)°.

In the crystal structure of (I), the molecules are linked by N—H···O and O—H···O hydrogen bonds (Table 1) to form two-dimensional slab-like networks propagating in the a and c directions (Fig. 2). These networks are linked via weak C—H···O interactions to form a three-dimensional structure (Table 1).

The molecular structure of (II), illustrated in Fig. 3, is very similar to that of (I). The two benzene rings, A (C1–C6) and B (C9–C14), are almost coplanar, with a dihedral angle of 9.81 (17)°, and the molecule has an E conformation about the C8═N2 bond. The mean plane of the N2—N1—C7═O1 segment [maximum deviation = 0.005 (3) Å For which atom?] is inclined to rings A and B by 28.29 (19) and 18.7 (2)°, respectively, while the C7—N1—N2═C8 torsion angle is 169.0 (3)°.

In the crystal structure of (II), the molecules are linked by N—H···O and O—H···O hydrogen bonds (Table 2) to form two-dimensional slab-like networks propagating in the a and c directions (Fig. 4 and Table 2). These networks are slightly futher apart than in (I), with the shortest C13—H13···O2ⁱ [symmetry code: (i) -x + 2, y - 1/2, -z + 3/2] H···A distance being 2.65 Å, compared with 2.52 Å in (I). Hence, no significant C—H···O interactions are present.

In (I) and (II), the molecules stack head-to-tail via π–π interactions involving the aromatic rings. The centroid-to-centroid distance in (I) is 3.7622 (14) Å [Cg1···Cg2ⁱⁱ, where Cg1 and Cg2 are the centroids of the C1–C6 and C9–C14 rings, respectively; symmetry code: (ii) x - 1, -y + 1/2, z - 1/2]. In (II) the same distance is 3.8021 (19) Å [Cg1···Cg2ⁱⁱⁱ, Cg defined as for (I); symmetry code: (iii) x + 1, -y + 1/2, z + 1/2].

The molecular structure of (III) is illustrated in Fig. 5. The molecule has an E conformation about the C8═N2 bond, with the two benzene rings, A (C1–C6) and B (C9–C14), inclined to one another by 77.27 (9)°, compared with 5.75 (12)° in (I) and 9.81 (17)° in (II). The mean plane of the N2—N1—C7═O1 segment [maximum deviation = 0.015 (2) Å For which atom?] is inclined to rings A and B by 36.85 (11) and 40.57 (11)°, respectively. Again, these angles are much larger than those observed in (I) and (II), while the C7—N1—N2═C8 torsion angle is smaller at 151.69 (17)°.

In the crystal structure of (III), the molecules are linked by N—H···O and O—H···O hydrogen bonds to form undulating two-dimensional networks extending in the b and c directions. These networks are stabilized by C—H···O hydrogen bonds (Fig. 6 and Table 3).

In (III), the molecules stack head-to-head via π–π interactions involving inversion-related benzene rings, with centroid-to-centroid distances of 3.6977 (12) [Cg2···Cg2^iv, Cg defined as for (I); symmetry code: (iv) -x, -y + 2, -z] and 3.8368 (11) Å [Cg1···Cg1^v; symmetry code: (v) -x + 1, -y + 1, -z].

A search of the Cambridge Structural Database (CSD, Version 5.33, Update 3, May 2012; Allen, 2002) gave more than 400 hits for the substructure benzylidenebenzohydrazide, excluding metal complexes. Of these there were 59 hits for benzylidene-4-hydroxybenzohydrazide and an even smaller number for 4-substituted benzylidene-4-hydroxybenzohydrazides. This later search included four compounds where the substituent is comparable in size with those in (I)–(III). They include the 4-nitro derivative, (IV) (Li & Ban, 2009b), the 4-methoxy derivative, (V) (Shi, 2009), and the methanol solvate of the 4-hydroxy derivative, (VI) (Li & Ban, 2009a), which all crystallize in centrosymmetric space groups, and finally the hemihydrate of the 4-dimethylamino derivative, (VII) (Liu, 2010), which crystallizes in the chiral monoclinic space group P2₁. Compound (III), the 4-diethylamino derivative, was prepared in the hope that it too would crystallize in a chiral or non-centrosymmetric space group, but this was not to be the case.

In compounds (IV), (VI) and (VII), the molecules are relatively planar, with the benzene rings being inclined to one another by 2.54 (7), 7.21 (7) and 7.67 (13)°, respectively. In (V) this same angle is larger, 46.56 (7)°, but still smaller than that found for (III) [77.27 (9)°].

In the crystal structures of (IV) and (V), O—H···O and N—H···O hydrogen bonds lead to the formation of two-dimensional networks, while for (VI) similar interactions lead to the formation of a three-dimensional structure. Compound (VII) crystallized with two independent molecules and one water molecule per asymmetric unit, and the water molecule links the two molecules via O—H···O hydrogen bonds. These units are then linked via N—H···O and O—H..O hydrogen bonds to form a three-dimensional structure. As in the crystal structures of (I)–(III), there are also weak π–π stacking interactions in the crystal structures of (IV)–(VII) [centroid-to-centroid distances vary between 3.6701 (11) Å in (V) to 3.9185 (7) Å in (VII)].

Related literature

For related literature, see: Abdul Alhadi, Ali & Ng (2009); Akitsu & Einaga (2006); Allen (2002); Bahner et al. (1968); Bhole & Bhusari (2011); Bhole et al. (2012); Butcher et al. (2005); Cao & Lu (2009); Chang (2008); Cukurovali et al. (2002); Galiano-Roth & Collum (1988); Hodnett & Mooney (1970); Huo et al. (2004); Karthikeyan et al. (2006); Katyal & Dutt (1975); Khattab (2005); Kitaev (1977); Kucukguzel et al. (2006); Kumar et al. (2009); Li & Ban (2009a, 2009b); Liu (2010); Merchant & Chothia (1970); Mohd Lair, Mohd Ali & Ng (2009); Okabe et al. (1993); Patil et al. (2011); Pradeep (2005); Qu & Cao (2009); Rajput (2012); Serbutoviez et al. (1995); Shi (2009); Sigman & Jacobsen (1998); Sugano et al. (2009).

S2. Experimental

Compound (I) was prepared by the reaction of 4-hydroxybenzohydrazide with 4-chlorobenzaldehyde (molar ratio 1:1) in methanol. The reaction mixture was heated and refluxed for 4 h and then filtered. Compounds (II) and (III) were prepared in the same manner, using 4-hydroxybenzohydrazide and 4-bromobenzaldehyde for (II), and 4-hydroxybenzohydrazide and 4-diethylaminobenzaldehyde for (III). In each case, crystals suitable for X-ray diffraction analysis were formed by slow evaporation of the solvent at room temperature over several days.

S3. Refinement

For all three compounds, the H atoms could be located in difference Fourier maps. The N- and O-bound H atoms were refined freely for (I) and (III), but with distance restraints for (II) [O—H = 0.82 (2) Å and N—H = 0.86 (2) Å]. C-bound H atoms were included in calculated positions and treated as riding atoms, with C—H = 0.93 Å for CH in (II) but 0.95 Å in (I) and (III), 0.99 Å for CH₂ and 0.98 Å for CH₃ H atoms, and with U_iso(H) = kU_eq(C), where k = 1.5 for CH₃ H atoms and 1.2 for other H atoms.

Computing details

Data collection: X-AREA (Stoe & Cie, 2009) for (I), (III); EXPOSE in IPDS I Bedienungshandbuch (Stoe & Cie, 2004) for (II). Cell refinement: X-AREA (Stoe & Cie, 2009) for (I), (III); CELL in IPDS I Bedienungshandbuch (Stoe & Cie, 2004) for (II). Data reduction: X-RED32 (Stoe & Cie, 2009) for (I), (III); INTEGRATE in IPDS I Bedienungshandbuch (Stoe & Cie, 2004) for (II). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures

Fig. 1. A view of the molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Fig. 2. A view, along the c axis, of the crystal packing of (I). O—H···O and N—H···O hydrogen bonds are shown as dashed lines (see Table 1 for details). H atoms not involved in these interactions have been omitted for clarity. Fig. 3. A view of the molecular structure of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Fig. 4. A view, along the c axis, of the crystal packing of (II). O—H···O and N—H···O hydrogen bonds are shown as dashed lines (see Table 2 for details). H atoms not involved in these interactions have been omitted for clarity. Fig. 5. A view of the molecular structure of (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Fig. 6. A view, along the c axis, of the crystal packing of (III). O—H···O and N—H···O hydrogen bonds and C—H···O interactions are shown as dashed lines (see Table 3 for details). H atoms not involved in these interactions have been omitted for clarity.

(I) (E)-N'-(4-Chlorobenzylidene)-4-hydroxybenzohydrazide

Crystal data

C14H11ClN2O2	F(000) = 568
Mr = 274.70	Dx = 1.464 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5627 reflections
a = 7.4201 (6) Å	θ = 1.7–26.1°
b = 24.1098 (14) Å	µ = 0.31 mm^−1
c = 7.8614 (6) Å	T = 173 K
β = 117.566 (6)°	Plate, colourless
V = 1246.73 (16) Å^3	0.40 × 0.27 × 0.05 mm
Z = 4

Data collection

Stoe IPDS II diffractometer	2336 independent reflections
Radiation source: fine-focus sealed tube	1698 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.060
ϕ and ω scans	θmax = 25.6°, θmin = 1.7°
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009)	h = −8→9
Tmin = 0.879, Tmax = 1.000	k = −26→29
7727 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.054P)^2] where P = (Fo^2 + 2Fc^2)/3
2336 reflections	(Δ/σ)max < 0.001
180 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.90972 (10)	0.01847 (3)	1.18343 (9)	0.0485 (2)
O1	0.1887 (2)	0.31605 (6)	0.56250 (19)	0.0288 (5)
O2	−0.5023 (2)	0.39208 (7)	−0.2418 (2)	0.0334 (5)
N1	0.1759 (3)	0.23805 (8)	0.3947 (2)	0.0262 (5)
N2	0.3041 (3)	0.20974 (7)	0.5612 (2)	0.0262 (5)
C1	−0.0290 (3)	0.31607 (9)	0.2243 (3)	0.0237 (6)
C2	−0.0411 (3)	0.37364 (9)	0.2069 (3)	0.0268 (6)
C3	−0.1951 (3)	0.39843 (9)	0.0461 (3)	0.0293 (6)
C4	−0.3424 (3)	0.36553 (9)	−0.0969 (3)	0.0268 (6)
C5	−0.3281 (3)	0.30811 (9)	−0.0849 (3)	0.0281 (7)
C6	−0.1714 (3)	0.28392 (9)	0.0757 (3)	0.0270 (6)
C7	0.1238 (3)	0.29075 (9)	0.4069 (3)	0.0246 (6)
C8	0.3126 (3)	0.15750 (9)	0.5409 (3)	0.0270 (6)
C9	0.4511 (3)	0.12285 (9)	0.7012 (3)	0.0273 (7)
C10	0.5956 (3)	0.14712 (9)	0.8705 (3)	0.0311 (7)
C11	0.7362 (3)	0.11509 (10)	1.0174 (3)	0.0335 (7)
C12	0.7304 (3)	0.05841 (10)	0.9964 (3)	0.0309 (7)
C13	0.5869 (4)	0.03248 (9)	0.8322 (3)	0.0372 (7)
C14	0.4478 (3)	0.06551 (9)	0.6846 (3)	0.0341 (7)
H1N	0.156 (4)	0.2231 (11)	0.282 (4)	0.049 (8)*
H2	0.05680	0.39610	0.30580	0.0320*
H2O	−0.590 (5)	0.3679 (13)	−0.309 (4)	0.067 (10)*
H3	−0.20030	0.43770	0.03330	0.0350*
H5	−0.42430	0.28570	−0.18520	0.0340*
H6	−0.16110	0.24460	0.08430	0.0320*
H8	0.22810	0.14090	0.42040	0.0320*
H10	0.59730	0.18630	0.88490	0.0370*
H11	0.83570	0.13200	1.13150	0.0400*
H13	0.58350	−0.00680	0.82060	0.0450*
H14	0.34880	0.04850	0.57040	0.0410*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0508 (4)	0.0384 (4)	0.0449 (4)	0.0163 (3)	0.0126 (3)	0.0144 (3)
O1	0.0294 (8)	0.0264 (8)	0.0249 (8)	0.0002 (6)	0.0078 (7)	−0.0029 (6)
O2	0.0295 (8)	0.0269 (8)	0.0325 (8)	0.0024 (7)	0.0047 (7)	0.0052 (7)
N1	0.0267 (9)	0.0262 (10)	0.0228 (9)	0.0062 (8)	0.0090 (8)	0.0026 (8)
N2	0.0257 (9)	0.0273 (10)	0.0245 (9)	0.0053 (8)	0.0106 (7)	0.0049 (7)
C1	0.0231 (10)	0.0246 (11)	0.0252 (10)	0.0003 (8)	0.0126 (9)	−0.0001 (8)
C2	0.0251 (11)	0.0250 (11)	0.0282 (11)	−0.0028 (8)	0.0105 (9)	−0.0022 (8)
C3	0.0316 (11)	0.0215 (11)	0.0343 (11)	−0.0003 (9)	0.0148 (10)	0.0026 (9)
C4	0.0242 (10)	0.0282 (12)	0.0254 (10)	0.0030 (9)	0.0093 (9)	0.0052 (9)
C5	0.0260 (11)	0.0267 (12)	0.0274 (11)	0.0000 (9)	0.0087 (9)	−0.0011 (9)
C6	0.0268 (11)	0.0202 (11)	0.0306 (11)	0.0018 (9)	0.0104 (9)	−0.0005 (8)
C7	0.0211 (10)	0.0268 (12)	0.0257 (10)	−0.0012 (9)	0.0106 (9)	0.0009 (9)
C8	0.0231 (10)	0.0276 (12)	0.0293 (11)	0.0007 (9)	0.0112 (9)	−0.0007 (9)
C9	0.0242 (11)	0.0274 (12)	0.0307 (11)	0.0006 (9)	0.0130 (9)	0.0030 (9)
C10	0.0361 (12)	0.0208 (11)	0.0313 (11)	0.0006 (10)	0.0114 (10)	−0.0008 (9)
C11	0.0318 (12)	0.0296 (13)	0.0311 (11)	0.0027 (10)	0.0077 (10)	0.0028 (10)
C12	0.0302 (12)	0.0298 (13)	0.0329 (12)	0.0055 (10)	0.0147 (10)	0.0080 (9)
C13	0.0432 (13)	0.0211 (12)	0.0436 (13)	0.0022 (10)	0.0170 (12)	0.0012 (10)
C14	0.0321 (12)	0.0268 (12)	0.0367 (12)	−0.0020 (10)	0.0103 (10)	−0.0009 (10)

Geometric parameters (Å, º)

Cl1—C12	1.746 (2)	C9—C14	1.388 (3)
O1—C7	1.247 (3)	C9—C10	1.394 (3)
O2—C4	1.365 (3)	C10—C11	1.380 (3)
O2—H2O	0.85 (3)	C11—C12	1.375 (3)
N1—N2	1.390 (2)	C12—C13	1.385 (3)
N1—C7	1.344 (3)	C13—C14	1.392 (3)
N2—C8	1.275 (3)	C2—H2	0.9500
N1—H1N	0.90 (3)	C3—H3	0.9500
C1—C7	1.487 (3)	C5—H5	0.9500
C1—C6	1.393 (3)	C6—H6	0.9500
C1—C2	1.394 (3)	C8—H8	0.9500
C2—C3	1.387 (3)	C10—H10	0.9500
C3—C4	1.397 (3)	C11—H11	0.9500
C4—C5	1.388 (3)	C13—H13	0.9500
C5—C6	1.388 (3)	C14—H14	0.9500
C8—C9	1.464 (3)
C4—O2—H2O	108 (2)	Cl1—C12—C13	119.57 (18)
N2—N1—C7	119.41 (16)	Cl1—C12—C11	118.54 (17)
N1—N2—C8	114.79 (16)	C11—C12—C13	121.9 (2)
N2—N1—H1N	117.3 (18)	C12—C13—C14	118.2 (2)
C7—N1—H1N	121.7 (17)	C9—C14—C13	121.2 (2)
C2—C1—C6	118.9 (2)	C1—C2—H2	120.00
C2—C1—C7	119.29 (19)	C3—C2—H2	120.00
C6—C1—C7	121.65 (19)	C2—C3—H3	120.00
C1—C2—C3	120.5 (2)	C4—C3—H3	120.00
C2—C3—C4	119.8 (2)	C4—C5—H5	120.00
O2—C4—C3	117.36 (19)	C6—C5—H5	120.00
O2—C4—C5	122.3 (2)	C1—C6—H6	119.00
C3—C4—C5	120.3 (2)	C5—C6—H6	119.00
C4—C5—C6	119.1 (2)	N2—C8—H8	120.00
C1—C6—C5	121.3 (2)	C9—C8—H8	120.00
N1—C7—C1	115.78 (18)	C9—C10—H10	120.00
O1—C7—C1	121.5 (2)	C11—C10—H10	120.00
O1—C7—N1	122.62 (19)	C10—C11—H11	120.00
N2—C8—C9	120.78 (19)	C12—C11—H11	120.00
C8—C9—C10	120.38 (19)	C12—C13—H13	121.00
C8—C9—C14	120.84 (19)	C14—C13—H13	121.00
C10—C9—C14	118.7 (2)	C9—C14—H14	119.00
C9—C10—C11	120.9 (2)	C13—C14—H14	119.00
C10—C11—C12	119.1 (2)
C7—N1—N2—C8	166.6 (2)	O2—C4—C5—C6	−174.0 (2)
N2—N1—C7—O1	1.2 (4)	C3—C4—C5—C6	3.2 (4)
N2—N1—C7—C1	−174.4 (2)	C4—C5—C6—C1	0.0 (4)
N1—N2—C8—C9	176.1 (2)	N2—C8—C9—C10	−8.9 (4)
C6—C1—C2—C3	1.4 (4)	N2—C8—C9—C14	174.2 (2)
C7—C1—C2—C3	−173.5 (2)	C8—C9—C10—C11	−175.4 (2)
C2—C1—C6—C5	−2.3 (4)	C14—C9—C10—C11	1.6 (4)
C7—C1—C6—C5	172.4 (2)	C8—C9—C14—C13	176.2 (2)
C2—C1—C7—O1	26.1 (4)	C10—C9—C14—C13	−0.8 (4)
C2—C1—C7—N1	−158.2 (2)	C9—C10—C11—C12	−1.1 (4)
C6—C1—C7—O1	−148.6 (2)	C10—C11—C12—Cl1	179.9 (2)
C6—C1—C7—N1	27.1 (3)	C10—C11—C12—C13	−0.3 (4)
C1—C2—C3—C4	1.8 (4)	Cl1—C12—C13—C14	−179.1 (2)
C2—C3—C4—O2	173.2 (2)	C11—C12—C13—C14	1.0 (4)
C2—C3—C4—C5	−4.2 (4)	C12—C13—C14—C9	−0.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.90 (3)	2.08 (3)	2.960 (2)	165 (3)
O2—H2O···O1^ii	0.85 (3)	1.94 (3)	2.778 (2)	171 (3)
C13—H13···O2^iii	0.95	2.52	3.456 (3)	169

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

(II) (E)-N'-(4-Bromobenzylidene)-4-hydroxybenzohydrazide

Crystal data

C14H11BrN2O2	F(000) = 640
Mr = 319.16	Dx = 1.655 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6613 reflections
a = 7.6046 (7) Å	θ = 2.5–26.0°
b = 24.2250 (18) Å	µ = 3.21 mm^−1
c = 7.9230 (7) Å	T = 293 K
β = 118.673 (9)°	Rod, colourless
V = 1280.60 (19) Å^3	0.42 × 0.27 × 0.23 mm
Z = 4

Data collection

Stoe IPDS I diffractometer	2509 independent reflections
Radiation source: fine-focus sealed tube	1626 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
ϕ rotation scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009)	h = −9→9
Tmin = 0.783, Tmax = 1.000	k = −29→29
10103 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0383P)^2] where P = (Fo^2 + 2Fc^2)/3
2509 reflections	(Δ/σ)max < 0.001
180 parameters	Δρmax = 0.45 e Å^−3
2 restraints	Δρmin = −0.46 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.91542 (6)	0.01798 (1)	1.19850 (5)	0.0724 (1)
O1	0.1703 (3)	0.31403 (7)	0.5594 (3)	0.0440 (6)
O2	−0.5204 (3)	0.38918 (9)	−0.2416 (3)	0.0520 (7)
N1	0.1521 (3)	0.23619 (10)	0.3944 (3)	0.0394 (7)
N2	0.2816 (3)	0.20835 (9)	0.5592 (3)	0.0380 (7)
C1	−0.0515 (4)	0.31330 (10)	0.2231 (4)	0.0338 (8)
C2	−0.0637 (4)	0.37043 (11)	0.2042 (4)	0.0391 (8)
C3	−0.2154 (4)	0.39459 (11)	0.0444 (4)	0.0455 (9)
C4	−0.3638 (4)	0.36263 (11)	−0.0976 (4)	0.0384 (8)
C5	−0.3507 (4)	0.30585 (11)	−0.0841 (4)	0.0413 (9)
C6	−0.1950 (4)	0.28173 (11)	0.0758 (4)	0.0406 (8)
C7	0.1012 (4)	0.28873 (11)	0.4048 (4)	0.0349 (8)
C8	0.2956 (4)	0.15655 (11)	0.5400 (4)	0.0398 (9)
C9	0.4356 (4)	0.12286 (11)	0.7001 (4)	0.0375 (8)
C10	0.5727 (4)	0.14700 (12)	0.8713 (4)	0.0479 (9)
C11	0.7139 (5)	0.11593 (12)	1.0172 (4)	0.0516 (10)
C12	0.7165 (4)	0.05989 (11)	0.9937 (4)	0.0461 (10)
C13	0.5815 (5)	0.03438 (12)	0.8286 (4)	0.0542 (11)
C14	0.4415 (5)	0.06631 (12)	0.6821 (5)	0.0530 (10)
H1N	0.123 (4)	0.2219 (11)	0.288 (3)	0.043 (9)*
H2	0.03210	0.39240	0.30080	0.0470*
H2O	−0.595 (4)	0.3659 (10)	−0.308 (4)	0.049 (10)*
H3	−0.21900	0.43280	0.03100	0.0550*
H5	−0.44580	0.28400	−0.18180	0.0500*
H6	−0.18650	0.24340	0.08460	0.0490*
H8	0.21470	0.14000	0.42160	0.0480*
H10	0.56860	0.18490	0.88730	0.0570*
H11	0.80710	0.13260	1.13100	0.0620*
H13	0.58400	−0.00370	0.81530	0.0650*
H14	0.34880	0.04940	0.56850	0.0640*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0706 (2)	0.0577 (2)	0.0638 (2)	0.0230 (2)	0.0120 (2)	0.0203 (2)
O1	0.0452 (11)	0.0426 (10)	0.0282 (10)	0.0005 (9)	0.0049 (9)	−0.0044 (9)
O2	0.0457 (12)	0.0423 (12)	0.0421 (12)	0.0050 (10)	0.0002 (10)	0.0085 (10)
N1	0.0429 (13)	0.0398 (13)	0.0261 (12)	0.0103 (11)	0.0090 (11)	0.0022 (11)
N2	0.0357 (12)	0.0402 (13)	0.0304 (12)	0.0070 (10)	0.0097 (10)	0.0074 (10)
C1	0.0323 (15)	0.0346 (13)	0.0284 (14)	0.0009 (11)	0.0098 (12)	0.0013 (11)
C2	0.0352 (14)	0.0351 (13)	0.0346 (15)	−0.0056 (12)	0.0067 (12)	−0.0025 (12)
C3	0.0457 (16)	0.0308 (14)	0.0493 (18)	−0.0006 (12)	0.0143 (14)	0.0064 (13)
C4	0.0344 (14)	0.0393 (15)	0.0329 (15)	0.0021 (12)	0.0093 (12)	0.0050 (12)
C5	0.0367 (15)	0.0378 (15)	0.0347 (15)	0.0018 (12)	0.0053 (13)	−0.0022 (12)
C6	0.0403 (15)	0.0312 (13)	0.0382 (16)	0.0001 (12)	0.0091 (13)	−0.0035 (12)
C7	0.0328 (14)	0.0354 (14)	0.0326 (15)	−0.0016 (11)	0.0126 (12)	0.0015 (12)
C8	0.0349 (15)	0.0399 (16)	0.0361 (16)	0.0016 (12)	0.0103 (13)	−0.0003 (12)
C9	0.0353 (14)	0.0364 (13)	0.0356 (15)	0.0030 (12)	0.0129 (12)	0.0065 (12)
C10	0.0522 (18)	0.0337 (14)	0.0410 (17)	0.0043 (13)	0.0089 (15)	0.0019 (13)
C11	0.0523 (18)	0.0459 (17)	0.0375 (17)	0.0010 (14)	0.0062 (14)	−0.0002 (14)
C12	0.0451 (17)	0.0404 (16)	0.0500 (19)	0.0075 (13)	0.0207 (15)	0.0098 (14)
C13	0.060 (2)	0.0307 (14)	0.057 (2)	0.0046 (14)	0.0162 (17)	0.0049 (14)
C14	0.0520 (18)	0.0381 (15)	0.0510 (19)	−0.0031 (14)	0.0104 (15)	−0.0024 (15)

Geometric parameters (Å, º)

Br1—C12	1.897 (3)	C9—C14	1.380 (4)
O1—C7	1.239 (3)	C9—C10	1.383 (4)
O2—C4	1.353 (4)	C10—C11	1.366 (4)
O2—H2O	0.79 (3)	C11—C12	1.372 (4)
N1—N2	1.377 (3)	C12—C13	1.363 (4)
N1—C7	1.344 (4)	C13—C14	1.376 (5)
N2—C8	1.275 (3)	C2—H2	0.9300
N1—H1N	0.84 (2)	C3—H3	0.9300
C1—C7	1.473 (4)	C5—H5	0.9300
C1—C6	1.384 (4)	C6—H6	0.9300
C1—C2	1.390 (4)	C8—H8	0.9300
C2—C3	1.369 (4)	C10—H10	0.9300
C3—C4	1.386 (4)	C11—H11	0.9300
C4—C5	1.380 (4)	C13—H13	0.9300
C5—C6	1.382 (4)	C14—H14	0.9300
C8—C9	1.454 (4)
C4—O2—H2O	106 (2)	Br1—C12—C13	120.2 (2)
N2—N1—C7	120.1 (2)	Br1—C12—C11	118.1 (2)
N1—N2—C8	115.6 (2)	C11—C12—C13	121.7 (3)
N2—N1—H1N	118.4 (19)	C12—C13—C14	118.4 (3)
C7—N1—H1N	120.6 (18)	C9—C14—C13	121.4 (3)
C2—C1—C6	118.3 (3)	C1—C2—H2	120.00
C2—C1—C7	119.2 (2)	C3—C2—H2	120.00
C6—C1—C7	122.3 (2)	C2—C3—H3	120.00
C1—C2—C3	120.5 (3)	C4—C3—H3	120.00
C2—C3—C4	120.6 (3)	C4—C5—H5	120.00
O2—C4—C3	117.6 (2)	C6—C5—H5	120.00
O2—C4—C5	122.8 (3)	C1—C6—H6	119.00
C3—C4—C5	119.6 (3)	C5—C6—H6	119.00
C4—C5—C6	119.4 (3)	N2—C8—H8	119.00
C1—C6—C5	121.4 (2)	C9—C8—H8	119.00
N1—C7—C1	116.0 (2)	C9—C10—H10	120.00
O1—C7—C1	121.9 (2)	C11—C10—H10	120.00
O1—C7—N1	122.1 (3)	C10—C11—H11	120.00
N2—C8—C9	121.1 (3)	C12—C11—H11	120.00
C8—C9—C10	120.7 (2)	C12—C13—H13	121.00
C8—C9—C14	120.9 (3)	C14—C13—H13	121.00
C10—C9—C14	118.3 (3)	C9—C14—H14	119.00
C9—C10—C11	120.9 (3)	C13—C14—H14	119.00
C10—C11—C12	119.2 (3)
C7—N1—N2—C8	169.0 (3)	O2—C4—C5—C6	−174.4 (3)
N2—N1—C7—O1	1.4 (5)	C3—C4—C5—C6	3.2 (5)
N2—N1—C7—C1	−174.9 (3)	C4—C5—C6—C1	0.0 (5)
N1—N2—C8—C9	176.4 (3)	N2—C8—C9—C10	−7.2 (5)
C6—C1—C2—C3	0.7 (5)	N2—C8—C9—C14	175.9 (3)
C7—C1—C2—C3	−173.9 (3)	C8—C9—C10—C11	−175.3 (3)
C2—C1—C6—C5	−1.9 (5)	C14—C9—C10—C11	1.7 (5)
C7—C1—C6—C5	172.5 (3)	C8—C9—C14—C13	176.0 (4)
C2—C1—C7—O1	25.6 (5)	C10—C9—C14—C13	−1.0 (6)
C2—C1—C7—N1	−158.2 (3)	C9—C10—C11—C12	−1.2 (5)
C6—C1—C7—O1	−148.8 (3)	C10—C11—C12—Br1	179.7 (3)
C6—C1—C7—N1	27.5 (5)	C10—C11—C12—C13	−0.1 (6)
C1—C2—C3—C4	2.6 (5)	Br1—C12—C13—C14	−179.0 (3)
C2—C3—C4—O2	173.2 (3)	C11—C12—C13—C14	0.8 (6)
C2—C3—C4—C5	−4.6 (5)	C12—C13—C14—C9	−0.2 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.84 (2)	2.19 (3)	2.983 (3)	158 (3)
O2—H2O···O1^ii	0.79 (3)	2.02 (3)	2.788 (3)	164 (3)

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

(III) (E)-N'-[4-(Diethylamino)benzylidene]-4-hydroxybenzohydrazide

Crystal data

C18H21N3O2	F(000) = 664
Mr = 311.38	Dx = 1.218 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7297 reflections
a = 14.8338 (10) Å	θ = 1.4–26.1°
b = 12.4571 (11) Å	µ = 0.08 mm^−1
c = 9.2935 (6) Å	T = 173 K
β = 98.687 (5)°	Rod, pale yellow
V = 1697.6 (2) Å^3	0.45 × 0.28 × 0.10 mm
Z = 4

Data collection

Stoe IPDS II diffractometer	3199 independent reflections
Radiation source: fine-focus sealed tube	2183 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.084
ϕ and ω scans	θmax = 25.6°, θmin = 1.4°
Absorption correction: multi-scan (MULABS in PLATON; Spek, 2009)	h = −18→16
Tmin = 0.868, Tmax = 1.000	k = −15→15
15142 measured reflections	l = −10→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0447P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3199 reflections	Δρmax = 0.17 e Å^−3
219 parameters	Δρmin = −0.17 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0104 (15)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. The OH and NH H atoms were located in a difference electron-density map and were freely refined. The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95, 0.98, and 0.99 Å for CH (aromatic), CH₃, and CH₂ H atoms, respectively, with U_iso(H) = kU_eq(parent C atom), where k = 1.5 for CH₃ H atoms and k = 1.2 for all other H atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.37129 (10)	0.68546 (10)	0.38111 (15)	0.0282 (5)
O2	0.68902 (9)	0.43456 (11)	0.13423 (16)	0.0269 (5)
N1	0.32947 (11)	0.71351 (12)	0.13930 (19)	0.0216 (5)
N2	0.25433 (11)	0.77393 (12)	0.16470 (18)	0.0221 (5)
N22	−0.15693 (12)	0.95604 (13)	0.1157 (2)	0.0348 (6)
C1	0.46596 (13)	0.61330 (14)	0.2188 (2)	0.0204 (6)
C2	0.49401 (13)	0.52351 (15)	0.3038 (2)	0.0231 (6)
C3	0.56761 (13)	0.46261 (15)	0.2779 (2)	0.0237 (6)
C4	0.61606 (13)	0.49196 (14)	0.1666 (2)	0.0208 (6)
C5	0.58960 (13)	0.58214 (14)	0.0819 (2)	0.0237 (6)
C6	0.51494 (13)	0.64178 (15)	0.1072 (2)	0.0225 (6)
C7	0.38654 (13)	0.67424 (14)	0.2546 (2)	0.0194 (6)
C8	0.18532 (13)	0.77041 (15)	0.0636 (2)	0.0235 (6)
C9	0.09977 (13)	0.82317 (14)	0.0758 (2)	0.0232 (6)
C10	0.08837 (14)	0.89382 (15)	0.1890 (2)	0.0252 (6)
C11	0.00461 (14)	0.93608 (15)	0.2029 (2)	0.0282 (7)
C12	−0.07410 (14)	0.91120 (15)	0.1033 (2)	0.0266 (6)
C13	−0.06237 (14)	0.84009 (16)	−0.0101 (3)	0.0331 (7)
C14	0.02219 (14)	0.79891 (16)	−0.0234 (2)	0.0313 (7)
C15	−0.16867 (17)	1.02374 (18)	0.2394 (3)	0.0466 (9)
C16	−0.1747 (2)	0.9610 (3)	0.3783 (3)	0.0738 (12)
C17	−0.23686 (15)	0.93648 (18)	0.0067 (3)	0.0441 (8)
C18	−0.28938 (19)	0.8349 (2)	0.0302 (4)	0.0685 (13)
H1N	0.3387 (15)	0.7028 (17)	0.050 (3)	0.036 (6)*
H2	0.46180	0.50400	0.38080	0.0280*
H2O	0.704 (2)	0.381 (2)	0.203 (3)	0.068 (9)*
H3	0.58520	0.40100	0.33570	0.0280*
H5	0.62290	0.60270	0.00670	0.0290*
H6	0.49670	0.70260	0.04820	0.0270*
H8	0.19050	0.73160	−0.02280	0.0280*
H10	0.13990	0.91300	0.25790	0.0300*
H11	−0.00040	0.98330	0.28150	0.0340*
H13	−0.11370	0.82010	−0.07880	0.0400*
H14	0.02780	0.75250	−0.10260	0.0380*
H15A	−0.22500	1.06670	0.21410	0.0560*
H15B	−0.11670	1.07430	0.25790	0.0560*
H16A	−0.11820	0.92040	0.40650	0.1110*
H16B	−0.22640	0.91120	0.36130	0.1110*
H16C	−0.18350	1.01090	0.45650	0.1110*
H17A	−0.21700	0.93250	−0.09020	0.0530*
H17B	−0.27860	0.99860	0.00560	0.0530*
H18A	−0.24850	0.77290	0.03380	0.1030*
H18B	−0.33970	0.82600	−0.05020	0.1030*
H18C	−0.31380	0.84030	0.12220	0.1030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0318 (8)	0.0329 (8)	0.0207 (8)	0.0077 (6)	0.0067 (7)	−0.0007 (6)
O2	0.0232 (8)	0.0293 (8)	0.0297 (8)	0.0084 (6)	0.0091 (7)	0.0052 (6)
N1	0.0194 (9)	0.0256 (8)	0.0202 (9)	0.0044 (7)	0.0046 (8)	−0.0003 (7)
N2	0.0184 (9)	0.0232 (8)	0.0255 (9)	0.0005 (7)	0.0064 (8)	0.0013 (7)
N22	0.0216 (10)	0.0315 (9)	0.0523 (12)	0.0072 (8)	0.0085 (9)	0.0036 (9)
C1	0.0182 (10)	0.0211 (9)	0.0211 (10)	−0.0006 (8)	0.0006 (8)	−0.0011 (8)
C2	0.0206 (10)	0.0295 (10)	0.0196 (10)	0.0000 (8)	0.0044 (9)	0.0014 (8)
C3	0.0239 (11)	0.0247 (10)	0.0222 (11)	0.0017 (8)	0.0027 (9)	0.0027 (8)
C4	0.0163 (10)	0.0238 (10)	0.0221 (10)	0.0004 (8)	0.0023 (9)	−0.0047 (8)
C5	0.0217 (11)	0.0266 (10)	0.0243 (11)	−0.0023 (8)	0.0079 (9)	0.0045 (8)
C6	0.0219 (11)	0.0217 (9)	0.0240 (11)	0.0005 (8)	0.0035 (9)	0.0026 (8)
C7	0.0200 (10)	0.0172 (9)	0.0211 (11)	−0.0036 (7)	0.0035 (9)	−0.0012 (8)
C8	0.0243 (11)	0.0233 (10)	0.0233 (11)	0.0009 (8)	0.0050 (9)	0.0003 (8)
C9	0.0199 (11)	0.0221 (9)	0.0277 (11)	0.0009 (8)	0.0044 (9)	0.0014 (8)
C10	0.0240 (11)	0.0251 (10)	0.0261 (11)	0.0012 (8)	0.0024 (9)	0.0004 (8)
C11	0.0289 (12)	0.0259 (10)	0.0311 (12)	0.0049 (9)	0.0084 (10)	−0.0009 (9)
C12	0.0229 (11)	0.0212 (10)	0.0368 (12)	0.0025 (8)	0.0083 (10)	0.0078 (8)
C13	0.0211 (11)	0.0324 (11)	0.0434 (14)	0.0029 (9)	−0.0024 (10)	−0.0034 (10)
C14	0.0282 (12)	0.0296 (11)	0.0358 (13)	0.0007 (9)	0.0037 (10)	−0.0059 (9)
C15	0.0364 (14)	0.0405 (13)	0.0664 (18)	0.0171 (11)	0.0188 (14)	−0.0057 (12)
C16	0.082 (2)	0.080 (2)	0.070 (2)	0.0156 (18)	0.046 (2)	−0.0014 (17)
C17	0.0222 (12)	0.0361 (12)	0.0726 (19)	0.0045 (10)	0.0031 (13)	0.0070 (12)
C18	0.0394 (16)	0.0489 (16)	0.115 (3)	−0.0101 (13)	0.0048 (17)	0.0098 (16)

Geometric parameters (Å, º)

O1—C7	1.238 (2)	C13—C14	1.378 (3)
O2—C4	1.368 (2)	C15—C16	1.523 (4)
O2—H2O	0.93 (3)	C17—C18	1.519 (3)
N1—C7	1.353 (3)	C2—H2	0.9500
N1—N2	1.394 (2)	C3—H3	0.9500
N2—C8	1.281 (3)	C5—H5	0.9500
N22—C12	1.370 (3)	C6—H6	0.9500
N22—C17	1.459 (3)	C8—H8	0.9500
N22—C15	1.457 (3)	C10—H10	0.9500
N1—H1N	0.87 (3)	C11—H11	0.9500
C1—C2	1.396 (3)	C13—H13	0.9500
C1—C7	1.481 (3)	C14—H14	0.9500
C1—C6	1.399 (3)	C15—H15A	0.9900
C2—C3	1.380 (3)	C15—H15B	0.9900
C3—C4	1.395 (3)	C16—H16A	0.9800
C4—C5	1.394 (3)	C16—H16B	0.9800
C5—C6	1.383 (3)	C16—H16C	0.9800
C8—C9	1.449 (3)	C17—H17A	0.9900
C9—C10	1.401 (3)	C17—H17B	0.9900
C9—C14	1.395 (3)	C18—H18A	0.9800
C10—C11	1.373 (3)	C18—H18B	0.9800
C11—C12	1.411 (3)	C18—H18C	0.9800
C12—C13	1.408 (3)
C4—O2—H2O	109.9 (18)	C4—C3—H3	120.00
N2—N1—C7	118.80 (16)	C4—C5—H5	120.00
N1—N2—C8	115.33 (16)	C6—C5—H5	120.00
C12—N22—C17	121.23 (17)	C1—C6—H6	120.00
C15—N22—C17	117.58 (18)	C5—C6—H6	120.00
C12—N22—C15	121.18 (18)	N2—C8—H8	119.00
C7—N1—H1N	122.0 (15)	C9—C8—H8	119.00
N2—N1—H1N	119.2 (15)	C9—C10—H10	119.00
C2—C1—C6	118.61 (17)	C11—C10—H10	119.00
C2—C1—C7	117.57 (17)	C10—C11—H11	119.00
C6—C1—C7	123.81 (16)	C12—C11—H11	119.00
C1—C2—C3	121.18 (17)	C12—C13—H13	119.00
C2—C3—C4	119.68 (17)	C14—C13—H13	119.00
C3—C4—C5	119.84 (17)	C9—C14—H14	119.00
O2—C4—C3	122.65 (16)	C13—C14—H14	119.00
O2—C4—C5	117.50 (17)	N22—C15—H15A	109.00
C4—C5—C6	120.10 (17)	N22—C15—H15B	109.00
C1—C6—C5	120.58 (17)	C16—C15—H15A	109.00
O1—C7—N1	121.94 (18)	C16—C15—H15B	109.00
N1—C7—C1	115.55 (16)	H15A—C15—H15B	108.00
O1—C7—C1	122.46 (17)	C15—C16—H16A	110.00
N2—C8—C9	122.64 (17)	C15—C16—H16B	109.00
C8—C9—C14	119.67 (17)	C15—C16—H16C	110.00
C8—C9—C10	123.38 (17)	H16A—C16—H16B	109.00
C10—C9—C14	116.83 (18)	H16A—C16—H16C	109.00
C9—C10—C11	121.66 (18)	H16B—C16—H16C	109.00
C10—C11—C12	121.67 (17)	N22—C17—H17A	109.00
C11—C12—C13	116.49 (19)	N22—C17—H17B	109.00
N22—C12—C11	121.27 (17)	C18—C17—H17A	109.00
N22—C12—C13	122.23 (18)	C18—C17—H17B	109.00
C12—C13—C14	121.2 (2)	H17A—C17—H17B	108.00
C9—C14—C13	122.11 (19)	C17—C18—H18A	109.00
N22—C15—C16	113.6 (2)	C17—C18—H18B	109.00
N22—C17—C18	114.8 (2)	C17—C18—H18C	109.00
C1—C2—H2	119.00	H18A—C18—H18B	109.00
C3—C2—H2	119.00	H18A—C18—H18C	109.00
C2—C3—H3	120.00	H18B—C18—H18C	110.00
C7—N1—N2—C8	−151.69 (17)	C6—C1—C7—N1	38.6 (3)
N2—N1—C7—O1	4.0 (3)	C1—C2—C3—C4	1.1 (3)
N2—N1—C7—C1	−178.50 (15)	C2—C3—C4—O2	−179.31 (17)
N1—N2—C8—C9	176.26 (16)	C2—C3—C4—C5	−0.3 (3)
C15—N22—C12—C11	−5.5 (3)	O2—C4—C5—C6	178.40 (17)
C15—N22—C12—C13	175.8 (2)	C3—C4—C5—C6	−0.6 (3)
C17—N22—C12—C11	175.44 (18)	C4—C5—C6—C1	0.8 (3)
C17—N22—C12—C13	−3.2 (3)	N2—C8—C9—C10	8.8 (3)
C12—N22—C15—C16	−76.9 (3)	N2—C8—C9—C14	−167.07 (18)
C17—N22—C15—C16	102.2 (2)	C8—C9—C10—C11	−175.07 (18)
C12—N22—C17—C18	85.6 (3)	C14—C9—C10—C11	0.9 (3)
C15—N22—C17—C18	−93.5 (2)	C8—C9—C14—C13	174.72 (19)
C6—C1—C2—C3	−0.9 (3)	C10—C9—C14—C13	−1.4 (3)
C7—C1—C2—C3	−179.77 (17)	C9—C10—C11—C12	−0.5 (3)
C2—C1—C6—C5	0.0 (3)	C10—C11—C12—N22	−178.18 (18)
C7—C1—C6—C5	178.71 (18)	C10—C11—C12—C13	0.6 (3)
C2—C1—C7—O1	34.9 (3)	N22—C12—C13—C14	177.67 (19)
C2—C1—C7—N1	−142.64 (18)	C11—C12—C13—C14	−1.1 (3)
C6—C1—C7—O1	−143.90 (19)	C12—C13—C14—C9	1.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1^i	0.87 (3)	2.21 (2)	2.859 (2)	131.6 (18)
N1—H1N···O2^ii	0.87 (3)	2.41 (2)	3.119 (2)	138.6 (19)
O2—H2O···N2^iii	0.93 (3)	1.86 (3)	2.780 (2)	174 (3)
C10—H10···O2^iv	0.95	2.60	3.496 (2)	158

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