Three N²-benzoyl­oxybenz­amidines: sheet structures built from hard and soft hydrogen bonds and aromatic [pi]-[pi] stacking interactions

Molecules of the title compounds N²-(benzoyl­oxy)­benz­ami­dine, C₁₄H₁₂N₂O₂, (I), N²-(2-hydroxy­benzoyl­oxy)­benz­ami­dine, C₁₄H₁₂N₂O₃, (II), and N²-benzoyloxy-2-hydroxybenzamidine, C₁₄H₁₂N₂O₃, (III), all have extended chain conformations, with the aryl groups remote from one another. In (I), the mol­ecules are linked into chains by a single N-H...N hydrogen bond [H...N = 2.15 Å, N...N = 3.029 (2) Å and N-H...N = 153°] and these chains are linked into sheets by means of aromatic [pi]-[pi] stacking interactions. There is one intramolecular O-H...O hydrogen bond in (II), and a combination of one three-centre N-H...(N,O) hydrogen bond [H...N = 2.46 Å, H...O = 2.31 Å, N...N = 3.190 (2) Å, N...O = 3.146 (2) Å, N-H...N = 138° and N-H...O = 154°] and one two-centre C-H...O hydrogen bond [H...O = 2.46 Å, C...O = 3.405 (2) Å and C-H...O = 173°] links the mol­ecules into sheets. In (III), an intramolecular O-H...N hydrogen bond and two N-H...O hydrogen bonds [H...O = 2.26 and 2.10 Å, N...O = 2.975 (2) and 2.954 (2) Å, and N-H...O = 138 and 163°] link the molecules into sheets.

S1. Comment

Acyloxyarylamidines, Ar¹C(O)ON=C(NH₂)Ar², can in principle adopt a wide range of conformations, depending on both the configuration at the C═N double bond, and the rotational freedom about the C—O and N—O single bonds. On the basis of ab initio calculations on the simple model compound HC(O)ON=CHNH₂ and qualitative estimates of 1,4 interactions in the aryl analogues Ar¹C(O)ON=C(NH₂)Ar², it has been suggested (Tucker et al., 2000) that the two most stable conformers, at least in the vapour phase, are those with chain-extended C(Ar)—C—O—N=C—C(Ar) spacer units. Consistent with this prediction, the structures of three derivatives [Ar¹ is 1-naphthyl and Ar² is 2-methylphenyl, Cambridge Structural Database (CSD; Allen, 2002) refcode QUNMER; Ar¹ is 1-naphthyl and Ar² is 2,6-dichlorophenyl, CSD refcode QUNMOB; Ar¹ is 2-methylphenyl and Ar² is 2,4-dichlorophenyl, CSD refcode QUNMIV] were all found to adopt nearly planar chain-extended conformations, with the aryl groups remote from one another. In this paper, we report the structure of three more compounds of this type, including the unsubstituted parent compound, N-benzoyloxybenzamidine, (I), and two isomeric hydroxy compounds, N-(2-hydroxybenzoyloxy)benzamidine, (II), and N-benzoyloxy-2-hydroxybenzamidine, (III). In these three compounds, there exists the possibility that the overall conformation may be influenced by intermolecular hydrogen bonding involving the substituted aryl rings.

The molecules of (I)–(III) (Figs. 1–3) all have chain-extended conformations, with the aryl groups remote from one another. In (III), the non-H atoms in the central spacer unit between atoms C11 and C21 are almost coplanar, as shown by the key torsion angles (Table 1), whereas in both (I) and (III), there is a modest twist about the central N2—O1 bond. The C—N and C—O distances in the spacer unit distinguish clearly between the formal single and double bonds; the C—N distances are, in addition, fully consistent with the location of the H atoms bonded to atom N4, as deduced from a difference map. The remaining bond distances and interbond angles show no unusual features.

Despite their very similar constitutions and their similar molecular geometries, the supramolecular structures of (I)–(III) are all different, with significant differences even between the isomeric compounds (II) and (III). No two structures employ the same combination of hard and soft (Desiraju & Steiner, 1999) interactions between the molecules.

In (I) (Fig. 1), where both aryl rings are unsubstituted, there are no intramolecular hydrogen bonds and only a single intermolecular hydrogen bond (N—H···O; Table 2). Amino atom N4 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H41, to imino atom N2 in the molecule at (0.5 + x, 0.5 − y, 0.5 + z), so producing a zigzag C(4) chain (Bernstein et al., 1995) running parallel to the [101] direction and generated by the n-glide plane at y = 0.25 (Fig. 4). The second N—H bond plays no role in the supramolecular aggregation, forming neither a hard N—H···O hydrogen bond nor a soft N—H···π(arene) hydrogen bond. Neither of the two O atoms plays any role in the supramolecular structure.

However, the chains in (I) are weakly linked into sheets by a single aromatic π···π stacking interaction. Phenyl rings C11–C16 and C21–C26 in the molecules at (x, y, z) and (0.5 + x, 0.5 − y, −0.5 + z), respectively, are nearly parallel, with an interplanar angle of only 5.1 (2)°; the ring-centroid separation is 3.852 (2) Å and the interplanar spacing is ca 3.50 Å, giving a centroid offset of ca 1.61 Å. Propagation of this interaction thus generates a chain running parallel to the [10–1] direction (Fig. 5), and the combination of [101] and [10–1] chains generates a (010) sheet. Two sheets pass through each unit cell, in the domains −0.02 < y < 0.52 and 0.48 < y < 1.02, but there are no direction-specific interactions between adjacent sheets.

There is an intramolecular hydrogen bond in (II) (Fig. 2) and there are two intermolecular hydrogen bonds, viz. one three-centred N—H···(N,O) bond and one two-centred C—H···O bond, both of which utilize the same O acceptor atom (Table 3). Amino atom N4 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atom H42, to imino atom N2 and to carbonyl atom O5, both in the molecule at (0.5 − x, 1 − y, −0.5 + z), thereby producing a C(4) C(7)[R²₁(5)] chain of rings running parallel to the [001] direction and generated by the 2₁ screw axis along (1/4, 1/2, z) (Fig. 6). At the same time, atom C12 at (x, y, z) acts as a hydrogen-bond donor to atom O5 in the molecule at (0.5 + x, y, 0.5 − z), so producing a zigzag C(8) chain parallel to [100] and generated by the a-glide plane at z = 0.25 (Fig. 7). The combination of the [100] and [001] chains generates a (010) sheet, two of which pass through each unit cell in the domains 0.26 < y < 0.74 and 0.76 < y < 1.24, respectively. There are no direction-specific interactions between adjacent sheets, although there is a single C—H···π(arene) hydrogen bond within the sheet (Table 3).

In (III), which is isomeric with (II), an intramolecular O—H···N hydrogen bond (Fig. 3) forms an S(6) motif and the supramolecular aggregation is dominated by two intermolecular N—H···O hydrogen bonds (Table 4). Amino atom N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor, via atoms H1A and H1B, respectively, to phenol atom O1 in the molecule at (−0.5 + x, 0.5 − y, 0.5 + z) and to carbonyl atom O3 in the molecule at (0.5 + x, 0.5 − y, 0.5 + z), thereby producing C(6) and C(7) chains running parallel to the [−101] and [101] directions, respectively. The combination of these two chains produces a (010) sheet in the form of a (4,4)-net (Batten & Robson, 1998) containing equal numbers of S(6) and R⁴₅(22) rings (Fig. 8). This sheet, which is generated by the n-glide plane at y = 1/4, lies in the domain −0.02 < y < 0.52. A second such sheet, related to the first by inversion, lies in the domain 0.48 < y 1.02, this sheet being generated by the n-glide plane at y = 0.75. However, there are no direction-specific interactions between adjacent sheets; in particular, there are neither X—H···π(arene) hydrogen bonds (X = C, N or O) nor aromatic π···π stacking interactions in the structure.

In summary, the overall conformations adopted by (I)–(III) are similar to those of the analogues reported previously; this conformation appears to be independent of the presence or absence of intermolecular hydrogen bonding involving the carbonyl O atom, previously suggested as a contributory factor in the determination of molecular conformation (Tucker et al., 2000).

S2. Experimental

Samples of (I)–(III) were prepared by heating, under reflux for 1 h, a mixture containing equimolar quantities of the appropriate acyl chloride and the appropriate benzamidoxime in dry tetrahydrofuran solution, in the presence of triethylamine. After removal of triethylammonium chloride and evaporation of the solvent, the solid products were crystallized from acetonitrile

S3. Refinement

For compounds (I) and (III), space group P2₁/n was uniquely assigned from the systematic absences; space group Pbca was likewise assigned for (II). All H atoms were located from difference maps, which showed clearly that the NH₂ groups were all pyramidal; all H atoms were then treated as riding atoms with C—H distances of 0.95 Å, N—H distances of 0.88–0.95 Å and O—H distances of 0.84 Å.

Computing details

For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003). Software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999) for (I), (II); SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999) for (III).

Figures

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The molecule of (III), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 4. Part of the crystal structure of (I), showing the formation of a C(4) hydrogen-bonded chain along [101]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (0.5 + x, 0.5 − y, 0.5 + z), (−0.5 + x, 0.5 − y, −0.5 + z) and (−1 + x, y, −1 + z), respectively.
	Fig. 5. A steroview of part of the crystal structure of (I), showing the formation of a π-stacked chain along [10–1]. For the sake of clarity, H atoms bonded to C atoms have been omitted.
	Fig. 6. Part of the crystal structure of (II), showing the formation of a chain of rings along [001], built from hard hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*), a hash (#) or an ampersand (&) are at the symmetry positions (0.5 − x, 1 − y, 0.5 + z), (0.5 − x, 1 − y, −0.5 + z) and (x, y, 1 + z), respectively.
	Fig. 7. Part of the crystal structure of (II), showing the formation of a C(8) chain along [100], built from soft hydrogen bonds. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (0.5 + x, y, 0.5 − z) and (−0.5 + x, y, 0.5 − z), respectively.
	Fig. 8. A stereoview of part of the crystal structure of (I), showing the formation of a (010) sheet of S(6) and R^45(22) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.

(I) N²-(Benzoyloxy)benzamidine

Crystal data

C14H12N2O2	F(000) = 504
Mr = 240.26	Dx = 1.381 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2614 reflections
a = 7.0415 (2) Å	θ = 3.2–27.5°
b = 21.4704 (7) Å	µ = 0.09 mm^−1
c = 8.0570 (3) Å	T = 120 K
β = 108.4804 (16)°	Plate, colourless
V = 1155.27 (7) Å^3	0.25 × 0.20 × 0.08 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2614 independent reflections
Radiation source: rotating anode	1708 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −9→9
Tmin = 0.967, Tmax = 0.993	k = −27→27
10316 measured reflections	l = −10→10

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.129	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0719P)^2 + 0.0022P] where P = (Fo^2 + 2Fc^2)/3
2614 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	0.68674 (18)	0.20793 (5)	1.03591 (14)	0.0222 (3)
O5	0.62128 (19)	0.11800 (5)	0.87945 (15)	0.0265 (3)
N2	0.6429 (2)	0.23953 (6)	0.86857 (17)	0.0220 (3)
N4	0.8343 (2)	0.31800 (7)	1.05407 (17)	0.0218 (3)
C3	0.7286 (2)	0.29369 (7)	0.8972 (2)	0.0186 (4)
C5	0.6621 (2)	0.14541 (8)	1.0169 (2)	0.0189 (4)
C11	0.6990 (2)	0.33248 (7)	0.7376 (2)	0.0180 (4)
C12	0.6842 (2)	0.30402 (8)	0.5786 (2)	0.0216 (4)
C13	0.6554 (2)	0.33948 (8)	0.4299 (2)	0.0252 (4)
C14	0.6435 (3)	0.40380 (8)	0.4378 (2)	0.0263 (4)
C15	0.6600 (3)	0.43238 (8)	0.5957 (2)	0.0254 (4)
C16	0.6863 (2)	0.39696 (8)	0.7450 (2)	0.0214 (4)
C21	0.6908 (2)	0.11529 (7)	1.1906 (2)	0.0182 (4)
C22	0.7371 (2)	0.14931 (8)	1.3457 (2)	0.0207 (4)
C23	0.7585 (3)	0.11870 (8)	1.5029 (2)	0.0244 (4)
C24	0.7311 (3)	0.05492 (8)	1.5044 (2)	0.0270 (4)
C25	0.6868 (3)	0.02098 (8)	1.3499 (2)	0.0283 (4)
C26	0.6678 (3)	0.05123 (8)	1.1937 (2)	0.0230 (4)
H12	0.6939	0.2600	0.5725	0.026*
H13	0.6437	0.3198	0.3216	0.030*
H14	0.6240	0.4281	0.3353	0.032*
H15	0.6534	0.4765	0.6017	0.030*
H16	0.6957	0.4168	0.8527	0.026*
H22	0.7540	0.1932	1.3441	0.025*
H23	0.7919	0.1416	1.6092	0.029*
H24	0.7426	0.0342	1.6114	0.032*
H25	0.6696	−0.0229	1.3515	0.034*
H26	0.6388	0.0280	1.0883	0.028*
H41	0.8959	0.2907	1.1487	0.026*
H42	0.9223	0.3516	1.0544	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0294 (6)	0.0216 (7)	0.0139 (6)	−0.0021 (5)	0.0044 (5)	0.0035 (5)
O5	0.0353 (7)	0.0260 (7)	0.0171 (6)	0.0000 (5)	0.0068 (5)	−0.0015 (5)
N4	0.0255 (8)	0.0222 (7)	0.0150 (7)	−0.0020 (6)	0.0028 (6)	0.0002 (6)
N2	0.0276 (8)	0.0231 (8)	0.0126 (7)	−0.0019 (6)	0.0026 (6)	0.0054 (5)
C3	0.0188 (8)	0.0208 (9)	0.0162 (8)	0.0012 (6)	0.0057 (7)	0.0006 (6)
C5	0.0154 (8)	0.0222 (9)	0.0185 (9)	−0.0008 (6)	0.0044 (6)	0.0020 (7)
C11	0.0151 (8)	0.0220 (9)	0.0163 (8)	−0.0013 (6)	0.0039 (7)	0.0013 (6)
C12	0.0229 (9)	0.0217 (9)	0.0195 (8)	−0.0009 (7)	0.0056 (7)	0.0000 (7)
C13	0.0255 (9)	0.0316 (10)	0.0183 (9)	−0.0023 (7)	0.0068 (7)	−0.0020 (7)
C14	0.0258 (9)	0.0308 (10)	0.0196 (9)	−0.0030 (7)	0.0032 (7)	0.0092 (7)
C15	0.0258 (9)	0.0207 (9)	0.0258 (9)	−0.0016 (7)	0.0029 (8)	0.0038 (7)
C16	0.0194 (8)	0.0239 (9)	0.0199 (9)	−0.0009 (7)	0.0045 (7)	−0.0014 (7)
C21	0.0134 (7)	0.0231 (9)	0.0168 (8)	0.0020 (6)	0.0030 (6)	0.0017 (6)
C22	0.0204 (8)	0.0208 (9)	0.0203 (8)	−0.0003 (7)	0.0054 (7)	0.0026 (7)
C23	0.0252 (9)	0.0299 (10)	0.0164 (8)	0.0026 (7)	0.0042 (7)	−0.0005 (7)
C24	0.0317 (10)	0.0275 (10)	0.0222 (9)	0.0036 (8)	0.0090 (8)	0.0094 (7)
C25	0.0366 (10)	0.0188 (9)	0.0294 (10)	0.0018 (8)	0.0104 (8)	0.0048 (8)
C26	0.0252 (9)	0.0216 (9)	0.0219 (9)	0.0002 (7)	0.0071 (7)	−0.0014 (7)

Geometric parameters (Å, º)

O1—C5	1.356 (2)	C14—H14	0.95
O1—N2	1.452 (2)	C15—C16	1.385 (2)
O5—C5	1.206 (2)	C15—H15	0.95
N4—C3	1.352 (2)	C16—H16	0.95
N4—H41	0.95	C21—C26	1.386 (2)
N4—H42	0.95	C21—C22	1.394 (2)
N2—C3	1.297 (2)	C22—C23	1.392 (2)
C3—C11	1.490 (2)	C22—H22	0.95
C5—C21	1.496 (2)	C23—C24	1.383 (2)
C11—C16	1.390 (2)	C23—H23	0.95
C11—C12	1.393 (2)	C24—C25	1.389 (3)
C12—C13	1.379 (2)	C24—H24	0.95
C12—H12	0.95	C25—C26	1.384 (2)
C13—C14	1.386 (3)	C25—H25	0.95
C13—H13	0.95	C26—H26	0.95
C14—C15	1.383 (3)
C5—O1—N2	112.07 (12)	C16—C15—H15	119.9
C3—N4—H41	119.2	C14—C15—H15	119.9
C3—N4—H42	117.4	C15—C16—C11	120.16 (16)
H41—N4—H42	109.5	C15—C16—H16	119.9
C3—N2—O1	107.69 (12)	C11—C16—H16	119.9
N2—C3—N4	126.84 (14)	C26—C21—C22	119.93 (15)
N2—C3—C11	114.70 (14)	C26—C21—C5	117.66 (14)
N4—C3—C11	118.43 (14)	C22—C21—C5	122.41 (15)
O5—C5—O1	124.86 (14)	C23—C22—C21	119.71 (16)
O5—C5—C21	124.77 (15)	C23—C22—H22	120.1
O1—C5—C21	110.37 (13)	C21—C22—H22	120.1
C16—C11—C12	119.28 (15)	C24—C23—C22	119.98 (16)
C16—C11—C3	120.87 (15)	C24—C23—H23	120.0
C12—C11—C3	119.84 (14)	C22—C23—H23	120.0
C13—C12—C11	120.28 (16)	C25—C24—C23	120.26 (16)
C13—C12—H12	119.9	C25—C24—H24	119.9
C11—C12—H12	119.9	C23—C24—H24	119.9
C12—C13—C14	120.28 (16)	C24—C25—C26	119.84 (16)
C12—C13—H13	119.9	C24—C25—H25	120.1
C14—C13—H13	119.9	C26—C25—H25	120.1
C15—C14—C13	119.72 (16)	C25—C26—C21	120.26 (16)
C15—C14—H14	120.1	C25—C26—H26	119.9
C13—C14—H14	120.1	C21—C26—H26	119.9
C16—C15—C14	120.27 (16)
C5—O1—N2—C3	−160.0 (2)	C12—C11—C16—C15	−0.2 (2)
O1—N2—C3—N4	−2.1 (2)	C3—C11—C16—C15	179.58 (15)
O1—N2—C3—C11	179.8 (2)	O5—C5—C21—C26	−0.4 (2)
N2—O1—C5—O5	4.5 (2)	O1—C5—C21—C26	179.11 (14)
N2—O1—C5—C21	−175.0 (2)	O5—C5—C21—C22	−179.73 (15)
N2—C3—C11—C16	146.99 (15)	O1—C5—C21—C22	−0.2 (2)
N4—C3—C11—C16	−31.2 (2)	C26—C21—C22—C23	−0.5 (2)
N2—C3—C11—C12	−33.2 (2)	C5—C21—C22—C23	178.86 (15)
N4—C3—C11—C12	148.57 (16)	C21—C22—C23—C24	−0.9 (2)
C16—C11—C12—C13	−0.6 (2)	C22—C23—C24—C25	1.5 (3)
C3—C11—C12—C13	179.58 (15)	C23—C24—C25—C26	−0.7 (3)
C11—C12—C13—C14	0.8 (3)	C24—C25—C26—C21	−0.6 (3)
C12—C13—C14—C15	−0.2 (3)	C22—C21—C26—C25	1.2 (2)
C13—C14—C15—C16	−0.7 (3)	C5—C21—C26—C25	−178.13 (16)
C14—C15—C16—C11	0.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···N2^i	0.95	2.15	3.029 (2)	153

Symmetry code: (i) x+1/2, −y+1/2, z+1/2.

(II) N²-(2-Hydroxybenzoyloxy)benzamidine

Crystal data

C14H12N2O3	F(000) = 1072
Mr = 256.26	Dx = 1.408 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2758 reflections
a = 9.3808 (1) Å	θ = 3.1–27.5°
b = 24.9553 (4) Å	µ = 0.10 mm^−1
c = 10.3277 (1) Å	T = 120 K
V = 2417.72 (5) Å^3	Block, colourless
Z = 8	0.55 × 0.32 × 0.28 mm

Data collection

Nonius KappaCCD diffractometer	2758 independent reflections
Radiation source: rotating anode	2308 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −12→9
Tmin = 0.966, Tmax = 0.972	k = −32→32
17440 measured reflections	l = −13→12

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.105	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0581P)^2 + 1.0166P] where P = (Fo^2 + 2Fc^2)/3
2758 reflections	(Δ/σ)max = 0.001
175 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

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

	x	y	z	Uiso*/Ueq
O1	0.16042 (9)	0.57063 (3)	0.07061 (8)	0.0186 (2)
O5	0.08972 (10)	0.58517 (3)	0.27676 (8)	0.0219 (2)
O22	−0.11487 (11)	0.65582 (4)	0.31260 (9)	0.0254 (2)
N2	0.24819 (12)	0.52822 (4)	0.12648 (10)	0.0185 (2)
N4	0.18746 (12)	0.48525 (4)	−0.07198 (10)	0.0200 (2)
C3	0.25882 (13)	0.48989 (5)	0.04147 (11)	0.0162 (3)
C5	0.09289 (13)	0.59851 (4)	0.16295 (12)	0.0164 (2)
C11	0.35734 (13)	0.44605 (5)	0.08089 (11)	0.0157 (2)
C12	0.48275 (13)	0.45869 (5)	0.14659 (12)	0.0183 (3)
C13	0.57522 (15)	0.41826 (5)	0.18447 (12)	0.0214 (3)
C14	0.54277 (15)	0.36493 (5)	0.15761 (13)	0.0221 (3)
C15	0.41747 (15)	0.35224 (5)	0.09349 (13)	0.0222 (3)
C16	0.32460 (14)	0.39244 (5)	0.05472 (12)	0.0193 (3)
C21	0.01932 (13)	0.64654 (4)	0.11252 (12)	0.0168 (3)
C22	−0.08237 (14)	0.67216 (5)	0.19139 (12)	0.0185 (3)
C23	−0.15664 (14)	0.71658 (5)	0.14315 (13)	0.0227 (3)
C24	−0.12627 (15)	0.73610 (5)	0.02098 (14)	0.0235 (3)
C25	−0.02321 (15)	0.71186 (5)	−0.05625 (13)	0.0232 (3)
C26	0.04785 (14)	0.66696 (5)	−0.01138 (12)	0.0203 (3)
H22	−0.0593	0.6311	0.3347	0.038*
H41	0.1309	0.5129	−0.0956	0.024*
H42	0.2302	0.4665	−0.1366	0.024*
H12	0.5049	0.4950	0.1654	0.022*
H13	0.6609	0.4270	0.2288	0.026*
H14	0.6065	0.3373	0.1832	0.027*
H15	0.3950	0.3158	0.0760	0.027*
H16	0.2390	0.3836	0.0105	0.023*
H23	−0.2280	0.7333	0.1945	0.027*
H24	−0.1764	0.7665	−0.0107	0.028*
H25	−0.0018	0.7261	−0.1394	0.028*
H26	0.1165	0.6498	−0.0649	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0240 (5)	0.0150 (4)	0.0166 (4)	0.0062 (3)	−0.0012 (3)	0.0003 (3)
O5	0.0300 (5)	0.0184 (4)	0.0174 (5)	0.0056 (4)	0.0018 (4)	0.0019 (3)
O22	0.0324 (5)	0.0234 (5)	0.0204 (5)	0.0085 (4)	0.0038 (4)	0.0003 (4)
N2	0.0233 (6)	0.0145 (5)	0.0178 (5)	0.0062 (4)	−0.0019 (4)	0.0015 (4)
N4	0.0230 (6)	0.0195 (5)	0.0175 (5)	0.0036 (4)	−0.0025 (4)	−0.0027 (4)
C3	0.0168 (6)	0.0161 (5)	0.0156 (5)	−0.0015 (5)	0.0024 (5)	0.0012 (4)
C5	0.0187 (6)	0.0133 (5)	0.0174 (6)	−0.0013 (4)	−0.0008 (5)	−0.0010 (4)
C11	0.0180 (6)	0.0149 (5)	0.0141 (5)	0.0008 (4)	0.0027 (4)	0.0000 (4)
C12	0.0222 (6)	0.0155 (5)	0.0171 (6)	−0.0019 (5)	0.0003 (5)	−0.0009 (4)
C13	0.0222 (6)	0.0211 (6)	0.0209 (6)	−0.0004 (5)	−0.0042 (5)	0.0005 (5)
C14	0.0263 (7)	0.0174 (6)	0.0227 (6)	0.0042 (5)	0.0010 (5)	0.0019 (5)
C15	0.0269 (7)	0.0138 (5)	0.0257 (7)	−0.0007 (5)	0.0018 (5)	−0.0021 (5)
C16	0.0204 (6)	0.0174 (6)	0.0199 (6)	−0.0019 (5)	0.0003 (5)	−0.0025 (5)
C21	0.0190 (6)	0.0128 (5)	0.0185 (6)	−0.0009 (4)	−0.0034 (5)	−0.0014 (4)
C22	0.0225 (6)	0.0143 (5)	0.0188 (6)	−0.0012 (5)	−0.0034 (5)	−0.0024 (4)
C23	0.0246 (7)	0.0161 (6)	0.0274 (7)	0.0038 (5)	−0.0040 (5)	−0.0053 (5)
C24	0.0278 (7)	0.0125 (5)	0.0303 (7)	0.0015 (5)	−0.0101 (6)	−0.0004 (5)
C25	0.0297 (7)	0.0177 (6)	0.0222 (6)	−0.0021 (5)	−0.0048 (6)	0.0041 (5)
C26	0.0224 (6)	0.0181 (6)	0.0202 (6)	−0.0018 (5)	−0.0006 (5)	0.0005 (5)

Geometric parameters (Å, º)

O1—C5	1.340 (2)	C13—H13	0.95
O1—N2	1.460 (2)	C14—C15	1.3858 (19)
O5—C5	1.222 (2)	C14—H14	0.95
O22—C22	1.3514 (15)	C15—C16	1.3876 (18)
O22—H22	0.84	C15—H15	0.95
N2—C3	1.302 (2)	C16—H16	0.95
N4—C3	1.354 (2)	C21—C26	1.4030 (17)
N4—H41	0.90	C21—C22	1.4080 (18)
N4—H42	0.91	C22—C23	1.4008 (17)
C3—C11	1.4890 (16)	C23—C24	1.382 (2)
C5—C21	1.4780 (16)	C23—H23	0.95
C11—C12	1.3942 (17)	C24—C25	1.392 (2)
C11—C16	1.3992 (16)	C24—H24	0.95
C12—C13	1.3868 (18)	C25—C26	1.3837 (18)
C12—H12	0.95	C25—H25	0.95
C13—C14	1.3932 (17)	C26—H26	0.95
C5—O1—N2	111.21 (9)	C16—C15—C14	120.36 (11)
C22—O22—H22	109.5	C16—C15—H15	119.8
C3—N2—O1	108.01 (9)	C14—C15—H15	119.8
C3—N4—H41	117.3	C15—C16—C11	119.84 (12)
C3—N4—H42	117.5	C15—C16—H16	120.1
H41—N4—H42	117.0	C11—C16—H16	120.1
N2—C3—N4	127.46 (11)	C26—C21—C22	119.47 (11)
N2—C3—C11	113.76 (10)	C26—C21—C5	121.79 (11)
N4—C3—C11	118.72 (10)	C22—C21—C5	118.74 (11)
O5—C5—O1	123.69 (11)	O22—C22—C23	117.13 (11)
O5—C5—C21	123.27 (11)	O22—C22—C21	123.48 (11)
O1—C5—C21	113.02 (10)	C23—C22—C21	119.38 (11)
C12—C11—C16	119.70 (11)	C24—C23—C22	120.07 (12)
C12—C11—C3	119.39 (10)	C24—C23—H23	120.0
C16—C11—C3	120.90 (11)	C22—C23—H23	120.0
C13—C12—C11	120.04 (11)	C23—C24—C25	120.87 (12)
C13—C12—H12	120.0	C23—C24—H24	119.6
C11—C12—H12	120.0	C25—C24—H24	119.6
C12—C13—C14	120.14 (12)	C26—C25—C24	119.65 (12)
C12—C13—H13	119.9	C26—C25—H25	120.2
C14—C13—H13	119.9	C24—C25—H25	120.2
C15—C14—C13	119.91 (12)	C25—C26—C21	120.51 (12)
C15—C14—H14	120.0	C25—C26—H26	119.7
C13—C14—H14	120.0	C21—C26—H26	119.7
C5—O1—N2—C3	152.4 (2)	C3—C11—C16—C15	−179.40 (11)
O1—N2—C3—N4	−8.37 (17)	O5—C5—C21—C26	166.77 (12)
O1—N2—C3—C11	174.47 (9)	O1—C5—C21—C26	−14.64 (16)
N2—O1—C5—O5	−9.63 (16)	O5—C5—C21—C22	−13.45 (18)
N2—O1—C5—C21	171.77 (9)	O1—C5—C21—C22	165.14 (11)
N2—C3—C11—C12	−38.13 (16)	C26—C21—C22—O22	−178.88 (11)
N4—C3—C11—C12	144.44 (12)	C5—C21—C22—O22	1.33 (18)
N2—C3—C11—C16	140.84 (12)	C26—C21—C22—C23	2.06 (18)
N4—C3—C11—C16	−36.59 (17)	C5—C21—C22—C23	−177.73 (11)
C16—C11—C12—C13	0.70 (18)	O22—C22—C23—C24	178.54 (12)
C3—C11—C12—C13	179.69 (11)	C21—C22—C23—C24	−2.34 (19)
C11—C12—C13—C14	−0.32 (19)	C22—C23—C24—C25	0.7 (2)
C12—C13—C14—C15	−0.3 (2)	C23—C24—C25—C26	1.3 (2)
C13—C14—C15—C16	0.6 (2)	C24—C25—C26—C21	−1.59 (19)
C14—C15—C16—C11	−0.23 (19)	C22—C21—C26—C25	−0.09 (18)
C12—C11—C16—C15	−0.43 (18)	C5—C21—C26—C25	179.69 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O22—H22···O5	0.84	1.90	2.632 (2)	144
N4—H42···O5^i	0.91	2.31	3.146 (2)	154
N4—H42···N2^i	0.91	2.46	3.190 (2)	138
C12—H12···O5^ii	0.95	2.46	3.405 (2)	173
C16—H16···Cg1^iii	0.95	2.68	3.529 (2)	149

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

(III) N²-Benzoyloxy-2-hydroxybenzamidine

Crystal data

C14H12N2O3	F(000) = 536
Mr = 256.26	Dx = 1.403 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2549 reflections
a = 4.6463 (3) Å	θ = 3.3–27.5°
b = 22.1280 (13) Å	µ = 0.10 mm^−1
c = 11.9551 (9) Å	T = 120 K
β = 99.202 (3)°	Plate, colourless
V = 1213.33 (14) Å^3	0.25 × 0.10 × 0.01 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	2549 independent reflections
Radiation source: rotating anode	1412 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 3.3°
Absorption correction: multi-scan (DENZO–SMN; Otwinowski & Minor, 1997)	h = −5→5
Tmin = 0.970, Tmax = 0.998	k = −27→28
8910 measured reflections	l = −15→15

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0626P)^2] where P = (Fo^2 + 2Fc^2)/3
2549 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

Special details

Experimental. ?.

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

	x	y	z	Uiso*/Ueq
O1	0.3688 (3)	0.18366 (6)	0.20049 (11)	0.0294 (4)
O5	0.2346 (3)	0.15005 (7)	0.02115 (12)	0.0383 (4)
O121	0.7525 (3)	0.28621 (7)	0.00167 (11)	0.0359 (4)
N2	0.5570 (4)	0.22553 (8)	0.15460 (14)	0.0289 (5)
N4	0.6513 (4)	0.25484 (8)	0.34554 (14)	0.0301 (5)
C3	0.6859 (4)	0.25965 (9)	0.23640 (17)	0.0240 (5)
C5	0.2209 (4)	0.14696 (9)	0.12101 (18)	0.0268 (5)
C11	0.8891 (4)	0.30561 (9)	0.20344 (16)	0.0241 (5)
C12	0.9117 (4)	0.31623 (9)	0.09000 (17)	0.0252 (5)
C13	1.1034 (5)	0.35978 (10)	0.06161 (17)	0.0314 (6)
C14	1.2743 (4)	0.39237 (9)	0.14485 (18)	0.0302 (5)
C15	1.2559 (5)	0.38254 (9)	0.25700 (18)	0.0305 (5)
C16	1.0651 (4)	0.33982 (10)	0.28583 (16)	0.0289 (5)
C21	0.0454 (4)	0.10209 (9)	0.17318 (17)	0.0270 (5)
C22	0.0324 (5)	0.10087 (10)	0.28767 (18)	0.0315 (6)
C23	−0.1280 (5)	0.05619 (10)	0.33122 (18)	0.0356 (6)
C24	−0.2764 (5)	0.01349 (10)	0.2605 (2)	0.0344 (6)
C25	−0.2657 (5)	0.01489 (10)	0.1465 (2)	0.0397 (6)
C26	−0.1052 (5)	0.05889 (10)	0.10217 (17)	0.0358 (6)
H121	0.6558	0.2587	0.0267	0.054*
H41	0.5067	0.2317	0.3590	0.045*
H42	0.7089	0.2848	0.3922	0.045*
H13	1.1162	0.3670	−0.0158	0.038*
H14	1.4057	0.4218	0.1248	0.036*
H15	1.3744	0.4051	0.3144	0.037*
H16	1.0528	0.3334	0.3635	0.035*
H22	0.1330	0.1305	0.3366	0.038*
H23	−0.1353	0.0551	0.4101	0.043*
H24	−0.3862	−0.0169	0.2907	0.041*
H25	−0.3689	−0.0145	0.0978	0.048*
H26	−0.0978	0.0596	0.0232	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0340 (9)	0.0321 (9)	0.0235 (8)	−0.0059 (7)	0.0090 (7)	0.0010 (7)
O5	0.0509 (10)	0.0413 (11)	0.0231 (9)	−0.0070 (8)	0.0071 (7)	0.0016 (7)
O121	0.0408 (9)	0.0445 (11)	0.0235 (9)	−0.0131 (8)	0.0087 (7)	−0.0048 (7)
N2	0.0319 (11)	0.0298 (11)	0.0271 (11)	−0.0067 (8)	0.0114 (9)	0.0013 (8)
N4	0.0347 (10)	0.0327 (11)	0.0237 (11)	−0.0038 (8)	0.0072 (8)	0.0001 (8)
C3	0.0241 (12)	0.0258 (13)	0.0228 (12)	0.0087 (9)	0.0058 (10)	0.0014 (9)
C5	0.0280 (12)	0.0285 (13)	0.0234 (12)	0.0044 (10)	0.0027 (9)	0.0021 (10)
C11	0.0236 (11)	0.0265 (12)	0.0231 (12)	0.0057 (9)	0.0062 (9)	0.0003 (9)
C12	0.0250 (12)	0.0287 (13)	0.0224 (12)	0.0025 (9)	0.0051 (9)	−0.0028 (10)
C13	0.0369 (13)	0.0361 (14)	0.0228 (12)	−0.0016 (11)	0.0101 (10)	0.0027 (10)
C14	0.0308 (13)	0.0285 (13)	0.0330 (14)	−0.0015 (10)	0.0105 (10)	0.0014 (10)
C15	0.0316 (12)	0.0308 (14)	0.0283 (13)	0.0003 (10)	0.0023 (10)	−0.0047 (10)
C16	0.0338 (13)	0.0326 (13)	0.0207 (11)	0.0046 (10)	0.0056 (10)	0.0014 (10)
C21	0.0267 (12)	0.0261 (13)	0.0279 (13)	0.0045 (10)	0.0038 (10)	0.0021 (10)
C22	0.0382 (13)	0.0271 (13)	0.0306 (13)	0.0003 (10)	0.0100 (10)	−0.0010 (10)
C23	0.0450 (14)	0.0328 (14)	0.0324 (13)	0.0042 (11)	0.0164 (11)	0.0040 (11)
C24	0.0321 (13)	0.0286 (14)	0.0442 (15)	−0.0003 (10)	0.0110 (11)	0.0062 (11)
C25	0.0408 (14)	0.0344 (15)	0.0408 (16)	−0.0078 (11)	−0.0035 (12)	0.0009 (12)
C26	0.0420 (14)	0.0385 (15)	0.0258 (13)	−0.0031 (11)	0.0019 (11)	0.0035 (11)

Geometric parameters (Å, º)

O1—C5	1.351 (2)	C14—C15	1.374 (3)
O1—N2	1.442 (2)	C14—H14	0.95
O5—C5	1.208 (2)	C15—C16	1.377 (3)
O121—C12	1.361 (2)	C15—H15	0.95
O121—H121	0.84	C16—H16	0.95
N2—C3	1.303 (2)	C21—C22	1.380 (3)
N4—C3	1.344 (2)	C21—C26	1.391 (3)
N4—H41	0.88	C22—C23	1.388 (3)
N4—H42	0.88	C22—H22	0.95
C3—C11	1.483 (3)	C23—C24	1.377 (3)
C5—C21	1.484 (3)	C23—H23	0.95
C11—C12	1.397 (3)	C24—C25	1.373 (3)
C11—C16	1.398 (3)	C24—H24	0.95
C12—C13	1.391 (3)	C25—C26	1.382 (3)
C13—C14	1.374 (3)	C25—H25	0.95
C13—H13	0.95	C26—H26	0.95
C5—O1—N2	112.95 (15)	C14—C15—C16	119.72 (19)
C12—O121—H121	109.5	C14—C15—H15	120.1
C3—N2—O1	108.71 (16)	C16—C15—H15	120.1
C3—N4—H41	115.9	C15—C16—C11	121.52 (19)
C3—N4—H42	119.0	C15—C16—H16	119.2
H41—N4—H42	119.1	C11—C16—H16	119.2
N2—C3—N4	124.81 (19)	C22—C21—C26	119.6 (2)
N2—C3—C11	115.69 (18)	C22—C21—C5	122.96 (19)
N4—C3—C11	119.48 (18)	C26—C21—C5	117.39 (19)
O5—C5—O1	124.06 (19)	C21—C22—C23	119.8 (2)
O5—C5—C21	124.93 (19)	C21—C22—H22	120.1
O1—C5—C21	111.00 (18)	C23—C22—H22	120.1
C12—C11—C16	117.83 (19)	C24—C23—C22	120.3 (2)
C12—C11—C3	121.54 (18)	C24—C23—H23	119.8
C16—C11—C3	120.63 (19)	C22—C23—H23	119.8
O121—C12—C13	116.01 (18)	C25—C24—C23	120.0 (2)
O121—C12—C11	123.73 (19)	C25—C24—H24	120.0
C13—C12—C11	120.26 (19)	C23—C24—H24	120.0
C14—C13—C12	120.36 (19)	C24—C25—C26	120.3 (2)
C14—C13—H13	119.8	C24—C25—H25	119.9
C12—C13—H13	119.8	C26—C25—H25	119.9
C13—C14—C15	120.3 (2)	C25—C26—C21	120.0 (2)
C13—C14—H14	119.8	C25—C26—H26	120.0
C15—C14—H14	119.8	C21—C26—H26	120.0
C5—O1—N2—C3	178.82 (16)	C13—C14—C15—C16	0.0 (3)
O1—N2—C3—N4	1.5 (3)	C14—C15—C16—C11	0.4 (3)
O1—N2—C3—C11	179.97 (15)	C12—C11—C16—C15	−0.2 (3)
N2—O1—C5—O5	−2.7 (3)	C3—C11—C16—C15	179.77 (18)
N2—O1—C5—C21	176.26 (14)	O5—C5—C21—C22	−178.9 (2)
N2—C3—C11—C12	7.6 (3)	O1—C5—C21—C22	2.1 (3)
N4—C3—C11—C12	−173.83 (17)	O5—C5—C21—C26	2.7 (3)
N2—C3—C11—C16	−172.38 (18)	O1—C5—C21—C26	−176.26 (17)
N4—C3—C11—C16	6.2 (3)	C26—C21—C22—C23	0.7 (3)
C16—C11—C12—O121	−179.81 (18)	C5—C21—C22—C23	−177.65 (19)
C3—C11—C12—O121	0.2 (3)	C21—C22—C23—C24	−0.6 (3)
C16—C11—C12—C13	−0.3 (3)	C22—C23—C24—C25	0.1 (3)
C3—C11—C12—C13	179.74 (19)	C23—C24—C25—C26	0.3 (3)
O121—C12—C13—C14	−179.80 (19)	C24—C25—C26—C21	−0.2 (3)
C11—C12—C13—C14	0.6 (3)	C22—C21—C26—C25	−0.3 (3)
C12—C13—C14—C15	−0.5 (3)	C5—C21—C26—C25	178.17 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H41···O121^i	0.88	2.26	2.975 (2)	138
N4—H42···O5^ii	0.88	2.10	2.954 (2)	163
O121—H121···N2	0.84	1.82	2.550 (2)	144

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