2,4-Di­nitro­phenyl­hydrazones of 2,4-di­hydroxy­benz­aldehyde, 2,4-di­hydroxy­aceto­phenone and 2,4-di­hydroxy­benzo­phenone

In 2,4-di­hydroxy­benz­aldehyde 2,4-di­nitro­phenyl­hydrazone N,N-di­methyl­form­amide solvate {or 4-[(2,4-di­nitro­phenyl)­hydrazono­methyl]­benzene-1,3-diol N,N-di­methyl­form­amide solvate}, C₁₃H₁₀N₄O₆·C₃H₇NO, (X), 2,4-di­hydroxy­aceto­phenone 2,4-di­nitro­phenyl­hydrazone N,N-di­methyl­form­am­ide solvate (or 4-{1-[(2,4-di­nitro­phenyl)hydrazono]ethyl}benzene-1,3-diol N,N-di­methyl­form­amide solvate), C₁₄H₁₂N₄O₆·C₃H₇NO, (XI), and 2,4-di­hydroxy­benzo­phenone 2,4-di­nitro­phenyl­hydrazone N,N-di­methyl­acet­amide solvate (or 4-­{[(2,4-di­nitro­phenyl)hydrazono]phenyl­methyl}benzene-1,3-diol N,N-di­methyl­acet­amide solvate), C₁₉H₁₄N₄O₆·C₄H₉NO, (XII), the molecules all lack a center of symmetry, crystallize in centrosymmetric space groups and have been observed to exhibit non-linear optical activity. In each case, the hydrazone skeleton is fairly planar, facilitated by the presence of two intramolecular hydrogen bonds and some partial N-N double-bond character. Each molecule is hydrogen bonded to one solvent mol­ecule.

S1. Comment

Hydrazone derivatives are an attractive class of nonlinear optical (NLO) crystalline materials because of their large molecular nonlinearities and their remarkable propensity to form noncentrosymmetric crystal systems (Serbutoviez et al., 1995). The current approach to the development of practical NLO materials has focused on the use of a dihydroxy functionalized hydrazone chromophore that can be easily synthesized and subsequently incorporated into a commercial epoxy polymer system. The preliminary goal was to provide for a systematic variation of the chromophore structure to study the resulting structure-property relationships. To this end, three hydrazones were synthesized by coupling 2,4-dinitrophenylhydrazine (2,4-DNPH) with three carbonyl compounds, namely, 2,4-dihydroxybenzaldehyde, 2,4-dihydroxyacetophenone and 2,4-dihydroxybenzophenone, to yield hydrazones (X), (XI) and (XII), respectively. \sch

To confirm the structures of the three hydrazones, which are part of a series of related compounds currently under investigation (including compounds I—IX which are still in progress), the single-crystal data for these compounds are given here. While each of the three compounds demonstrates NLO properties, it should be noted that each crystallizes in a centrosymmetric space group and that each molecule lacks a center of symmetry.

As seen in Figs. 1–3, all three compounds crystallize in a 1:1 ratio with solvent molecules [N,N-dimethylformamide (DMF) for (X) and (XI), and N,N-dimethylacetamide (DMAc) for (XII)], which accept a hydrogen bond at atom O7 from atom H1A of the para-hydroxy group of the hydrazone. In each case, across the C7═N1 bond, N2 is E to C4; simultaneously, each R substituent on C7 is Z to N2. In each molecule, two intramolecular hydrogen bonds, H2A···N1 and H2B···O3, help to facilitate the planarity of each hydrazone.

The 23-atom hydrazone skeleton [atoms O1—O6, N1—N4 and C1—C13, plus C14 for (XI) and (XII)] of (X) is the most planar of the three compounds, as it has an r.m.s. deviation of 0.061 Å, with atoms O2 and C5 having the largest deviations [0.137 (3) and 0.117 (3) Å, respectively] from the plane. On the other hand, (XI) and (XII) display some buckling. They have larger r.m.s. deviations [0.190 and 0.122 Å, respectively], in part due to atoms with larger deviations from the plane of the skeleton. For example, in (XI), atoms O2 and O6 have deviations of 0.488 (2) and 0.491 (2) Å, respectively, while in (XII), atoms O5 and C5 have deviations of 0.330 (3) and 0.180 (3) Å, respectively, from the 23-atom plane of the skeleton.

In the case of compound (X), even the solvent molecule is coplanar with the plane of the hydrazone molecule; the r.m.s. deviation for all non-H atoms is 0.081 Å. However, neither solvent molecule in compounds (XI) and (XII) is coplanar with the hydrazone molecule (Figs. 2 and 3; Tables 3 and 5). The phenyl substituent (C14—C19) in compound (XII) is nearly perpendicular (Table 5) to the plane of the hydrazone skeleton, likely due in large part to steric problems around C7.

While the intramolecular hydrogen bonding minimizes the rotational freedom about the C4—C7 and N2—C8 bonds, rotation about N1—N2 is also reduced. The average of the C7═N1 bond lengths (Table 6) is ~3σ longer than the average of 13 C═N bond lengths (in PhC═NH coordination compounds) gleaned from the Cambridge Structural Database (CSD, Version?; Allen, 2002). Similarly, the average of the N1—N2 bond lengths (Table 6) is ~20σ shorter than the average of five N—N bond lengths in hydrazine-solvated compounds in the CSD. This likely implies some N1—N2 double-bond character, thus reducing rotational mobility. The extent of this character changes as substituents vary on C7. The range of C7═N1 bond lengths is 0.020 Å (~7σ), while N1—N2 is 0.015 Å (~5σ).

As seen in Table 6, some bond lengths near C7 are affected significantly (>= 3σ) by changes in the R substituent on C7. Specifically, increases in bond lengths are noted for C7═N1, C4—C7 and C4≐C5, concomitant with decreases in the N1—N2 and O2—C3 bond lengths as the R substituent goes from –H to –CH₃ to –Ph. The effect of going from H to alkyl to aromatic groups is felt as much as three bonds away from the C7—R bond.

Table 1. Hydrogen-bonding geometry (Å, °) for (X).

Table 2. Hydrogen-bonding geometry (Å, °) for (XI).

Table 3. Selected RMS deviations (Å) and dihedral angle (°) for (XI).

Table 4. Hydrogen-bonding geometry (Å, °) for (XII).

Table 5. Selected RMS deviations (Å) and dihedral angles (°) for (XII).

Table 6. Selected interatomic distances (Å) for compounds (X)-(XII): the effects of changing C7—R = –H to –CH₃ to –Ph.

S2. Experimental

The three hydrazones were synthesized according to a known procedure (Vogel, 1989) by mixing a solution of 2,4-DNPH in an ethanol-tetrahydrofuran solvent mixture [1:1 for (X), 3:1 for (XI) and 2:1 for (XII)] with the three dihydroxy carbonyl compounds in a 1:1.05 mole ratio with concentrated HCl as a catalyst. The decomposition points (>523 K for each of the three hydrazones) were determined on a Thermal Analysis differential scanning calorimeter at a heating rate of 10 K min⁻¹. Crystals suitable for diffraction were grown by slow evaporation of a saturated solution, in DMF for hydrazones (X) and (XI), and in DMAc for hydrazone (XII). Each crystal was placed into a capillary and sealed with mother liquor.

S3. Refinement

In all three cases, the approximate positions of the two hydroxy H atoms were first obtained from a difference map. These atoms were then placed in `ideal' positions and refined as a rotating group. Bond lengths were constrained (AFIX 43) at 0.93 Å for aromatic C—H, 0.96 Å (AFIX 137) for methyl C—H, 0.86 Å (AFIX 43) for N—H and 0.82 Å (AFIX 147) for O—H. U_iso(H) values were fixed at 1.5U_eq for OH and methyl H atoms, and 1.2 U_eq for all other H atoms. In the final stages of refinement for all three compounds, a few very small or negative F_o values were deemed to be in strong disagreement with their F_c values. The corresponding nine, 12, and 22 reflections for (X), (XI), and (XII), respectively, were eliminated from the final refinement. The percentage decay of the three standards was calculated as the average of their σ(I) values.

Computing details

For all compounds, data collection: P3/P4-PC Diffractometer Program (Siemens, 1991); cell refinement: P3/P4-PC Diffractometer Program; data reduction: XDISK (Siemens, 1991); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990b); software used to prepare material for publication: SHELXTL/PC and SHELXL97.

Figures

	Fig. 1. A view of the asymmetric unit of (X), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level, and significant H atoms are labeled and drawn as small spheres of arbitrary radii.
	Fig. 2. A view of the asymmetric unit of (XI), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level, and significant H atoms are labeled and drawn as small spheres of arbitrary radii.
	Fig. 3. A view of the asymmetric unit of (XII), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level, and significant H atoms are labeled and drawn as small spheres of arbitrary radii.

(X) 2,4-dihydroxybenzaldehyde 2,4-dinitrophenylhydrazone N,N-dimethylformamide solvate

Crystal data

C13H10N4O6·C3H7NO	F(000) = 816
Mr = 391.35	Dx = 1.448 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 49 reflections
a = 19.697 (4) Å	θ = 7.8–17.5°
b = 7.152 (1) Å	µ = 0.12 mm^−1
c = 12.949 (3) Å	T = 293 K
β = 100.34 (2)°	Block cut from larger crystal, red-orange
V = 1794.5 (6) Å^3	0.50 × 0.39 × 0.13 mm
Z = 4

Data collection

Siemens P4 diffractometer	Rint = 0.013
Radiation source: normal-focus sealed tube	θmax = 25.0°, θmin = 2.1°
Graphite monochromator	h = −23→23
θ/2θ scans	k = −8→2
3504 measured reflections	l = 0→15
3119 independent reflections	3 standard reflections every 50 reflections
1774 reflections with I > 2σ(I)	intensity decay: 2.3%

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)] = 0.051	H-atom parameters constrained
wR(F^2) = 0.137	w = 1/[σ^2(Fo^2) + (0.0658P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3110 reflections	Δρmax = 0.21 e Å^−3
258 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0059 (11)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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
O1	−0.20622 (9)	0.4970 (3)	0.63510 (14)	0.0618 (6)
H1A	−0.2393	0.5232	0.5893	0.093*
O2	0.01956 (10)	0.2631 (4)	0.68351 (14)	0.0707 (7)
H2A	0.0494	0.2288	0.6509	0.106*
O3	0.16439 (11)	0.0749 (3)	0.27547 (15)	0.0693 (7)
O4	0.26547 (12)	−0.0371 (4)	0.27488 (17)	0.0992 (10)
O5	0.41862 (12)	−0.2099 (4)	0.5822 (2)	0.0946 (9)
O6	0.38850 (12)	−0.1867 (4)	0.7335 (2)	0.1021 (10)
N1	0.07225 (11)	0.1772 (3)	0.51162 (16)	0.0425 (6)
N2	0.12061 (11)	0.1243 (3)	0.45155 (17)	0.0447 (6)
H2B	0.1103	0.1332	0.3843	0.054*
N3	0.22003 (13)	0.0131 (4)	0.32216 (19)	0.0594 (7)
N4	0.37704 (13)	−0.1689 (4)	0.6381 (3)	0.0692 (8)
C1	−0.15366 (13)	0.4325 (4)	0.5899 (2)	0.0442 (7)
C2	−0.09374 (14)	0.3789 (4)	0.6552 (2)	0.0489 (7)
H2	−0.0906	0.3878	0.7276	0.059*
C3	−0.03840 (13)	0.3122 (4)	0.6147 (2)	0.0452 (7)
C4	−0.04186 (12)	0.2989 (4)	0.50534 (19)	0.0378 (6)
C5	−0.10279 (13)	0.3554 (4)	0.4422 (2)	0.0439 (7)
H5	−0.1061	0.3480	0.3697	0.053*
C6	−0.15855 (13)	0.4217 (4)	0.4815 (2)	0.0456 (7)
H6	−0.1986	0.4585	0.4367	0.055*
C7	0.01475 (13)	0.2344 (4)	0.4583 (2)	0.0413 (7)
H7	0.0094	0.2342	0.3855	0.050*
C8	0.18308 (13)	0.0594 (4)	0.4956 (2)	0.0403 (7)
C9	0.20271 (13)	0.0459 (4)	0.6059 (2)	0.0491 (8)
H9	0.1726	0.0885	0.6485	0.059*
C10	0.26483 (14)	−0.0283 (4)	0.6514 (2)	0.0526 (8)
H10	0.2764	−0.0374	0.7241	0.063*
C11	0.31078 (13)	−0.0903 (4)	0.5886 (2)	0.0505 (8)
C12	0.29525 (14)	−0.0766 (4)	0.4821 (2)	0.0519 (8)
H12	0.3266	−0.1175	0.4411	0.062*
C13	0.23262 (13)	−0.0015 (4)	0.43541 (19)	0.0440 (7)
O7	−0.32368 (12)	0.6028 (4)	0.5204 (2)	0.0875 (8)
N5	−0.40595 (14)	0.6777 (4)	0.3823 (3)	0.0777 (9)
C14	−0.34287 (19)	0.6195 (5)	0.4276 (3)	0.0757 (10)
H14	−0.3118	0.5899	0.3838	0.091*
C15	−0.45853 (19)	0.7223 (7)	0.4422 (3)	0.1127 (16)
H15A	−0.4430	0.6880	0.5142	0.169*
H15B	−0.4999	0.6547	0.4146	0.169*
H15C	−0.4678	0.8541	0.4377	0.169*
C16	−0.4236 (2)	0.6872 (6)	0.2695 (4)	0.1119 (15)
H16A	−0.3832	0.6642	0.2396	0.168*
H16B	−0.4415	0.8091	0.2489	0.168*
H16C	−0.4580	0.5945	0.2448	0.168*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0501 (12)	0.0895 (17)	0.0494 (12)	0.0104 (12)	0.0189 (10)	−0.0009 (12)
O2	0.0580 (12)	0.114 (2)	0.0399 (11)	0.0272 (13)	0.0068 (10)	0.0106 (12)
O3	0.0648 (14)	0.0999 (19)	0.0434 (12)	0.0031 (14)	0.0098 (10)	−0.0029 (12)
O4	0.0826 (16)	0.167 (3)	0.0586 (14)	0.0218 (18)	0.0405 (13)	−0.0050 (16)
O5	0.0561 (14)	0.115 (2)	0.114 (2)	0.0212 (15)	0.0206 (15)	−0.0033 (18)
O6	0.0678 (16)	0.149 (3)	0.0830 (19)	0.0151 (17)	−0.0043 (14)	0.0246 (19)
N1	0.0437 (12)	0.0447 (14)	0.0423 (12)	−0.0024 (11)	0.0160 (11)	0.0004 (11)
N2	0.0467 (13)	0.0514 (15)	0.0379 (12)	−0.0008 (12)	0.0131 (10)	−0.0036 (11)
N3	0.0584 (16)	0.079 (2)	0.0446 (14)	−0.0084 (15)	0.0194 (13)	−0.0093 (14)
N4	0.0452 (15)	0.076 (2)	0.084 (2)	−0.0042 (15)	0.0040 (15)	0.0018 (18)
C1	0.0445 (15)	0.0491 (18)	0.0404 (15)	−0.0061 (14)	0.0115 (12)	0.0004 (13)
C2	0.0527 (16)	0.064 (2)	0.0320 (14)	−0.0014 (15)	0.0121 (13)	0.0049 (13)
C3	0.0451 (16)	0.0533 (19)	0.0372 (15)	−0.0001 (14)	0.0073 (12)	0.0073 (14)
C4	0.0412 (14)	0.0374 (16)	0.0353 (14)	−0.0057 (12)	0.0085 (12)	0.0007 (12)
C5	0.0491 (16)	0.0490 (18)	0.0340 (14)	−0.0059 (14)	0.0083 (12)	−0.0034 (13)
C6	0.0429 (15)	0.0517 (19)	0.0404 (15)	−0.0048 (14)	0.0030 (12)	−0.0025 (13)
C7	0.0475 (16)	0.0409 (17)	0.0356 (14)	−0.0060 (14)	0.0074 (13)	−0.0019 (12)
C8	0.0420 (15)	0.0356 (16)	0.0448 (16)	−0.0071 (13)	0.0119 (12)	−0.0045 (13)
C9	0.0440 (16)	0.060 (2)	0.0453 (16)	−0.0016 (15)	0.0135 (13)	−0.0040 (15)
C10	0.0516 (17)	0.062 (2)	0.0450 (16)	−0.0054 (16)	0.0093 (13)	0.0029 (15)
C11	0.0369 (15)	0.0509 (19)	0.064 (2)	−0.0047 (14)	0.0097 (14)	0.0006 (16)
C12	0.0446 (16)	0.055 (2)	0.0604 (19)	−0.0031 (15)	0.0206 (14)	−0.0087 (16)
C13	0.0451 (15)	0.0478 (18)	0.0416 (15)	−0.0067 (14)	0.0142 (12)	−0.0053 (14)
O7	0.0690 (16)	0.102 (2)	0.0882 (19)	0.0046 (14)	0.0040 (14)	0.0070 (16)
N5	0.0511 (16)	0.072 (2)	0.104 (2)	0.0023 (15)	0.0003 (16)	0.0019 (19)
C14	0.066 (2)	0.068 (3)	0.094 (3)	−0.006 (2)	0.014 (2)	−0.012 (2)
C15	0.075 (3)	0.127 (4)	0.140 (4)	0.008 (3)	0.030 (3)	0.014 (3)
C16	0.097 (3)	0.121 (4)	0.107 (4)	0.008 (3)	−0.010 (3)	−0.009 (3)

Geometric parameters (Å, º)

O1—C1	1.358 (3)	C6—H6	0.9300
O1—H1A	0.8200	C7—H7	0.9300
O2—C3	1.362 (3)	C8—C9	1.414 (4)
O2—H2A	0.8200	C8—C13	1.422 (3)
O3—N3	1.234 (3)	C9—C10	1.366 (4)
O4—N3	1.225 (3)	C9—H9	0.9300
O5—N4	1.223 (3)	C10—C11	1.393 (4)
O6—N4	1.221 (3)	C10—H10	0.9300
N1—C7	1.283 (3)	C11—C12	1.362 (4)
N1—N2	1.386 (3)	C12—C13	1.381 (4)
N2—C8	1.343 (3)	C12—H12	0.9300
N2—H2B	0.8600	O7—C14	1.200 (4)
N3—C13	1.447 (3)	N5—C14	1.341 (4)
N4—C11	1.459 (4)	N5—C15	1.436 (4)
C1—C2	1.377 (4)	N5—C16	1.442 (5)
C1—C6	1.392 (3)	C14—H14	0.9300
C2—C3	1.377 (4)	C15—H15A	0.9600
C2—H2	0.9300	C15—H15B	0.9600
C3—C4	1.408 (3)	C15—H15C	0.9600
C4—C5	1.386 (3)	C16—H16A	0.9600
C4—C7	1.439 (3)	C16—H16B	0.9600
C5—C6	1.375 (3)	C16—H16C	0.9600
C5—H5	0.9300
C1—O1—H1A	109.5	C9—C8—C13	116.3 (2)
C3—O2—H2A	109.5	C10—C9—C8	121.6 (2)
C7—N1—N2	114.5 (2)	C10—C9—H9	119.2
C8—N2—N1	121.7 (2)	C8—C9—H9	119.2
C8—N2—H2B	119.2	C9—C10—C11	119.8 (3)
N1—N2—H2B	119.2	C9—C10—H10	120.1
O4—N3—O3	121.6 (3)	C11—C10—H10	120.1
O4—N3—C13	118.5 (3)	C12—C11—C10	121.1 (3)
O3—N3—C13	119.9 (2)	C12—C11—N4	119.5 (3)
O6—N4—O5	123.5 (3)	C10—C11—N4	119.3 (3)
O6—N4—C11	118.2 (3)	C11—C12—C13	119.5 (3)
O5—N4—C11	118.3 (3)	C11—C12—H12	120.3
O1—C1—C2	117.8 (2)	C13—C12—H12	120.3
O1—C1—C6	122.2 (2)	C12—C13—C8	121.7 (2)
C2—C1—C6	120.0 (3)	C12—C13—N3	116.7 (2)
C1—C2—C3	120.8 (2)	C8—C13—N3	121.6 (2)
C1—C2—H2	119.6	C14—N5—C15	122.3 (4)
C3—C2—H2	119.6	C14—N5—C16	119.6 (4)
O2—C3—C2	117.9 (2)	C15—N5—C16	118.0 (3)
O2—C3—C4	121.6 (2)	O7—C14—N5	124.7 (4)
C2—C3—C4	120.5 (2)	O7—C14—H14	117.7
C5—C4—C3	117.0 (2)	N5—C14—H14	117.7
C5—C4—C7	119.9 (2)	N5—C15—H15A	109.5
C3—C4—C7	123.1 (2)	N5—C15—H15B	109.5
C6—C5—C4	123.1 (2)	H15A—C15—H15B	109.5
C6—C5—H5	118.4	N5—C15—H15C	109.5
C4—C5—H5	118.4	H15A—C15—H15C	109.5
C5—C6—C1	118.5 (3)	H15B—C15—H15C	109.5
C5—C6—H6	120.7	N5—C16—H16A	109.5
C1—C6—H6	120.7	N5—C16—H16B	109.5
N1—C7—C4	123.4 (2)	H16A—C16—H16B	109.5
N1—C7—H7	118.3	N5—C16—H16C	109.5
C4—C7—H7	118.3	H16A—C16—H16C	109.5
N2—C8—C9	121.1 (2)	H16B—C16—H16C	109.5
N2—C8—C13	122.6 (2)
C7—N1—N2—C8	−179.3 (2)	C8—C9—C10—C11	0.9 (4)
O1—C1—C2—C3	−180.0 (3)	C9—C10—C11—C12	0.7 (4)
C6—C1—C2—C3	−0.7 (4)	C9—C10—C11—N4	179.9 (3)
C1—C2—C3—O2	179.4 (3)	O6—N4—C11—C12	−177.0 (3)
C1—C2—C3—C4	0.5 (4)	O5—N4—C11—C12	4.4 (5)
O2—C3—C4—C5	−178.9 (3)	O6—N4—C11—C10	3.8 (5)
C2—C3—C4—C5	0.0 (4)	O5—N4—C11—C10	−174.8 (3)
O2—C3—C4—C7	−0.3 (4)	C10—C11—C12—C13	−0.6 (4)
C2—C3—C4—C7	178.6 (3)	N4—C11—C12—C13	−179.7 (3)
C3—C4—C5—C6	−0.1 (4)	C11—C12—C13—C8	−1.1 (4)
C7—C4—C5—C6	−178.8 (3)	C11—C12—C13—N3	178.6 (3)
C4—C5—C6—C1	−0.1 (4)	N2—C8—C13—C12	−176.7 (3)
O1—C1—C6—C5	179.8 (3)	C9—C8—C13—C12	2.5 (4)
C2—C1—C6—C5	0.5 (4)	N2—C8—C13—N3	3.7 (4)
N2—N1—C7—C4	−178.8 (2)	C9—C8—C13—N3	−177.1 (3)
C5—C4—C7—N1	−178.8 (3)	O4—N3—C13—C12	−1.6 (4)
C3—C4—C7—N1	2.6 (4)	O3—N3—C13—C12	178.3 (3)
N1—N2—C8—C9	−1.3 (4)	O4—N3—C13—C8	178.0 (3)
N1—N2—C8—C13	177.8 (2)	O3—N3—C13—C8	−2.1 (4)
N2—C8—C9—C10	176.8 (3)	C15—N5—C14—O7	−1.7 (6)
C13—C8—C9—C10	−2.4 (4)	C16—N5—C14—O7	−178.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7	0.82	1.83	2.626 (3)	163
O2—H2A···N1	0.82	1.97	2.691 (3)	146
N2—H2B···O3	0.86	1.96	2.603 (3)	131

(XI) 2,4-dihydroxyacetophenone 2,4-dinitrophenylhydrazone N,N-dimethylformamide solvate

Crystal data

C14H12N4O6·C3H7NO	Z = 2
Mr = 405.37	F(000) = 424
Triclinic, P1	Dx = 1.418 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.928 (1) Å	Cell parameters from 50 reflections
b = 9.146 (1) Å	θ = 9.6–18.8°
c = 14.362 (2) Å	µ = 0.11 mm^−1
α = 104.45 (1)°	T = 293 K
β = 91.04 (1)°	Block cut from larger crystal, red-orange
γ = 108.80 (1)°	0.54 × 0.43 × 0.31 mm
V = 949.1 (2) Å^3

Data collection

Siemens Bruker P4 diffractometer	Rint = 0.011
Radiation source: normal-focus sealed tube	θmax = 25.1°, θmin = 2.4°
Graphite monochromator	h = −3→9
θ/2θ scans	k = −10→10
4336 measured reflections	l = −17→17
3310 independent reflections	3 standard reflections every 50 reflections
2207 reflections with I > 2σ(I)	intensity decay: 1.5%

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)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.142	w = 1/[σ^2(Fo^2) + (0.0747P)^2 + 0.1707P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
3298 reflections	Δρmax = 0.18 e Å^−3
268 parameters	Δρmin = −0.16 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.026 (4)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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
O1	0.9344 (3)	1.0729 (2)	−0.25434 (15)	0.0768 (6)
H1A	0.8857	1.1136	−0.2865	0.115*
O2	0.8256 (2)	0.7735 (2)	−0.02812 (13)	0.0605 (5)
H2A	0.7522	0.7418	0.0082	0.091*
O3	0.0896 (2)	0.5561 (2)	0.16163 (12)	0.0587 (5)
O4	0.0454 (2)	0.4155 (2)	0.26474 (14)	0.0677 (5)
O5	0.5254 (3)	0.3544 (2)	0.43731 (14)	0.0751 (6)
O6	0.7907 (3)	0.5222 (3)	0.44086 (15)	0.0835 (7)
N1	0.5179 (2)	0.7115 (2)	0.04011 (13)	0.0455 (5)
N2	0.4009 (2)	0.6433 (2)	0.09896 (13)	0.0475 (5)
H2B	0.2886	0.6279	0.0881	0.057*
N3	0.1458 (3)	0.4964 (2)	0.21849 (14)	0.0488 (5)
N4	0.6333 (3)	0.4564 (3)	0.40639 (15)	0.0586 (6)
C1	0.8128 (4)	0.9926 (3)	−0.20335 (17)	0.0543 (6)
C2	0.8725 (3)	0.9207 (3)	−0.14189 (17)	0.0531 (6)
H2	0.9914	0.9254	−0.1386	0.064*
C3	0.7567 (3)	0.8418 (3)	−0.08513 (15)	0.0449 (5)
C4	0.5752 (3)	0.8332 (2)	−0.08865 (14)	0.0420 (5)
C5	0.5206 (3)	0.9046 (3)	−0.15349 (16)	0.0518 (6)
H5	0.4014	0.8988	−0.1587	0.062*
C6	0.6347 (4)	0.9830 (3)	−0.20983 (17)	0.0569 (6)
H6	0.5929	1.0292	−0.2520	0.068*
C7	0.4505 (3)	0.7573 (2)	−0.02643 (15)	0.0411 (5)
C8	0.4583 (3)	0.5995 (2)	0.17369 (15)	0.0410 (5)
C9	0.6413 (3)	0.6257 (3)	0.19676 (16)	0.0477 (6)
H9	0.7253	0.6747	0.1598	0.057*
C10	0.6973 (3)	0.5810 (3)	0.27173 (16)	0.0496 (6)
H10	0.8189	0.6020	0.2867	0.060*
C11	0.5733 (3)	0.5038 (3)	0.32605 (15)	0.0466 (6)
C12	0.3934 (3)	0.4741 (3)	0.30675 (16)	0.0474 (6)
H12	0.3112	0.4212	0.3430	0.057*
C13	0.3364 (3)	0.5241 (2)	0.23255 (15)	0.0420 (5)
C14	0.2557 (3)	0.7358 (3)	−0.04015 (18)	0.0570 (6)
H8A	0.2281	0.8119	0.0110	0.086*
H8B	0.1855	0.6289	−0.0391	0.086*
H8C	0.2284	0.7526	−0.1012	0.086*
O7	0.7850 (3)	1.2001 (2)	−0.36761 (14)	0.0889 (7)
N5	0.7922 (3)	1.1047 (3)	−0.52750 (15)	0.0649 (6)
C15	0.8120 (4)	1.2182 (3)	−0.44816 (18)	0.0595 (7)
H15	0.8505	1.3229	−0.4534	0.071*
C16	0.8313 (6)	1.1434 (6)	−0.6188 (2)	0.1163 (15)
H16A	0.8711	1.2576	−0.6084	0.174*
H16B	0.7249	1.0948	−0.6638	0.174*
H16C	0.9235	1.1032	−0.6445	0.174*
C17	0.7288 (7)	0.9375 (4)	−0.5270 (3)	0.1239 (15)
H17A	0.6983	0.9296	−0.4636	0.186*
H17B	0.8213	0.8922	−0.5439	0.186*
H17C	0.6248	0.8801	−0.5731	0.186*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0817 (14)	0.0814 (14)	0.0867 (14)	0.0332 (11)	0.0406 (11)	0.0471 (11)
O2	0.0495 (10)	0.0771 (12)	0.0691 (12)	0.0273 (9)	0.0118 (8)	0.0363 (10)
O3	0.0433 (10)	0.0763 (12)	0.0596 (10)	0.0209 (9)	0.0044 (8)	0.0230 (9)
O4	0.0473 (10)	0.0772 (12)	0.0839 (13)	0.0161 (9)	0.0228 (9)	0.0364 (10)
O5	0.0892 (15)	0.0759 (13)	0.0760 (13)	0.0311 (12)	0.0191 (11)	0.0434 (11)
O6	0.0645 (13)	0.1172 (18)	0.0811 (14)	0.0315 (12)	−0.0039 (11)	0.0480 (13)
N1	0.0470 (11)	0.0475 (10)	0.0434 (10)	0.0164 (9)	0.0085 (8)	0.0138 (8)
N2	0.0413 (11)	0.0549 (11)	0.0495 (11)	0.0163 (9)	0.0080 (9)	0.0191 (9)
N3	0.0401 (11)	0.0508 (11)	0.0523 (11)	0.0135 (9)	0.0105 (9)	0.0102 (9)
N4	0.0673 (15)	0.0657 (14)	0.0550 (12)	0.0332 (12)	0.0110 (11)	0.0230 (11)
C1	0.0635 (16)	0.0493 (13)	0.0510 (13)	0.0190 (12)	0.0175 (12)	0.0145 (11)
C2	0.0487 (14)	0.0542 (14)	0.0612 (14)	0.0224 (12)	0.0149 (11)	0.0166 (11)
C3	0.0471 (13)	0.0425 (12)	0.0444 (12)	0.0161 (10)	0.0039 (10)	0.0094 (10)
C4	0.0452 (13)	0.0411 (11)	0.0381 (11)	0.0151 (10)	0.0044 (9)	0.0074 (9)
C5	0.0503 (14)	0.0601 (14)	0.0479 (13)	0.0228 (12)	0.0026 (11)	0.0144 (11)
C6	0.0683 (17)	0.0630 (15)	0.0492 (13)	0.0289 (13)	0.0111 (12)	0.0235 (12)
C7	0.0409 (12)	0.0403 (11)	0.0382 (11)	0.0138 (10)	0.0010 (9)	0.0038 (9)
C8	0.0435 (12)	0.0376 (11)	0.0409 (11)	0.0155 (9)	0.0067 (9)	0.0063 (9)
C9	0.0436 (13)	0.0529 (13)	0.0466 (12)	0.0145 (11)	0.0124 (10)	0.0152 (10)
C10	0.0447 (13)	0.0562 (14)	0.0511 (13)	0.0216 (11)	0.0057 (11)	0.0139 (11)
C11	0.0546 (15)	0.0467 (13)	0.0432 (12)	0.0227 (11)	0.0081 (10)	0.0128 (10)
C12	0.0538 (14)	0.0413 (12)	0.0464 (12)	0.0153 (11)	0.0154 (10)	0.0109 (10)
C13	0.0400 (12)	0.0407 (12)	0.0442 (12)	0.0140 (10)	0.0079 (9)	0.0089 (9)
C14	0.0441 (14)	0.0728 (16)	0.0526 (14)	0.0161 (12)	0.0007 (11)	0.0190 (12)
O7	0.146 (2)	0.0820 (14)	0.0552 (11)	0.0520 (14)	0.0239 (12)	0.0291 (10)
N5	0.0743 (15)	0.0663 (14)	0.0563 (13)	0.0305 (12)	0.0104 (11)	0.0112 (11)
C15	0.0704 (18)	0.0541 (14)	0.0565 (15)	0.0206 (13)	0.0074 (13)	0.0201 (12)
C16	0.164 (4)	0.170 (4)	0.0591 (19)	0.107 (3)	0.038 (2)	0.041 (2)
C17	0.163 (4)	0.059 (2)	0.127 (3)	0.028 (2)	0.018 (3)	−0.003 (2)

Geometric parameters (Å, º)

O1—C1	1.358 (3)	C7—C14	1.496 (3)
O1—H1A	0.8200	C8—C9	1.411 (3)
O2—C3	1.347 (3)	C8—C13	1.420 (3)
O2—H2A	0.8200	C9—C10	1.358 (3)
O3—N3	1.237 (2)	C9—H9	0.9300
O4—N3	1.228 (2)	C10—C11	1.388 (3)
O5—N4	1.227 (3)	C10—H10	0.9300
O6—N4	1.229 (3)	C11—C12	1.373 (3)
N1—C7	1.303 (3)	C12—C13	1.381 (3)
N1—N2	1.372 (2)	C12—H12	0.9300
N2—C8	1.354 (3)	C14—H8A	0.9600
N2—H2B	0.8600	C14—H8B	0.9600
N3—C13	1.450 (3)	C14—H8C	0.9600
N4—C11	1.452 (3)	O7—C15	1.222 (3)
C1—C2	1.382 (3)	N5—C15	1.303 (3)
C1—C6	1.386 (4)	N5—C17	1.449 (4)
C2—C3	1.386 (3)	N5—C16	1.455 (4)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.415 (3)	C16—H16A	0.9600
C4—C5	1.397 (3)	C16—H16B	0.9600
C4—C7	1.469 (3)	C16—H16C	0.9600
C5—C6	1.373 (3)	C17—H17A	0.9600
C5—H5	0.9300	C17—H17B	0.9600
C6—H6	0.9300	C17—H17C	0.9600
C1—O1—H1A	109.5	C8—C9—H9	119.3
C3—O2—H2A	109.5	C9—C10—C11	120.1 (2)
C7—N1—N2	116.62 (19)	C9—C10—H10	119.9
C8—N2—N1	121.46 (19)	C11—C10—H10	119.9
C8—N2—H2B	119.3	C12—C11—C10	121.2 (2)
N1—N2—H2B	119.3	C12—C11—N4	118.7 (2)
O4—N3—O3	121.99 (19)	C10—C11—N4	120.1 (2)
O4—N3—C13	118.6 (2)	C11—C12—C13	118.9 (2)
O3—N3—C13	119.41 (18)	C11—C12—H12	120.6
O5—N4—O6	123.0 (2)	C13—C12—H12	120.6
O5—N4—C11	119.0 (2)	C12—C13—C8	121.6 (2)
O6—N4—C11	117.9 (2)	C12—C13—N3	116.44 (19)
O1—C1—C2	117.7 (2)	C8—C13—N3	121.92 (19)
O1—C1—C6	122.5 (2)	C7—C14—H8A	109.5
C2—C1—C6	119.8 (2)	C7—C14—H8B	109.5
C1—C2—C3	120.6 (2)	H8A—C14—H8B	109.5
C1—C2—H2	119.7	C7—C14—H8C	109.5
C3—C2—H2	119.7	H8A—C14—H8C	109.5
O2—C3—C2	116.7 (2)	H8B—C14—H8C	109.5
O2—C3—C4	122.5 (2)	C15—N5—C17	120.8 (3)
C2—C3—C4	120.8 (2)	C15—N5—C16	120.5 (3)
C5—C4—C3	116.3 (2)	C17—N5—C16	118.6 (3)
C5—C4—C7	121.2 (2)	O7—C15—N5	126.2 (3)
C3—C4—C7	122.48 (19)	O7—C15—H15	116.9
C6—C5—C4	123.1 (2)	N5—C15—H15	116.9
C6—C5—H5	118.5	N5—C16—H16A	109.5
C4—C5—H5	118.5	N5—C16—H16B	109.5
C5—C6—C1	119.4 (2)	H16A—C16—H16B	109.5
C5—C6—H6	120.3	N5—C16—H16C	109.5
C1—C6—H6	120.3	H16A—C16—H16C	109.5
N1—C7—C4	117.0 (2)	H16B—C16—H16C	109.5
N1—C7—C14	122.6 (2)	N5—C17—H17A	109.5
C4—C7—C14	120.38 (19)	N5—C17—H17B	109.5
N2—C8—C9	121.9 (2)	H17A—C17—H17B	109.5
N2—C8—C13	121.4 (2)	N5—C17—H17C	109.5
C9—C8—C13	116.72 (19)	H17A—C17—H17C	109.5
C10—C9—C8	121.4 (2)	H17B—C17—H17C	109.5
C10—C9—H9	119.3
C7—N1—N2—C8	−176.36 (19)	C13—C8—C9—C10	−0.1 (3)
O1—C1—C2—C3	177.7 (2)	C8—C9—C10—C11	1.7 (3)
C6—C1—C2—C3	−1.3 (4)	C9—C10—C11—C12	−1.3 (3)
C1—C2—C3—O2	179.3 (2)	C9—C10—C11—N4	−179.8 (2)
C1—C2—C3—C4	−0.1 (3)	O5—N4—C11—C12	20.2 (3)
O2—C3—C4—C5	−177.8 (2)	O6—N4—C11—C12	−159.2 (2)
C2—C3—C4—C5	1.5 (3)	O5—N4—C11—C10	−161.3 (2)
O2—C3—C4—C7	3.6 (3)	O6—N4—C11—C10	19.4 (3)
C2—C3—C4—C7	−177.1 (2)	C10—C11—C12—C13	−0.8 (3)
C3—C4—C5—C6	−1.6 (3)	N4—C11—C12—C13	177.74 (19)
C7—C4—C5—C6	177.0 (2)	C11—C12—C13—C8	2.5 (3)
C4—C5—C6—C1	0.2 (4)	C11—C12—C13—N3	−177.15 (19)
O1—C1—C6—C5	−177.6 (2)	N2—C8—C13—C12	177.70 (19)
C2—C1—C6—C5	1.3 (4)	C9—C8—C13—C12	−2.1 (3)
N2—N1—C7—C4	178.92 (17)	N2—C8—C13—N3	−2.7 (3)
N2—N1—C7—C14	−0.8 (3)	C9—C8—C13—N3	177.56 (19)
C5—C4—C7—N1	−171.7 (2)	O4—N3—C13—C12	−8.1 (3)
C3—C4—C7—N1	6.8 (3)	O3—N3—C13—C12	170.96 (19)
C5—C4—C7—C14	8.0 (3)	O4—N3—C13—C8	172.25 (19)
C3—C4—C7—C14	−173.4 (2)	O3—N3—C13—C8	−8.7 (3)
N1—N2—C8—C9	1.8 (3)	C17—N5—C15—O7	1.5 (5)
N1—N2—C8—C13	−177.93 (18)	C16—N5—C15—O7	−179.3 (3)
N2—C8—C9—C10	−179.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7	0.82	1.86	2.677 (3)	175
O2—H2A···N1	0.82	1.88	2.590 (2)	146
N2—H2B···O3	0.86	1.94	2.590 (2)	131

(XII) 2,4-dihydroxybenzophenone 2,4-dinitrophenylhydrazone N,N-dimethylformamide solvate

Crystal data

C19H14N4O6·C4H9NO	Z = 2
Mr = 481.46	F(000) = 504
Triclinic, P1	Dx = 1.343 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8155 (9) Å	Cell parameters from 50 reflections
b = 11.549 (2) Å	θ = 6.3–20.7°
c = 13.904 (2) Å	µ = 0.10 mm^−1
α = 100.38 (1)°	T = 293 K
β = 95.80 (1)°	Parallelepiped, red-orange
γ = 102.74 (1)°	0.50 × 0.38 × 0.38 mm
V = 1191.0 (3) Å^3

Data collection

Siemens Bruker P4 diffractometer	Rint = 0.013
Radiation source: normal-focus sealed tube	θmax = 25.1°, θmin = 1.9°
Graphite monochromator	h = −1→9
θ/2θ scans	k = −13→13
5472 measured reflections	l = −16→16
4175 independent reflections	3 standard reflections every 50 reflections
2517 reflections with I > 2σ(I)	intensity decay: 1.7%

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)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.171	w = 1/[σ^2(Fo^2) + (0.0921P)^2 + 0.1171P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4153 reflections	Δρmax = 0.51 e Å^−3
322 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.025 (4)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 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
O1	−0.0917 (2)	0.85518 (18)	0.88073 (15)	0.0696 (6)
H1A	−0.1408	0.7856	0.8516	0.104*
O2	0.3744 (2)	0.75907 (14)	0.71470 (15)	0.0600 (5)
H2A	0.4668	0.7919	0.6973	0.090*
O3	1.0752 (3)	1.16489 (18)	0.68486 (17)	0.0780 (6)
O4	1.2959 (3)	1.1313 (2)	0.61352 (18)	0.0860 (7)
O5	1.3489 (4)	0.7414 (3)	0.47710 (19)	0.1036 (9)
O6	1.1203 (5)	0.5896 (3)	0.4476 (3)	0.1322 (12)
N1	0.6439 (3)	0.93863 (18)	0.71068 (15)	0.0504 (5)
N2	0.8051 (3)	0.98722 (18)	0.68505 (16)	0.0536 (5)
H2B	0.8495	1.0642	0.7026	0.064*
N3	1.1508 (3)	1.0953 (2)	0.63832 (18)	0.0607 (6)
N4	1.1946 (5)	0.6961 (3)	0.4824 (2)	0.0863 (9)
C1	0.0719 (3)	0.8868 (2)	0.85512 (18)	0.0518 (6)
C2	0.1461 (3)	0.8052 (2)	0.79855 (18)	0.0495 (6)
H2	0.0845	0.7242	0.7785	0.059*
C3	0.3120 (3)	0.8436 (2)	0.77159 (18)	0.0466 (6)
C4	0.4087 (3)	0.9661 (2)	0.80232 (17)	0.0457 (6)
C5	0.3297 (3)	1.0445 (2)	0.86099 (19)	0.0547 (7)
H5	0.3912	1.1253	0.8831	0.066*
C6	0.1655 (4)	1.0074 (3)	0.8873 (2)	0.0597 (7)
H6	0.1169	1.0623	0.9264	0.072*
C7	0.5811 (3)	1.0113 (2)	0.77263 (17)	0.0448 (6)
C8	0.8960 (3)	0.9176 (2)	0.63307 (17)	0.0467 (6)
C9	0.8263 (4)	0.7911 (2)	0.59983 (19)	0.0566 (7)
H9	0.7135	0.7557	0.6116	0.068*
C10	0.9212 (4)	0.7200 (3)	0.5508 (2)	0.0631 (7)
H10	0.8738	0.6368	0.5302	0.076*
C11	1.0894 (4)	0.7723 (3)	0.5317 (2)	0.0608 (7)
C12	1.1614 (4)	0.8936 (3)	0.56060 (19)	0.0584 (7)
H12	1.2739	0.9270	0.5472	0.070*
C13	1.0668 (3)	0.9669 (2)	0.60987 (18)	0.0486 (6)
C14	0.6808 (3)	1.1406 (2)	0.81436 (18)	0.0465 (6)
C15	0.6833 (4)	1.2285 (2)	0.7587 (2)	0.0575 (7)
H15	0.6204	1.2085	0.6951	0.069*
C16	0.7792 (4)	1.3461 (3)	0.7976 (2)	0.0692 (8)
H16	0.7800	1.4053	0.7602	0.083*
C17	0.8731 (4)	1.3761 (3)	0.8906 (2)	0.0748 (9)
H17	0.9377	1.4555	0.9163	0.090*
C18	0.8721 (5)	1.2890 (3)	0.9462 (2)	0.0808 (10)
H18	0.9361	1.3097	1.0095	0.097*
C19	0.7766 (4)	1.1711 (2)	0.9087 (2)	0.0645 (8)
H19	0.7765	1.1122	0.9464	0.077*
O7	−0.2812 (3)	0.63959 (19)	0.78644 (17)	0.0800 (7)
N5	−0.5480 (4)	0.5175 (3)	0.7565 (3)	0.1017 (11)
C20	−0.4245 (5)	0.5980 (3)	0.8137 (3)	0.0830 (10)
C21	−0.4541 (6)	0.6467 (4)	0.9208 (3)	0.1134 (14)
H21A	−0.3421	0.6887	0.9602	0.170*
H21B	−0.5085	0.5800	0.9488	0.170*
H21C	−0.5302	0.7015	0.9197	0.170*
C22	−0.5264 (6)	0.4805 (3)	0.6525 (3)	0.1085 (14)
H22A	−0.4041	0.5078	0.6450	0.163*
H22B	−0.5981	0.5160	0.6119	0.163*
H22C	−0.5628	0.3937	0.6327	0.163*
C23	−0.7257 (6)	0.4719 (4)	0.7852 (5)	0.158 (2)
H23A	−0.7244	0.5056	0.8537	0.237*
H23B	−0.7525	0.3850	0.7749	0.237*
H23C	−0.8143	0.4958	0.7456	0.237*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0572 (12)	0.0733 (13)	0.0722 (13)	0.0057 (10)	0.0248 (10)	0.0035 (10)
O2	0.0555 (11)	0.0406 (9)	0.0846 (13)	0.0124 (8)	0.0235 (10)	0.0068 (9)
O3	0.0700 (14)	0.0516 (12)	0.1065 (17)	0.0032 (10)	0.0221 (12)	0.0106 (11)
O4	0.0540 (12)	0.0851 (15)	0.1169 (18)	−0.0049 (11)	0.0223 (12)	0.0372 (13)
O5	0.0955 (19)	0.128 (2)	0.1073 (19)	0.0483 (17)	0.0591 (16)	0.0259 (16)
O6	0.162 (3)	0.0796 (19)	0.169 (3)	0.0409 (19)	0.095 (2)	0.0092 (19)
N1	0.0414 (11)	0.0461 (12)	0.0605 (13)	0.0055 (9)	0.0099 (10)	0.0073 (10)
N2	0.0460 (12)	0.0435 (11)	0.0668 (14)	0.0049 (9)	0.0124 (10)	0.0049 (10)
N3	0.0487 (14)	0.0606 (14)	0.0705 (16)	0.0008 (12)	0.0034 (12)	0.0260 (12)
N4	0.105 (2)	0.092 (2)	0.0827 (19)	0.0447 (19)	0.0479 (18)	0.0266 (17)
C1	0.0466 (14)	0.0626 (17)	0.0458 (14)	0.0088 (12)	0.0110 (11)	0.0139 (12)
C2	0.0508 (15)	0.0438 (13)	0.0520 (14)	0.0055 (11)	0.0068 (12)	0.0129 (11)
C3	0.0469 (14)	0.0474 (14)	0.0480 (13)	0.0138 (11)	0.0069 (11)	0.0137 (11)
C4	0.0460 (14)	0.0438 (13)	0.0443 (13)	0.0071 (11)	0.0040 (11)	0.0076 (10)
C5	0.0558 (16)	0.0457 (14)	0.0575 (16)	0.0070 (12)	0.0131 (13)	0.0011 (12)
C6	0.0597 (17)	0.0605 (17)	0.0557 (16)	0.0145 (14)	0.0176 (13)	−0.0014 (13)
C7	0.0438 (13)	0.0446 (13)	0.0454 (13)	0.0111 (11)	0.0026 (11)	0.0096 (11)
C8	0.0451 (14)	0.0512 (14)	0.0446 (13)	0.0117 (11)	0.0051 (11)	0.0126 (11)
C9	0.0526 (15)	0.0519 (15)	0.0607 (16)	0.0056 (12)	0.0119 (13)	0.0072 (13)
C10	0.0743 (19)	0.0537 (16)	0.0596 (17)	0.0161 (14)	0.0148 (15)	0.0042 (13)
C11	0.0695 (18)	0.0697 (19)	0.0544 (16)	0.0293 (15)	0.0255 (14)	0.0173 (14)
C12	0.0514 (16)	0.078 (2)	0.0550 (16)	0.0204 (14)	0.0163 (13)	0.0273 (14)
C13	0.0450 (13)	0.0566 (15)	0.0482 (14)	0.0118 (12)	0.0061 (11)	0.0221 (12)
C14	0.0419 (13)	0.0442 (13)	0.0506 (14)	0.0089 (10)	0.0058 (11)	0.0048 (11)
C15	0.0597 (17)	0.0495 (15)	0.0606 (16)	0.0113 (13)	0.0024 (13)	0.0103 (13)
C16	0.077 (2)	0.0491 (16)	0.081 (2)	0.0128 (15)	0.0115 (17)	0.0166 (15)
C17	0.077 (2)	0.0504 (17)	0.079 (2)	−0.0050 (15)	0.0074 (18)	−0.0051 (15)
C18	0.089 (2)	0.070 (2)	0.0605 (18)	−0.0067 (18)	−0.0072 (17)	−0.0023 (16)
C19	0.0702 (19)	0.0559 (16)	0.0592 (17)	0.0029 (14)	−0.0014 (14)	0.0122 (13)
O7	0.0623 (13)	0.0670 (13)	0.1046 (17)	0.0009 (10)	0.0322 (12)	0.0091 (11)
N5	0.077 (2)	0.0558 (16)	0.169 (3)	0.0126 (15)	0.015 (2)	0.0208 (19)
C20	0.075 (2)	0.0539 (18)	0.122 (3)	0.0144 (17)	0.013 (2)	0.0262 (19)
C21	0.118 (3)	0.120 (3)	0.104 (3)	0.015 (3)	0.055 (3)	0.026 (3)
C22	0.119 (3)	0.076 (2)	0.111 (3)	0.025 (2)	−0.006 (3)	−0.022 (2)
C23	0.076 (3)	0.103 (3)	0.280 (7)	−0.014 (2)	0.056 (4)	0.027 (4)

Geometric parameters (Å, º)

O1—C1	1.352 (3)	C10—H10	0.9300
O1—H1A	0.8200	C11—C12	1.358 (4)
O2—C3	1.351 (3)	C12—C13	1.380 (4)
O2—H2A	0.8200	C12—H12	0.9300
O3—N3	1.230 (3)	C14—C15	1.381 (4)
O4—N3	1.225 (3)	C14—C19	1.387 (4)
O5—N4	1.219 (4)	C15—C16	1.380 (4)
O6—N4	1.225 (4)	C15—H15	0.9300
N1—C7	1.302 (3)	C16—C17	1.366 (4)
N1—N2	1.371 (3)	C16—H16	0.9300
N2—C8	1.348 (3)	C17—C18	1.374 (4)
N2—H2B	0.8600	C17—H17	0.9300
N3—C13	1.447 (3)	C18—C19	1.379 (4)
N4—C11	1.461 (4)	C18—H18	0.9300
C1—C2	1.382 (3)	C19—H19	0.9300
C1—C6	1.391 (4)	O7—C20	1.242 (4)
C2—C3	1.386 (3)	N5—C20	1.268 (4)
C2—H2	0.9300	N5—C22	1.470 (5)
C3—C4	1.414 (3)	N5—C23	1.494 (5)
C4—C5	1.396 (3)	C20—C21	1.554 (5)
C4—C7	1.462 (3)	C21—H21A	0.9600
C5—C6	1.369 (4)	C21—H21B	0.9600
C5—H5	0.9300	C21—H21C	0.9600
C6—H6	0.9300	C22—H22A	0.9600
C7—C14	1.502 (3)	C22—H22B	0.9600
C8—C9	1.415 (4)	C22—H22C	0.9600
C8—C13	1.424 (3)	C23—H23A	0.9600
C9—C10	1.363 (4)	C23—H23B	0.9600
C9—H9	0.9300	C23—H23C	0.9600
C10—C11	1.393 (4)
C1—O1—H1A	109.5	C13—C12—H12	120.2
C3—O2—H2A	109.5	C12—C13—C8	121.3 (2)
C7—N1—N2	116.17 (19)	C12—C13—N3	116.8 (2)
C8—N2—N1	121.8 (2)	C8—C13—N3	121.9 (2)
C8—N2—H2B	119.1	C15—C14—C19	119.6 (2)
N1—N2—H2B	119.1	C15—C14—C7	120.8 (2)
O4—N3—O3	122.0 (2)	C19—C14—C7	119.5 (2)
O4—N3—C13	118.1 (3)	C16—C15—C14	119.9 (3)
O3—N3—C13	119.9 (2)	C16—C15—H15	120.1
O5—N4—O6	123.7 (3)	C14—C15—H15	120.1
O5—N4—C11	119.1 (3)	C17—C16—C15	120.4 (3)
O6—N4—C11	117.2 (3)	C17—C16—H16	119.8
O1—C1—C2	122.7 (2)	C15—C16—H16	119.8
O1—C1—C6	117.3 (2)	C16—C17—C18	120.0 (3)
C2—C1—C6	120.0 (2)	C16—C17—H17	120.0
C1—C2—C3	120.3 (2)	C18—C17—H17	120.0
C1—C2—H2	119.9	C17—C18—C19	120.4 (3)
C3—C2—H2	119.9	C17—C18—H18	119.8
O2—C3—C2	116.9 (2)	C19—C18—H18	119.8
O2—C3—C4	122.4 (2)	C18—C19—C14	119.7 (3)
C2—C3—C4	120.8 (2)	C18—C19—H19	120.2
C5—C4—C3	116.8 (2)	C14—C19—H19	120.2
C5—C4—C7	120.6 (2)	C20—N5—C22	118.7 (3)
C3—C4—C7	122.5 (2)	C20—N5—C23	123.1 (4)
C6—C5—C4	122.7 (2)	C22—N5—C23	117.5 (4)
C6—C5—H5	118.7	O7—C20—N5	122.1 (4)
C4—C5—H5	118.7	O7—C20—C21	119.0 (3)
C5—C6—C1	119.4 (2)	N5—C20—C21	119.0 (4)
C5—C6—H6	120.3	C20—C21—H21A	109.5
C1—C6—H6	120.3	C20—C21—H21B	109.5
N1—C7—C4	119.2 (2)	H21A—C21—H21B	109.5
N1—C7—C14	121.8 (2)	C20—C21—H21C	109.5
C4—C7—C14	119.1 (2)	H21A—C21—H21C	109.5
N2—C8—C9	121.3 (2)	H21B—C21—H21C	109.5
N2—C8—C13	122.1 (2)	N5—C22—H22A	109.5
C9—C8—C13	116.7 (2)	N5—C22—H22B	109.5
C10—C9—C8	121.3 (3)	H22A—C22—H22B	109.5
C10—C9—H9	119.4	N5—C22—H22C	109.5
C8—C9—H9	119.4	H22A—C22—H22C	109.5
C9—C10—C11	119.8 (3)	H22B—C22—H22C	109.5
C9—C10—H10	120.1	N5—C23—H23A	109.5
C11—C10—H10	120.1	N5—C23—H23B	109.5
C12—C11—C10	121.3 (3)	H23A—C23—H23B	109.5
C12—C11—N4	118.5 (3)	N5—C23—H23C	109.5
C10—C11—N4	120.2 (3)	H23A—C23—H23C	109.5
C11—C12—C13	119.6 (3)	H23B—C23—H23C	109.5
C11—C12—H12	120.2
C7—N1—N2—C8	170.4 (2)	O6—N4—C11—C10	9.6 (4)
O1—C1—C2—C3	177.8 (2)	C10—C11—C12—C13	0.0 (4)
C6—C1—C2—C3	−1.6 (4)	N4—C11—C12—C13	−178.1 (2)
C1—C2—C3—O2	−178.8 (2)	C11—C12—C13—C8	1.4 (4)
C1—C2—C3—C4	0.8 (4)	C11—C12—C13—N3	−179.8 (2)
O2—C3—C4—C5	−180.0 (2)	N2—C8—C13—C12	177.0 (2)
C2—C3—C4—C5	0.5 (4)	C9—C8—C13—C12	−2.3 (4)
O2—C3—C4—C7	1.8 (4)	N2—C8—C13—N3	−1.8 (4)
C2—C3—C4—C7	−177.7 (2)	C9—C8—C13—N3	178.9 (2)
C3—C4—C5—C6	−1.0 (4)	O4—N3—C13—C12	3.0 (3)
C7—C4—C5—C6	177.3 (2)	O3—N3—C13—C12	−178.0 (2)
C4—C5—C6—C1	0.2 (4)	O4—N3—C13—C8	−178.2 (2)
O1—C1—C6—C5	−178.3 (2)	O3—N3—C13—C8	0.8 (4)
C2—C1—C6—C5	1.1 (4)	N1—C7—C14—C15	77.5 (3)
N2—N1—C7—C4	179.3 (2)	C4—C7—C14—C15	−102.4 (3)
N2—N1—C7—C14	−0.6 (3)	N1—C7—C14—C19	−100.2 (3)
C5—C4—C7—N1	−173.8 (2)	C4—C7—C14—C19	79.9 (3)
C3—C4—C7—N1	4.4 (4)	C19—C14—C15—C16	−0.7 (4)
C5—C4—C7—C14	6.1 (3)	C7—C14—C15—C16	−178.4 (2)
C3—C4—C7—C14	−175.7 (2)	C14—C15—C16—C17	0.5 (5)
N1—N2—C8—C9	1.9 (4)	C15—C16—C17—C18	−0.1 (5)
N1—N2—C8—C13	−177.3 (2)	C16—C17—C18—C19	0.0 (5)
N2—C8—C9—C10	−177.3 (2)	C17—C18—C19—C14	−0.2 (5)
C13—C8—C9—C10	2.0 (4)	C15—C14—C19—C18	0.6 (4)
C8—C9—C10—C11	−0.7 (4)	C7—C14—C19—C18	178.3 (3)
C9—C10—C11—C12	−0.3 (4)	C22—N5—C20—O7	−5.5 (5)
C9—C10—C11—N4	177.8 (3)	C23—N5—C20—O7	−175.9 (4)
O5—N4—C11—C12	6.9 (4)	C22—N5—C20—C21	174.0 (3)
O6—N4—C11—C12	−172.2 (3)	C23—N5—C20—C21	3.6 (5)
O5—N4—C11—C10	−171.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7	0.82	1.82	2.630 (3)	172
O2—H2A···N1	0.82	1.90	2.623 (3)	146
N2—H2B···O3	0.86	1.95	2.600 (3)	131