4,5-Di­azafluoren-9-one benzoyl­hydrazone monohydrate

The title compound, C₁₈H₁₂N₄O·H₂O, adopts the keto tautomeric form and the azomethine C=N double bond is in the E configuration. The dihedral angle between the planes of the di­aza­fluorene moiety and the phenyl ring is 11.3 (1)°. In the solid state, the mol­ecules form infinite chain-like structures via O-H...N hydrogen bonds involving the water mol­ecules and di­aza­fluorene moieties.

S1. Comment

Aroylhydrazones have continued to attract extensive attention of chemists because of their wide biological activities and their strong abilities to chelate to transition metal ions, lanthanide metal ions and main group metal ions forming metal complexes (Fun et al., 1999; Lu et al., 1999; Sangeetha et al., 1996; Ainscough et al., 1998). On the other hand, 4,5-diazafluoren-9-one and its derivatives are also strong chelating agents and has been used as ligands to form functional ruthenium complexes (Chao et al., 1999). The combination of the two functional group yielding ligands capable of forming polymetallic complexes would therefore be of interest for their potential multi-redox, catalytic, electronic and energy transfer properties. As part of studies on the synthesis and characterization of new aroylhydrazone derivatives, we report here the crystal structure of 4,5-diaza-9-fluorenone benzoylhydrazone monohydrate, (I). \sch

The bond lengths and angles observed in this structure are normal and comparable to those found in the structures of other benzoylhydrazine (Fun et al., 1997) and 4,5-diazafluorene derivatives (Lu et al., 1996). The molecule is in keto tautomeric form. The dihedral angles between the diazafluorene moiety and the phenyl ring is 11.3 (1)°, and the two fragments make 13.2 (1) and 23.2 (1)°, respectively, with the cetral hydrazone moiety. In the solid state, the molecules form infinite chain-like structures via O—H···N hydrogen bonds involving the water molecules and diazafluorene moieties.

We have observed previously that due to the possibility of different charge concentrations between the two pyridinyl N atoms of the diazaflurene moiety, the one with greater charge is involved in the stronger hydrogen bonds, whereas the other may be involved in only a weak interaction (Fun et al., 1995; Lu et al., 1995). But in this structure, both the N atoms are involved in a similar type of O—H···N hydrogen bond with the water molecule. We also note that the aroylhydrazine derivatives crystallize in hydrated forms only.

S2. Experimental

The synthesis of the compound was carried out by reaction of 4,5-diazafluren-9-one and benzoylhydrazine in ethanol solution under reflux for 5 h. Single crystals were obtained by recrystallization from ethanol.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).

Figures

Fig. 1. The structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.

4,5-Diaza-9-fluorenone Benzoylhydrazone Monohydrate

Crystal data

C18H12N4O·H2O	F(000) = 664
Mr = 318.33	Dx = 1.375 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.4880 (2) Å	Cell parameters from 3585 reflections
b = 22.7523 (2) Å	θ = 1.8–28.3°
c = 8.7810 (2) Å	µ = 0.09 mm^−1
β = 114.929 (1)°	T = 293 K
V = 1537.80 (5) Å^3	Needle, yellow
Z = 4	0.38 × 0.18 × 0.12 mm

Data collection

Siemens SMART CCD area detector diffractometer	1870 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.078
Graphite monochromator	θmax = 28.3°, θmin = 1.8°
Detector resolution: 8.33 pixels mm^-1	h = −9→11
ω scans	k = −29→27
10723 measured reflections	l = −11→11
3729 independent reflections

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)] = 0.061	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0695P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max < 0.001
3729 reflections	Δρmax = 0.29 e Å^−3
226 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (2)

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.

The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was −35°. Coverage of the unique set is over 99% complete. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

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

	x	y	z	Uiso*/Ueq
N1	1.2290 (2)	0.57696 (9)	−0.1370 (2)	0.0388 (5)
N2	1.2709 (2)	0.52004 (8)	0.1917 (2)	0.0379 (5)
N3	0.7533 (2)	0.64431 (9)	−0.0334 (2)	0.0394 (5)
N4	0.6726 (2)	0.64123 (9)	0.0728 (3)	0.0422 (5)
H4A	0.7005	0.6151	0.1506	0.051*
O1	0.5059 (2)	0.71954 (9)	−0.0606 (2)	0.0633 (6)
C1	1.1873 (3)	0.61027 (11)	−0.2742 (3)	0.0474 (7)
H1A	1.2598	0.6086	−0.3293	0.057*
C2	1.0443 (4)	0.64703 (12)	−0.3401 (3)	0.0511 (7)
H2A	1.0233	0.6691	−0.4359	0.061*
C3	0.9327 (3)	0.65059 (11)	−0.2620 (3)	0.0444 (6)
H3A	0.8347	0.6745	−0.3039	0.053*
C4	0.9730 (3)	0.61730 (10)	−0.1199 (3)	0.0339 (5)
C5	0.8896 (3)	0.61279 (10)	−0.0029 (3)	0.0343 (5)
C6	1.0022 (3)	0.57315 (10)	0.1337 (3)	0.0318 (5)
C7	1.0036 (3)	0.55506 (11)	0.2851 (3)	0.0406 (6)
H7A	0.9170	0.5665	0.3174	0.049*
C8	1.1394 (3)	0.51917 (11)	0.3863 (3)	0.0445 (6)
H8A	1.1458	0.5065	0.4895	0.053*
C9	1.2649 (3)	0.50218 (11)	0.3345 (3)	0.0434 (6)
H9A	1.3512	0.4766	0.4032	0.052*
C10	1.1398 (3)	0.55455 (10)	0.0955 (3)	0.0306 (5)
C11	1.1208 (3)	0.58223 (10)	−0.0623 (3)	0.0328 (5)
C12	0.5447 (3)	0.68221 (11)	0.0484 (3)	0.0420 (6)
C13	0.4626 (3)	0.68010 (10)	0.1692 (3)	0.0416 (6)
C14	0.3023 (3)	0.70743 (11)	0.1213 (4)	0.0505 (7)
H14A	0.2461	0.7235	0.0143	0.061*
C15	0.2264 (4)	0.71070 (12)	0.2336 (4)	0.0612 (8)
H15A	0.1180	0.7283	0.2007	0.073*
C16	0.3093 (4)	0.68845 (13)	0.3912 (5)	0.0650 (8)
H16A	0.2591	0.6922	0.4665	0.078*
C17	0.4663 (4)	0.66050 (13)	0.4403 (4)	0.0638 (8)
H17A	0.5206	0.6443	0.5473	0.077*
C18	0.5440 (3)	0.65644 (12)	0.3289 (4)	0.0529 (7)
H18A	0.6508	0.6378	0.3620	0.063*
O1W	0.6154 (2)	0.52798 (9)	0.1980 (2)	0.0484 (5)
H1W1	0.636 (4)	0.4933 (15)	0.152 (4)	0.089 (11)*
H2W1	0.502 (5)	0.5253 (15)	0.173 (5)	0.113 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0433 (12)	0.0411 (12)	0.0456 (12)	0.0036 (9)	0.0320 (10)	0.0005 (10)
N2	0.0332 (11)	0.0428 (12)	0.0416 (11)	0.0027 (8)	0.0197 (9)	0.0055 (10)
N3	0.0401 (11)	0.0409 (12)	0.0502 (12)	0.0060 (9)	0.0317 (10)	0.0010 (9)
N4	0.0427 (12)	0.0445 (13)	0.0538 (13)	0.0100 (9)	0.0342 (11)	0.0072 (10)
O1	0.0689 (13)	0.0576 (13)	0.0865 (14)	0.0240 (10)	0.0553 (11)	0.0231 (11)
C1	0.0580 (17)	0.0518 (17)	0.0535 (16)	0.0043 (13)	0.0440 (14)	0.0063 (14)
C2	0.0686 (18)	0.0507 (17)	0.0481 (15)	0.0073 (13)	0.0384 (14)	0.0121 (13)
C3	0.0531 (15)	0.0413 (15)	0.0479 (15)	0.0120 (11)	0.0301 (13)	0.0091 (12)
C4	0.0375 (13)	0.0341 (13)	0.0386 (13)	0.0032 (10)	0.0245 (11)	0.0004 (11)
C5	0.0355 (13)	0.0349 (13)	0.0404 (13)	0.0000 (10)	0.0237 (11)	−0.0005 (11)
C6	0.0327 (12)	0.0327 (13)	0.0365 (12)	−0.0012 (9)	0.0209 (10)	−0.0020 (10)
C7	0.0383 (13)	0.0521 (16)	0.0412 (14)	−0.0023 (11)	0.0264 (12)	0.0011 (12)
C8	0.0433 (15)	0.0568 (17)	0.0360 (13)	−0.0072 (12)	0.0193 (12)	0.0054 (12)
C9	0.0369 (13)	0.0486 (16)	0.0434 (14)	0.0028 (11)	0.0157 (12)	0.0110 (12)
C10	0.0311 (12)	0.0315 (12)	0.0332 (12)	−0.0007 (9)	0.0175 (10)	−0.0022 (10)
C11	0.0363 (13)	0.0324 (13)	0.0391 (13)	−0.0006 (10)	0.0252 (11)	−0.0022 (10)
C12	0.0416 (14)	0.0366 (15)	0.0598 (17)	0.0030 (11)	0.0332 (13)	−0.0007 (13)
C13	0.0378 (13)	0.0358 (14)	0.0632 (17)	−0.0030 (10)	0.0331 (13)	−0.0100 (12)
C14	0.0474 (15)	0.0357 (15)	0.083 (2)	0.0016 (11)	0.0422 (15)	−0.0045 (13)
C15	0.0539 (17)	0.0458 (17)	0.111 (3)	0.0034 (13)	0.0617 (19)	−0.0010 (18)
C16	0.076 (2)	0.0556 (19)	0.098 (2)	−0.0038 (16)	0.070 (2)	−0.0063 (18)
C17	0.072 (2)	0.071 (2)	0.070 (2)	0.0039 (16)	0.0511 (18)	0.0004 (16)
C18	0.0453 (15)	0.0640 (19)	0.0588 (17)	0.0076 (13)	0.0312 (14)	−0.0038 (15)
O1W	0.0393 (11)	0.0476 (12)	0.0678 (13)	0.0062 (8)	0.0318 (10)	0.0010 (10)

Geometric parameters (Å, º)

N1—C1	1.339 (3)	C7—C8	1.386 (3)
N1—C11	1.340 (3)	C7—H7A	0.9300
N2—C10	1.332 (3)	C8—C9	1.379 (3)
N2—C9	1.339 (3)	C8—H8A	0.9300
N3—C5	1.290 (3)	C9—H9A	0.9300
N3—N4	1.371 (3)	C10—C11	1.467 (3)
N4—C12	1.378 (3)	C12—C13	1.496 (3)
N4—H4A	0.8600	C13—C18	1.384 (4)
O1—C12	1.216 (3)	C13—C14	1.390 (3)
C1—C2	1.384 (4)	C14—C15	1.390 (4)
C1—H1A	0.9300	C14—H14A	0.9300
C2—C3	1.387 (3)	C15—C16	1.358 (4)
C2—H2A	0.9300	C15—H15A	0.9300
C3—C4	1.374 (3)	C16—C17	1.372 (4)
C3—H3A	0.9300	C16—H16A	0.9300
C4—C11	1.390 (3)	C17—C18	1.394 (4)
C4—C5	1.476 (3)	C17—H17A	0.9300
C5—C6	1.483 (3)	C18—H18A	0.9300
C6—C7	1.387 (3)	O1W—H1W1	0.94 (4)
C6—C10	1.410 (3)	O1W—H2W1	0.90 (4)
C1—N1—C11	114.5 (2)	N2—C9—H9A	117.9
C10—N2—C9	114.97 (19)	C8—C9—H9A	117.9
C5—N3—N4	119.4 (2)	N2—C10—C6	125.4 (2)
N3—N4—C12	116.5 (2)	N2—C10—C11	125.61 (19)
N3—N4—H4A	121.8	C6—C10—C11	108.87 (19)
C12—N4—H4A	121.8	N1—C11—C4	125.0 (2)
N1—C1—C2	124.8 (2)	N1—C11—C10	126.7 (2)
N1—C1—H1A	117.6	C4—C11—C10	108.27 (18)
C2—C1—H1A	117.6	O1—C12—N4	122.0 (2)
C1—C2—C3	119.3 (2)	O1—C12—C13	121.8 (2)
C1—C2—H2A	120.3	N4—C12—C13	116.1 (2)
C3—C2—H2A	120.3	C18—C13—C14	119.2 (2)
C4—C3—C2	117.2 (2)	C18—C13—C12	123.3 (2)
C4—C3—H3A	121.4	C14—C13—C12	117.4 (2)
C2—C3—H3A	121.4	C15—C14—C13	119.8 (3)
C3—C4—C11	119.2 (2)	C15—C14—H14A	120.1
C3—C4—C5	131.4 (2)	C13—C14—H14A	120.1
C11—C4—C5	109.31 (19)	C16—C15—C14	120.5 (3)
N3—C5—C4	117.9 (2)	C16—C15—H15A	119.8
N3—C5—C6	136.2 (2)	C14—C15—H15A	119.8
C4—C5—C6	105.69 (18)	C15—C16—C17	120.7 (3)
C7—C6—C10	117.8 (2)	C15—C16—H16A	119.6
C7—C6—C5	134.2 (2)	C17—C16—H16A	119.6
C10—C6—C5	107.83 (19)	C16—C17—C18	119.6 (3)
C8—C7—C6	117.2 (2)	C16—C17—H17A	120.2
C8—C7—H7A	121.4	C18—C17—H17A	120.2
C6—C7—H7A	121.4	C13—C18—C17	120.2 (2)
C9—C8—C7	120.2 (2)	C13—C18—H18A	119.9
C9—C8—H8A	119.9	C17—C18—H18A	119.9
C7—C8—H8A	119.9	H1W1—O1W—H2W1	102 (3)
N2—C9—C8	124.3 (2)
C5—N3—N4—C12	170.4 (2)	C5—C6—C10—C11	1.0 (2)
C11—N1—C1—C2	−1.0 (4)	C1—N1—C11—C4	1.9 (3)
N1—C1—C2—C3	−0.2 (4)	C1—N1—C11—C10	−175.5 (2)
C1—C2—C3—C4	0.8 (4)	C3—C4—C11—N1	−1.4 (4)
C2—C3—C4—C11	−0.1 (4)	C5—C4—C11—N1	−178.7 (2)
C2—C3—C4—C5	176.6 (2)	C3—C4—C11—C10	176.4 (2)
N4—N3—C5—C4	−179.95 (19)	C5—C4—C11—C10	−0.9 (3)
N4—N3—C5—C6	−5.5 (4)	N2—C10—C11—N1	1.0 (4)
C3—C4—C5—N3	0.6 (4)	C6—C10—C11—N1	177.6 (2)
C11—C4—C5—N3	177.5 (2)	N2—C10—C11—C4	−176.7 (2)
C3—C4—C5—C6	−175.4 (2)	C6—C10—C11—C4	−0.1 (3)
C11—C4—C5—C6	1.5 (3)	N3—N4—C12—O1	−0.6 (3)
N3—C5—C6—C7	−0.7 (5)	N3—N4—C12—C13	−177.6 (2)
C4—C5—C6—C7	174.2 (2)	O1—C12—C13—C18	−153.0 (3)
N3—C5—C6—C10	−176.4 (3)	N4—C12—C13—C18	24.0 (4)
C4—C5—C6—C10	−1.5 (2)	O1—C12—C13—C14	22.0 (4)
C10—C6—C7—C8	−1.0 (3)	N4—C12—C13—C14	−161.0 (2)
C5—C6—C7—C8	−176.4 (2)	C18—C13—C14—C15	0.1 (4)
C6—C7—C8—C9	−0.8 (4)	C12—C13—C14—C15	−175.1 (2)
C10—N2—C9—C8	−2.7 (3)	C13—C14—C15—C16	1.4 (4)
C7—C8—C9—N2	2.9 (4)	C14—C15—C16—C17	−2.4 (4)
C9—N2—C10—C6	0.7 (3)	C15—C16—C17—C18	1.9 (5)
C9—N2—C10—C11	176.8 (2)	C14—C13—C18—C17	−0.5 (4)
C7—C6—C10—N2	1.1 (3)	C12—C13—C18—C17	174.4 (3)
C5—C6—C10—N2	177.6 (2)	C16—C17—C18—C13	−0.5 (4)
C7—C6—C10—C11	−175.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1W	0.86	2.21	2.921 (3)	140
O1W—H1W1···N1^i	0.94 (3)	2.00 (4)	2.886 (3)	157 (3)
O1W—H2W1···N2^ii	0.89 (5)	2.04 (5)	2.907 (3)	163 (4)

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