N,N′-Bis[2-(quinolin-8-yl­oxy)aceto­yl]hydrazine dihydrate

In the title compound, C₂₂H₁₈N₄O₄·2H₂O, the hydrazine mol­ecule lies across a twofold rotation axis, the mean planes of the two quinoline ring systems forming a dihedral angle of 64.1 (2)°. The hydrazine mol­ecules and two water mol­ecules are linked into infinite chains by O—H...O, O—H...N and N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.039
• wR factor = 0.088
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

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PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.99

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S1. Comment

8-Hydroxyquinoline and its derivatives are amongst the most extensively investigated ligands in coordination chemistry (Chen & Shi, 1998). In the course of our studies on 8-hydroxyquinoline derivatives, the title compound was synthesized and its crystal structure determined.

In the crystal, the hydrazine molecule lies across a twofold rotation axis (Fig. 1). The mean planes of the two quinoline rings make a dihedral angle of 64.1 (2)°. The hydrazine molecules and the two water molecules are linked into infinite chains by O—H···O, O—H···N and N—H···O hydrogen bonds (Fig. 2).

Related literature

For general literature concerning 8-hydroxyquinolines, see: Chen & Shi (1998).

S2. Experimental

Sodium carbonate (0.01 mol) and 2-(quinolin-8-yloxy)acetyl chloride (0.014 mol) were added to a solution of 2-(quinolin-8-yloxy)acetohydrazide (0.01 mol) in tetrahydrofuran (20 ml) and water (20 ml). The solution was stirred at 313 K for 10 h, then poured into water (100 ml). The precipitated solid was filtered and recrystallized from ethanol (m.p. 368 K). Elemental analysis calculated: C 60.26, H 5.06, N 12.77%; found: C 60.24, H 5.08, N 12.76%. Crystals suitable for single-crystal X-ray analysis were selected directly from the sample after recrystallization.

S3. Refinement

All H atoms were placed in idealized positions (C—H = 0.93–0.97 Å, O—H = 0.85 Å, N—H = 0.87 Å) and refined as riding atoms. For those bound to C, U_iso(H) = 1.2U_eq(C). while for those bound to O or N, an isotropic displacement parameter was refined.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997.

Figures

	Fig. 1. The molecular structure with displacement ellipsoids drawn at the 50% probability level for non-H atoms. The dashed lines indicate hydrogen bonds.
	Fig. 2. The structure of the infinite chains formed via hydrogen bonds (dashed lines). H atoms are omitted.

N,N'-Bis[2-(quinolin-8-yloxy)acetoyl]hydrazine dihydrate

Crystal data

C22H18N4O4·2H2O	F(000) = 920
Mr = 438.44	Dx = 1.413 Mg m^−3
Monoclinic, C2/c	Melting point: 368 K
Hall symbol: -c 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 21.687 (3) Å	Cell parameters from 1050 reflections
b = 8.3203 (11) Å	θ = 2.7–23.7°
c = 13.8618 (17) Å	µ = 0.11 mm^−1
β = 124.528 (2)°	T = 295 K
V = 2060.7 (5) Å^3	Block, colourless
Z = 4	0.29 × 0.25 × 0.22 mm

Data collection

Bruker SMART CCD diffractometer	1824 independent reflections
Radiation source: fine-focus sealed tube	1263 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ϕ and ω scans	θmax = 25.1°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→25
Tmin = 0.970, Tmax = 0.988	k = −8→9
5251 measured reflections	l = −16→16

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)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.0279P)^2 + 1.2115P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
1824 reflections	Δρmax = 0.17 e Å^−3
146 parameters	Δρmin = −0.14 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0018 (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
N1	0.24176 (8)	0.20341 (19)	0.30918 (12)	0.0450 (4)
N2	0.03903 (8)	0.0311 (2)	0.28690 (13)	0.0485 (4)
H11	0.0611	0.0808	0.2592	0.058*
O1	0.18629 (6)	0.04914 (16)	0.41376 (10)	0.0442 (4)
O2	0.03928 (7)	−0.1099 (2)	0.42604 (12)	0.0648 (5)
O3	0.08291 (7)	0.20984 (19)	0.16292 (11)	0.0654 (5)
H12	0.1305	0.2125	0.2074	0.098*
H13	0.0732	0.1821	0.0966	0.098*
C1	0.26269 (9)	0.0511 (2)	0.47287 (14)	0.0371 (4)
C2	0.31124 (10)	−0.0184 (2)	0.57907 (15)	0.0472 (5)
H2	0.2928	−0.0705	0.6170	0.057*
C3	0.38840 (11)	−0.0123 (3)	0.63189 (18)	0.0605 (6)
H3	0.4204	−0.0610	0.7044	0.073*
C4	0.41744 (11)	0.0627 (3)	0.57978 (18)	0.0604 (6)
H4	0.4690	0.0652	0.6161	0.073*
C5	0.36924 (10)	0.1372 (2)	0.47012 (16)	0.0461 (5)
C6	0.39571 (12)	0.2199 (3)	0.41171 (19)	0.0596 (6)
H6	0.4468	0.2252	0.4446	0.071*
C7	0.34666 (13)	0.2913 (3)	0.3079 (2)	0.0623 (6)
H7	0.3635	0.3473	0.2690	0.075*
C8	0.27014 (12)	0.2799 (3)	0.25997 (18)	0.0555 (6)
H8	0.2371	0.3298	0.1884	0.067*
C9	0.29094 (9)	0.1327 (2)	0.41529 (14)	0.0385 (4)
C10	0.15646 (9)	−0.0393 (2)	0.46586 (15)	0.0426 (5)
H10A	0.1736	0.0080	0.5411	0.051*
H10B	0.1749	−0.1488	0.4795	0.051*
C11	0.07242 (10)	−0.0411 (2)	0.39007 (16)	0.0439 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0467 (9)	0.0482 (10)	0.0398 (8)	−0.0047 (8)	0.0243 (8)	−0.0014 (8)
N2	0.0291 (8)	0.0727 (12)	0.0425 (9)	−0.0036 (8)	0.0196 (7)	0.0027 (8)
O1	0.0308 (7)	0.0596 (9)	0.0409 (7)	−0.0028 (6)	0.0196 (6)	0.0066 (6)
O2	0.0462 (8)	0.0922 (12)	0.0624 (9)	−0.0092 (8)	0.0346 (8)	0.0119 (8)
O3	0.0474 (8)	0.0945 (12)	0.0508 (8)	0.0049 (8)	0.0257 (7)	0.0052 (8)
C1	0.0303 (10)	0.0417 (11)	0.0372 (9)	−0.0058 (8)	0.0178 (8)	−0.0070 (8)
C2	0.0395 (11)	0.0552 (13)	0.0417 (11)	−0.0051 (10)	0.0198 (9)	0.0028 (10)
C3	0.0385 (12)	0.0743 (17)	0.0482 (12)	−0.0027 (11)	0.0122 (10)	0.0075 (11)
C4	0.0320 (11)	0.0773 (17)	0.0592 (13)	−0.0040 (11)	0.0182 (10)	0.0008 (12)
C5	0.0396 (11)	0.0490 (13)	0.0517 (11)	−0.0101 (10)	0.0271 (10)	−0.0102 (10)
C6	0.0516 (13)	0.0716 (16)	0.0660 (14)	−0.0215 (12)	0.0397 (12)	−0.0167 (13)
C7	0.0758 (16)	0.0670 (16)	0.0645 (14)	−0.0253 (13)	0.0520 (13)	−0.0134 (12)
C8	0.0706 (15)	0.0541 (14)	0.0480 (11)	−0.0118 (12)	0.0373 (11)	−0.0014 (10)
C9	0.0377 (10)	0.0390 (11)	0.0392 (10)	−0.0060 (8)	0.0220 (9)	−0.0081 (9)
C10	0.0388 (10)	0.0505 (12)	0.0402 (10)	−0.0041 (9)	0.0233 (9)	−0.0007 (9)
C11	0.0383 (11)	0.0537 (13)	0.0432 (11)	−0.0039 (10)	0.0253 (9)	−0.0053 (10)

Geometric parameters (Å, º)

N1—C8	1.313 (2)	C3—C4	1.351 (3)
N1—C9	1.367 (2)	C3—H3	0.930
N2—C11	1.325 (2)	C4—C5	1.409 (3)
N2—N2^i	1.396 (3)	C4—H4	0.930
N2—H11	0.870	C5—C6	1.409 (3)
O1—C1	1.3704 (19)	C5—C9	1.414 (2)
O1—C10	1.418 (2)	C6—C7	1.349 (3)
O2—C11	1.224 (2)	C6—H6	0.930
O3—H12	0.850	C7—C8	1.398 (3)
O3—H13	0.850	C7—H7	0.930
C1—C2	1.361 (2)	C8—H8	0.930
C1—C9	1.424 (2)	C10—C11	1.502 (2)
C2—C3	1.396 (3)	C10—H10A	0.970
C2—H2	0.930	C10—H10B	0.970
C8—N1—C9	117.26 (16)	C7—C6—C5	119.74 (19)
C11—N2—N2^i	119.00 (16)	C7—C6—H6	120.1
C11—N2—H11	126.3	C5—C6—H6	120.1
N2^i—N2—H11	114.7	C6—C7—C8	118.9 (2)
C1—O1—C10	116.58 (13)	C6—C7—H7	120.5
H12—O3—H13	104.3	C8—C7—H7	120.5
C2—C1—O1	125.01 (16)	N1—C8—C7	124.4 (2)
C2—C1—C9	119.59 (16)	N1—C8—H8	117.8
O1—C1—C9	115.40 (15)	C7—C8—H8	117.8
C1—C2—C3	120.95 (18)	N1—C9—C5	122.26 (16)
C1—C2—H2	119.5	N1—C9—C1	119.16 (15)
C3—C2—H2	119.5	C5—C9—C1	118.58 (16)
C4—C3—C2	121.31 (19)	O1—C10—C11	111.84 (14)
C4—C3—H3	119.3	O1—C10—H10A	109.2
C2—C3—H3	119.3	C11—C10—H10A	109.2
C3—C4—C5	119.64 (18)	O1—C10—H10B	109.2
C3—C4—H4	120.2	C11—C10—H10B	109.2
C5—C4—H4	120.2	H10A—C10—H10B	107.9
C6—C5—C4	122.68 (18)	O2—C11—N2	124.29 (17)
C6—C5—C9	117.40 (18)	O2—C11—C10	118.66 (17)
C4—C5—C9	119.92 (17)	N2—C11—C10	117.04 (16)
C10—O1—C1—C2	−3.3 (3)	C8—N1—C9—C1	178.83 (17)
C10—O1—C1—C9	176.44 (15)	C6—C5—C9—N1	0.7 (3)
O1—C1—C2—C3	178.99 (18)	C4—C5—C9—N1	179.78 (18)
C9—C1—C2—C3	−0.8 (3)	C6—C5—C9—C1	−179.47 (18)
C1—C2—C3—C4	0.2 (3)	C4—C5—C9—C1	−0.4 (3)
C2—C3—C4—C5	0.2 (3)	C2—C1—C9—N1	−179.35 (17)
C3—C4—C5—C6	178.9 (2)	O1—C1—C9—N1	0.9 (2)
C3—C4—C5—C9	−0.1 (3)	C2—C1—C9—C5	0.9 (3)
C4—C5—C6—C7	−178.7 (2)	O1—C1—C9—C5	−178.91 (16)
C9—C5—C6—C7	0.3 (3)	C1—O1—C10—C11	−176.56 (15)
C5—C6—C7—C8	−0.7 (3)	N2^i—N2—C11—O2	0.4 (3)
C9—N1—C8—C7	1.0 (3)	N2^i—N2—C11—C10	179.43 (14)
C6—C7—C8—N1	0.0 (3)	O1—C10—C11—O2	−178.11 (18)
C8—N1—C9—C5	−1.4 (3)	O1—C10—C11—N2	2.8 (2)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H13···O2^ii	0.85	2.13	2.9745 (19)	175
O3—H12···N1	0.85	1.99	2.840 (1)	176
N2—H11···O3	0.87	1.97	2.815 (2)	164

Symmetry code: (ii) x, −y, z−1/2.