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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o397.
Published online 2008 January 9. doi:  10.1107/S1600536808000032
PMCID: PMC2960396

2′-Amino-3,6-dihydroxyxanthene-9-spiro-1′-isoindolin-3′-one monohydrate

Abstract

The title compound, C20H14N2O4·H2O, was synthesized by the reaction of fluorescein and hydrazine hydrate in ethanol. In the crystal structure, the organic mol­ecules are linked into extended two-dimensional networks by inter­molecular hydrogen bonding. Additional face-to-face π–π stacking inter­actions between the phenolic benzene rings in two adjacent mol­ecules [centroid-to-centroid separation = 3.773 (3) Å] link the mol­ecules into a three-dimensional framework.

Related literature

For general background, see: Chen et al. (2006 [triangle]); Yang et al. (2005 [triangle]); Adamczyk et al. (2000 [triangle]). For related literature, see: Orndorff et al. (1927 [triangle]).

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Object name is e-64-0o397-scheme1.jpg

Experimental

Crystal data

  • C20H14N2O4·H2O
  • M r = 364.35
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o397-efi1.jpg
  • a = 7.8524 (9) Å
  • b = 10.7077 (13) Å
  • c = 11.2137 (13) Å
  • α = 103.857 (2)°
  • β = 110.432 (2)°
  • γ = 99.704 (2)°
  • V = 824.22 (17) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 293 (2) K
  • 0.32 × 0.26 × 0.22 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.967, T max = 0.977
  • 4192 measured reflections
  • 2892 independent reflections
  • 1975 reflections with I > 2σ(I)
  • R int = 0.020

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.161
  • S = 1.01
  • 2892 reflections
  • 256 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT-Plus (Bruker, 1997 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP (Bruker, 1997 [triangle]); software used to prepare material for publication: SHELXTL (Bruker, 1997 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808000032/at2528sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808000032/at2528Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Project No. 20775003) and the Natural Science Foundation of the Education Committee of Anhui Province, China (Project No. 2002 K J201).

supplementary crystallographic information

Comment

The development of fluorescent probes for determining various analytes with high selectivity and sensitivity has attracted much attention in recent years (Chen, et al., 2006). So, an enormous amount of research has gone into the design and synthesis of fluorescent probes. Fluoresein is one of the most popular dyes, because fluorescein has many advantages, including high fluorescence quantum efficiency, high extinction coefficient around 490 nm, and high water solubility under physiological conditions, therefore, it is usually utilized as reporting group in routine optical analysis (Yang et al., 2005; Adamczyk et al., 2000). For example, The title compound can be a probe to detect copper(II), cobalt(II) and hydrogen peroxide. This promoted us to attempt to prepare and obtain the crystals of the other fluorescein derivatives and characterized their crystal structures. In the title compound, C20H14N2O4.H2O, termed "fluorescein hydrazide", was prepared by reaction of fluorescein with hydrazine hydrate. Although fluorescein hydrazide has been reported by others, there is no report about the crystal of fluorescein hydrazide suitable for single-crystal X-ray diffraction. Herein, we report the crystal structural details on fluorescein hydrazide.

The fluorescein hydrazide was confirmed to have a five-membered spirolactam structure. The spiro form fluorescein hydrazide bearing a cleavable active bond is characterized by single-crystal X-ray diffraction.

The asymmetric unit contains one organic molecule and one water molecule. The benzene ring of phenol deviates only slightly from planarity with a dihedral angle of 10.18 (3)°. The water O atom acts as a hydrogen bond acceptor and donor from the hydroxy group in a neighouring organic molecule, thereby forming extended 2-D networks (Table1, Fig.2). The crystal packing is characterized by π···π stacking interactions. The molecules are stacked in an antiparalled fashion, with phenyl ring of phenol centroid-centroid separation of 3.773 (3) Å. Together with the hydrogen bonds, these interactions lead to a three-dimensional supramolecular network pattern (Fig. 2).

Experimental

For the synthesis of fluorescein hydrazide, different procedures have been reported (Orndorff et al., 1927). In this work, a modified literature procedure was used to produce fluorescein hydrazide. A solution of fluorescein (1.0 g, 3.0 mmol) in absolute ethanol (50 ml) was stirred and 4.0 ml (excess) hydrazine hydrate (85%) was then added dropwise with vigorous stirring over 5 minutes. The solution was refluxed for 5 h. The reaction mixture was cooled and the solvent was removed under reduced pressure to give dark orange oil. Then, 30 ml of ethanol/water (v:v = 7:3) was added to the oil, a light orange crystal suitable for single-crystal X– ray diffraction was obtained by evaporating the resulting solution in air for several days. The resulting light orange crystal was filtered, washed with ethanol, and then dried in vacuo, affording of the title compound [yield: 0.98 g, 90%]. The product is stable in air.

Refinement

All H atoms were positioned geometrically (C—H = 0.93 Å and O—H = 0.82 Å), and refined using a riding model, with Uiso(H) = 1.2Ueq(C or O).

Figures

Fig. 1.
The asymmetric unit, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A packing diagram for (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C20H14N2O4·H2OZ = 2
Mr = 364.35F000 = 380
Triclinic, P1Dx = 1.468 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 7.8524 (9) ÅCell parameters from 988 reflections
b = 10.7077 (13) Åθ = 2.4–24.3º
c = 11.2137 (13) ŵ = 0.11 mm1
α = 103.857 (2)ºT = 293 (2) K
β = 110.432 (2)ºBlock, light orange
γ = 99.704 (2)º0.32 × 0.26 × 0.22 mm
V = 824.22 (17) Å3

Data collection

Bruker SAMRT Apex CCD area-detector diffractometer2892 independent reflections
Radiation source: sealed tube1975 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.020
T = 293(2) Kθmax = 25.1º
phi and ω scansθmin = 2.0º
Absorption correction: multi-scan(SADABS; Bruker, 1997)h = −9→8
Tmin = 0.967, Tmax = 0.977k = −12→12
4192 measured reflectionsl = −11→13

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.161  w = 1/[σ2(Fo2) + (0.0787P)2 + 0.372P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2892 reflectionsΔρmax = 0.23 e Å3
256 parametersΔρmin = −0.21 e Å3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods

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 (Å2)

xyzUiso*/Ueq
C10.7582 (4)0.8546 (3)1.0078 (3)0.0383 (7)
C20.8972 (4)0.7821 (3)0.9920 (3)0.0363 (7)
C31.0760 (4)0.7941 (3)1.0832 (3)0.0480 (8)
H31.12610.85471.16990.058*
C41.1785 (4)0.7131 (3)1.0418 (3)0.0537 (9)
H41.29930.71931.10120.064*
C51.1019 (4)0.6226 (3)0.9121 (3)0.0514 (8)
H51.17250.56880.88590.062*
C60.9215 (4)0.6111 (3)0.8207 (3)0.0425 (7)
H60.87090.55100.73370.051*
C70.8206 (4)0.6910 (3)0.8629 (3)0.0342 (6)
C80.6212 (4)0.6958 (2)0.7840 (2)0.0323 (6)
C90.4728 (4)0.5651 (3)0.7417 (2)0.0322 (6)
C100.4807 (4)0.4862 (3)0.8257 (3)0.0375 (7)
H100.58250.51370.90890.045*
C110.3430 (4)0.3696 (3)0.7891 (3)0.0409 (7)
H110.35220.31950.84710.049*
C120.1896 (4)0.3268 (3)0.6649 (3)0.0398 (7)
C130.1775 (4)0.4022 (3)0.5803 (3)0.0426 (7)
H130.07530.37470.49730.051*
C140.3180 (4)0.5193 (3)0.6192 (3)0.0354 (6)
C150.4389 (4)0.6917 (3)0.5467 (3)0.0340 (6)
C160.4123 (4)0.7408 (3)0.4402 (3)0.0384 (7)
H160.30180.70340.36210.046*
C170.5519 (4)0.8459 (3)0.4512 (3)0.0372 (7)
C180.7171 (4)0.9011 (3)0.5690 (3)0.0415 (7)
H180.81120.97230.57700.050*
C190.7401 (4)0.8499 (3)0.6729 (3)0.0399 (7)
H190.85110.88700.75070.048*
C200.6026 (4)0.7444 (2)0.6654 (2)0.0332 (6)
N10.4419 (4)0.8470 (3)0.8590 (3)0.0480 (7)
N20.6013 (3)0.7991 (2)0.8911 (2)0.0360 (6)
O10.7722 (3)0.9475 (2)1.1028 (2)0.0588 (7)
O20.0591 (3)0.2089 (2)0.6320 (2)0.0560 (6)
H2−0.00620.18220.55090.084*
O30.2926 (3)0.5867 (2)0.52644 (19)0.0460 (6)
O40.5213 (3)0.8911 (2)0.34392 (19)0.0501 (6)
H4A0.60730.95780.36370.075*
O1W0.1874 (3)0.9043 (2)0.6353 (2)0.0548 (6)
H1A0.379 (6)0.820 (4)0.896 (4)0.072 (14)*
H1B0.481 (4)0.936 (3)0.889 (2)0.091 (14)*
H1WA0.26750.86150.66000.16 (3)*
H1WB0.15860.94390.70030.13 (2)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0487 (17)0.0328 (14)0.0279 (14)0.0084 (13)0.0136 (13)0.0054 (12)
C20.0392 (16)0.0332 (14)0.0284 (14)0.0057 (12)0.0089 (12)0.0061 (11)
C30.0485 (18)0.0438 (17)0.0339 (16)0.0090 (15)0.0035 (14)0.0043 (13)
C40.0378 (17)0.063 (2)0.0484 (19)0.0163 (16)0.0036 (15)0.0157 (16)
C50.0401 (18)0.0547 (19)0.055 (2)0.0219 (15)0.0148 (15)0.0115 (15)
C60.0410 (17)0.0423 (16)0.0359 (15)0.0126 (14)0.0117 (13)0.0034 (13)
C70.0353 (15)0.0317 (14)0.0300 (14)0.0065 (12)0.0095 (12)0.0078 (11)
C80.0351 (15)0.0309 (13)0.0261 (13)0.0099 (12)0.0100 (11)0.0044 (11)
C90.0293 (14)0.0337 (14)0.0300 (14)0.0100 (12)0.0104 (11)0.0061 (11)
C100.0374 (16)0.0418 (16)0.0289 (14)0.0120 (13)0.0103 (12)0.0081 (12)
C110.0458 (17)0.0408 (16)0.0390 (16)0.0125 (14)0.0186 (14)0.0153 (13)
C120.0347 (16)0.0394 (16)0.0427 (16)0.0064 (13)0.0168 (13)0.0098 (13)
C130.0350 (16)0.0464 (17)0.0368 (16)0.0057 (13)0.0069 (13)0.0127 (13)
C140.0335 (15)0.0383 (15)0.0322 (14)0.0091 (12)0.0115 (12)0.0113 (12)
C150.0315 (15)0.0325 (14)0.0335 (15)0.0059 (12)0.0112 (12)0.0082 (11)
C160.0364 (16)0.0400 (15)0.0310 (15)0.0084 (13)0.0064 (12)0.0105 (12)
C170.0424 (16)0.0368 (15)0.0338 (15)0.0152 (13)0.0146 (13)0.0120 (12)
C180.0407 (17)0.0352 (15)0.0400 (16)0.0036 (13)0.0120 (13)0.0086 (12)
C190.0355 (16)0.0391 (15)0.0317 (15)0.0033 (13)0.0054 (12)0.0057 (12)
C200.0335 (15)0.0305 (14)0.0292 (14)0.0081 (12)0.0089 (12)0.0051 (11)
N10.0478 (17)0.0555 (19)0.0450 (15)0.0277 (14)0.0185 (13)0.0150 (13)
N20.0363 (13)0.0395 (13)0.0299 (12)0.0183 (11)0.0110 (10)0.0057 (10)
O10.0704 (15)0.0539 (13)0.0362 (12)0.0245 (12)0.0133 (10)−0.0055 (10)
O20.0523 (14)0.0523 (13)0.0484 (13)−0.0072 (11)0.0124 (11)0.0178 (11)
O30.0350 (11)0.0515 (12)0.0369 (11)−0.0028 (9)0.0006 (9)0.0206 (9)
O40.0568 (14)0.0488 (13)0.0396 (12)0.0090 (10)0.0116 (10)0.0214 (10)
O1W0.0552 (14)0.0654 (14)0.0384 (12)0.0146 (12)0.0160 (11)0.0133 (11)

Geometric parameters (Å, °)

C1—O11.229 (3)C12—O21.362 (3)
C1—N21.356 (3)C12—C131.375 (4)
C1—C21.477 (4)C13—C141.384 (4)
C2—C31.381 (4)C13—H130.9300
C2—C71.388 (4)C14—O31.380 (3)
C3—C41.385 (4)C15—O31.377 (3)
C3—H30.9300C15—C161.382 (4)
C4—C51.391 (4)C15—C201.394 (4)
C4—H40.9300C16—C171.381 (4)
C5—C61.393 (4)C16—H160.9300
C5—H50.9300C17—O41.362 (3)
C6—C71.371 (4)C17—C181.396 (4)
C6—H60.9300C18—C191.373 (4)
C7—C81.523 (4)C18—H180.9300
C8—N21.497 (3)C19—C201.389 (4)
C8—C201.511 (4)C19—H190.9300
C8—C91.513 (4)N1—N21.396 (3)
C9—C141.384 (4)N1—H1A0.81 (4)
C9—C101.400 (4)N1—H1B0.89 (3)
C10—C111.373 (4)O2—H20.8200
C10—H100.9300O4—H4A0.8200
C11—C121.391 (4)O1W—H1WA0.8473
C11—H110.9300O1W—H1WB0.8723
O1—C1—N2124.0 (3)O2—C12—C11117.6 (3)
O1—C1—C2130.1 (3)C13—C12—C11119.4 (3)
N2—C1—C2105.9 (2)C12—C13—C14119.8 (3)
C3—C2—C7121.4 (3)C12—C13—H13120.1
C3—C2—C1129.7 (3)C14—C13—H13120.1
C7—C2—C1108.8 (2)O3—C14—C9122.5 (2)
C2—C3—C4118.0 (3)O3—C14—C13115.0 (2)
C2—C3—H3121.0C9—C14—C13122.4 (3)
C4—C3—H3121.0O3—C15—C16115.0 (2)
C3—C4—C5120.5 (3)O3—C15—C20122.6 (2)
C3—C4—H4119.8C16—C15—C20122.3 (3)
C5—C4—H4119.8C17—C16—C15119.2 (2)
C4—C5—C6121.2 (3)C17—C16—H16120.4
C4—C5—H5119.4C15—C16—H16120.4
C6—C5—H5119.4O4—C17—C16117.5 (2)
C7—C6—C5117.9 (3)O4—C17—C18122.6 (3)
C7—C6—H6121.0C16—C17—C18119.9 (3)
C5—C6—H6121.0C19—C18—C17119.7 (3)
C6—C7—C2121.0 (2)C19—C18—H18120.2
C6—C7—C8128.1 (2)C17—C18—H18120.2
C2—C7—C8110.9 (2)C18—C19—C20122.0 (2)
N2—C8—C20109.8 (2)C18—C19—H19119.0
N2—C8—C9109.7 (2)C20—C19—H19119.0
C20—C8—C9110.8 (2)C19—C20—C15117.0 (2)
N2—C8—C799.09 (19)C19—C20—C8121.8 (2)
C20—C8—C7113.7 (2)C15—C20—C8121.0 (2)
C9—C8—C7113.1 (2)N2—N1—H1A108 (3)
C14—C9—C10116.4 (2)N2—N1—H1B108.0 (14)
C14—C9—C8121.5 (2)H1A—N1—H1B110 (3)
C10—C9—C8122.1 (2)C1—N2—N1124.5 (2)
C11—C10—C9122.1 (2)C1—N2—C8115.0 (2)
C11—C10—H10118.9N1—N2—C8119.5 (2)
C9—C10—H10118.9C12—O2—H2109.5
C10—C11—C12119.8 (3)C15—O3—C14118.9 (2)
C10—C11—H11120.1C17—O4—H4A109.5
C12—C11—H11120.1H1WA—O1W—H1WB112.6
O2—C12—C13123.0 (3)
O1—C1—C2—C34.5 (5)C8—C9—C14—C13−177.9 (2)
N2—C1—C2—C3−176.3 (3)C12—C13—C14—O3179.6 (3)
O1—C1—C2—C7−175.8 (3)C12—C13—C14—C9−0.2 (4)
N2—C1—C2—C73.3 (3)O3—C15—C16—C17−179.8 (2)
C7—C2—C3—C40.6 (5)C20—C15—C16—C17−0.2 (4)
C1—C2—C3—C4−179.8 (3)C15—C16—C17—O4179.6 (2)
C2—C3—C4—C5−0.2 (5)C15—C16—C17—C18−0.1 (4)
C3—C4—C5—C60.1 (5)O4—C17—C18—C19−179.3 (3)
C4—C5—C6—C7−0.6 (5)C16—C17—C18—C190.4 (4)
C5—C6—C7—C21.0 (4)C17—C18—C19—C20−0.5 (4)
C5—C6—C7—C8−178.8 (3)C18—C19—C20—C150.2 (4)
C3—C2—C7—C6−1.1 (4)C18—C19—C20—C8−174.9 (3)
C1—C2—C7—C6179.2 (3)O3—C15—C20—C19179.7 (2)
C3—C2—C7—C8178.8 (3)C16—C15—C20—C190.1 (4)
C1—C2—C7—C8−0.9 (3)O3—C15—C20—C8−5.2 (4)
C6—C7—C8—N2178.2 (3)C16—C15—C20—C8175.3 (2)
C2—C7—C8—N2−1.7 (3)N2—C8—C20—C1969.3 (3)
C6—C7—C8—C20−65.4 (4)C9—C8—C20—C19−169.3 (2)
C2—C7—C8—C20114.7 (3)C7—C8—C20—C19−40.6 (3)
C6—C7—C8—C962.1 (4)N2—C8—C20—C15−105.5 (3)
C2—C7—C8—C9−117.8 (2)C9—C8—C20—C1515.8 (3)
N2—C8—C9—C14106.9 (3)C7—C8—C20—C15144.5 (2)
C20—C8—C9—C14−14.5 (3)O1—C1—N2—N15.6 (5)
C7—C8—C9—C14−143.5 (3)C2—C1—N2—N1−173.6 (3)
N2—C8—C9—C10−70.9 (3)O1—C1—N2—C8174.5 (3)
C20—C8—C9—C10167.7 (2)C2—C1—N2—C8−4.7 (3)
C7—C8—C9—C1038.7 (3)C20—C8—N2—C1−115.3 (3)
C14—C9—C10—C110.0 (4)C9—C8—N2—C1122.7 (2)
C8—C9—C10—C11178.0 (2)C7—C8—N2—C14.0 (3)
C9—C10—C11—C120.1 (4)C20—C8—N2—N154.2 (3)
C10—C11—C12—O2178.5 (3)C9—C8—N2—N1−67.8 (3)
C10—C11—C12—C13−0.2 (4)C7—C8—N2—N1173.5 (3)
O2—C12—C13—C14−178.3 (3)C16—C15—O3—C14170.9 (2)
C11—C12—C13—C140.3 (4)C20—C15—O3—C14−8.7 (4)
C10—C9—C14—O3−179.7 (2)C9—C14—O3—C1510.1 (4)
C8—C9—C14—O32.3 (4)C13—C14—O3—C15−169.6 (2)
C10—C9—C14—C130.0 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O4—H4A···O1Wi0.821.992.790 (3)165
N1—H1B···O1ii0.89 (3)2.534 (16)3.025 (3)115.4 (19)
O2—H2···O1Wiii0.821.952.760 (3)170
O1W—H1WA···N10.852.232.883 (3)134
O1W—H1WB···O1ii0.872.062.861 (3)152

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2528).

References

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