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Acta Cryst. (2008). E64, m266    [ doi:10.1107/S1600536807067323 ]

Diaquabis(9-oxo-4,5-diazafluoren-3-olato-[kappa]2N4,O3)cadmium(II)

Y.-H. Zhao, X. Yuan, W.-C. Qin, L.-X. Sheng and Y.-Z. Ding

Abstract top

The title compound, [Cd(C11H5N2O2)2(H2O)2], is a mononuclear complex consisting of a CdII atom, two 3-hydroxy-4,5-diazafluoren-9-one ligands and two coordinated water molecules. The CdII atom, lying on a twofold axis, displays a distorted octahedral coordintion. Adjacent molecules are linked by O-H...O hydrogen bonds and [pi]-[pi] interactions [centroid-centroid distance = 3.84 (1) Å], leading to a one-dimensional chain. Weak C-H...O hydrogen bonds connect the chains into a two-dimensional supramolecular structure.

Comment top

The structures of 4,5-diazafluoren-9-one and its metal complexes have been reported (Li et al., 2006; Rillema et al., 2007; Tershansy et al., 2006; Zhao et al., 2006). However, no studies of its derivative, 3-hydroxyl-4,5-diazafluoren-9-one, and any metal complexes of the ligand are known to date. In this paper, we present the crystal structure of the title compound, [Cd(C11H5N2O2)2(H2O)2].

The title compound is a neutral mononuclear complex. The CdII atom is six-coordinate and exhibits a distorted octahedral coordintion geometry, defined by two N atoms and two O atoms from two 3-hydroxyl-4,5-diazafluoren-9-one ligands and two O atoms from two aqua ligands (Fig. 1). The Cd—O distances are in the range of 2.233 (2)–2.410 (2)Å and the Cd—N length is 2.322 (2) Å (Table 1). Adjacent molecules are linked by O—H···O hydrogen bonds and π–π interactions [centroid–centroid distance 3.84 (1) Å], leading to a one-dimensional chain. Weak C—H···O hydrogen bonds connect the chains into a two-dimensional supramolecular structure (Fig. 2; Table 2).

Related literature top

For related literature, see: Li et al. (2006); Rillema et al. (2007); Tershansy et al. (2006); Zhao et al. (2006).

Experimental top

Cadmium(II) acetate dihydrate (0.080 g, 0.3 mmol), 3-hydroxyl-4,5-diazafluoren-9-one (0.040 g, 0.2 mmol), sodium hydroxide (0.024 g, 0.4 mmol) and water (14 ml) were placed in a 23 ml Teflon-lined autoclave, which was heated at 423 K for 3 d. After cooling slowly to room temperature at a rate of 10 K h-1, colorless crystals of the title compound were obtained. Analysis calculated for C22H14CdN4O6: C 48.64, H 2.58, N 10.32%; found: C 48.51, H 2.67, N 10.42%.

Refinement top

H atoms on C atoms were positioned geometrically and refined as riding, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C). H atoms of water molecule were located on a difference Fourier map and refined isotropically with a restraint of O—H = 0.82 (1) Å.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x + 2, y, -z + 1/2.]
[Figure 2] Fig. 2. A packing diagram for the two-dimensional supramolecular structure via hydrogen bonds (dashed lines).
Diaquabis(9-oxo-4,5-diazafluoren-3-olato- κ2N4,O3)cadmium(II) top
Crystal data top
[Cd(C11H5N2O2)2(H2O)2]F000 = 1080
Mr = 542.77Dx = 1.760 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 4465 reflections
a = 28.190 (5) Åθ = 3.0–28.3º
b = 5.572 (4) ŵ = 1.12 mm−1
c = 13.933 (5) ÅT = 293 (2) K
β = 110.622 (5)ºBlock, colorless
V = 2048.3 (17) Å30.26 × 0.21 × 0.17 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2406 independent reflections
Radiation source: rotation anode1965 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 293(2) Kθmax = 28.3º
ω scansθmin = 3.0º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −26→37
Tmin = 0.760, Tmax = 0.833k = −7→7
5972 measured reflectionsl = −18→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.082  w = 1/[σ2(Fo2) + (0.0433P)2 + 1.5483P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2406 reflectionsΔρmax = 0.62 e Å−3
158 parametersΔρmin = −0.36 e Å−3
2 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Cd(C11H5N2O2)2(H2O)2]V = 2048.3 (17) Å3
Mr = 542.77Z = 4
Monoclinic, C2/cMo Kα
a = 28.190 (5) ŵ = 1.12 mm−1
b = 5.572 (4) ÅT = 293 (2) K
c = 13.933 (5) Å0.26 × 0.21 × 0.17 mm
β = 110.622 (5)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2406 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		1965 reflections with I > 2σ(I)
Tmin = 0.760, Tmax = 0.833Rint = 0.021
5972 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0292 restraints
wR(F2) = 0.082H atoms treated by a mixture of
independent and constrained refinement
S = 1.02Δρmax = 0.62 e Å−3
2406 reflectionsΔρmin = −0.36 e Å−3
158 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd11.00000.24267 (5)0.25000.04153 (11)
N10.91692 (7)0.1412 (4)0.15373 (15)0.0337 (4)
N20.90481 (8)0.5376 (4)−0.00770 (16)0.0400 (5)
O20.95401 (7)−0.0756 (3)0.29552 (14)0.0455 (4)
O30.75172 (7)0.0883 (4)−0.09790 (15)0.0553 (5)
C10.91486 (9)−0.0461 (4)0.21600 (18)0.0358 (5)
C20.87029 (11)−0.1903 (5)0.1904 (2)0.0430 (6)
H20.8695−0.32030.23170.052*
C30.82874 (10)−0.1395 (5)0.1061 (2)0.0423 (6)
H30.7995−0.23220.08970.051*
C40.83130 (9)0.0555 (5)0.04508 (18)0.0366 (5)
C50.79449 (9)0.1567 (5)−0.0489 (2)0.0404 (6)
C60.82108 (9)0.3654 (5)−0.07684 (18)0.0377 (5)
C70.80569 (10)0.5278 (5)−0.1560 (2)0.0470 (6)
H70.77310.5249−0.20450.056*
C80.84113 (12)0.6963 (5)−0.1601 (2)0.0501 (7)
H80.83250.8102−0.21220.060*
C90.88918 (12)0.6950 (5)−0.0868 (2)0.0460 (7)
H90.91220.8091−0.09200.055*
C100.87021 (9)0.3786 (4)−0.00494 (17)0.0334 (5)
C110.87612 (9)0.1865 (4)0.07194 (19)0.0327 (5)
O10.99406 (8)0.4960 (4)0.36946 (16)0.0505 (5)
H1A1.0223 (8)0.519 (6)0.412 (2)0.065 (10)*
H1B0.9809 (13)0.630 (4)0.353 (3)0.067 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02980 (15)0.03837 (17)0.04841 (18)0.0000.00383 (11)0.000
N10.0281 (10)0.0314 (10)0.0377 (11)−0.0028 (8)0.0066 (8)0.0013 (9)
N20.0387 (11)0.0401 (12)0.0400 (11)−0.0032 (9)0.0125 (9)0.0036 (9)
O20.0427 (10)0.0407 (10)0.0454 (10)0.0028 (8)0.0058 (8)0.0076 (8)
O30.0343 (10)0.0707 (14)0.0495 (11)−0.0142 (9)0.0005 (8)−0.0081 (10)
C10.0369 (12)0.0317 (12)0.0382 (13)0.0023 (10)0.0124 (10)0.0002 (10)
C20.0489 (16)0.0348 (13)0.0490 (15)−0.0056 (11)0.0218 (13)0.0017 (11)
C30.0385 (14)0.0400 (14)0.0494 (15)−0.0123 (11)0.0168 (12)−0.0068 (12)
C40.0296 (11)0.0403 (13)0.0385 (13)−0.0051 (10)0.0103 (10)−0.0061 (11)
C50.0331 (13)0.0464 (14)0.0396 (13)−0.0031 (11)0.0100 (11)−0.0089 (12)
C60.0317 (12)0.0444 (15)0.0345 (12)−0.0003 (10)0.0085 (10)−0.0048 (11)
C70.0415 (14)0.0581 (17)0.0355 (13)0.0076 (12)0.0062 (11)0.0035 (12)
C80.0597 (18)0.0509 (16)0.0383 (14)0.0123 (14)0.0154 (13)0.0101 (12)
C90.0500 (16)0.0423 (15)0.0499 (16)0.0011 (12)0.0227 (13)0.0083 (12)
C100.0318 (11)0.0350 (13)0.0312 (11)−0.0004 (9)0.0086 (9)−0.0022 (10)
C110.0296 (12)0.0320 (12)0.0353 (12)−0.0025 (9)0.0097 (10)−0.0030 (10)
O10.0448 (12)0.0426 (11)0.0532 (12)0.0076 (9)0.0039 (10)−0.0025 (10)
Geometric parameters (Å, °) top
Cd1—O12.233 (2)C3—C41.397 (4)
Cd1—O1i2.233 (2)C3—H30.9300
Cd1—N1i2.3217 (19)C4—C111.391 (3)
Cd1—N12.3217 (19)C4—C51.468 (4)
Cd1—O22.410 (2)C5—C61.507 (4)
Cd1—O2i2.410 (2)C6—C71.374 (4)
N1—C111.327 (3)C6—C101.396 (3)
N1—C11.371 (3)C7—C81.386 (4)
N2—C101.328 (3)C7—H70.9300
N2—C91.355 (3)C8—C91.380 (4)
O2—C11.269 (3)C8—H80.9300
O3—C51.219 (3)C9—H90.9300
C1—C21.427 (4)C10—C111.482 (4)
C2—C31.365 (4)O1—H1A0.817 (18)
C2—H20.9300O1—H1B0.832 (19)
O1—Cd1—O1i101.59 (13)C4—C3—H3120.9
O1—Cd1—N1i92.77 (7)C11—C4—C3118.8 (2)
O1i—Cd1—N1i105.03 (8)C11—C4—C5109.1 (2)
O1—Cd1—N1105.03 (8)C3—C4—C5132.1 (2)
O1i—Cd1—N192.77 (7)O3—C5—C4128.9 (3)
N1i—Cd1—N1151.82 (11)O3—C5—C6125.5 (3)
O1—Cd1—O294.62 (9)C4—C5—C6105.5 (2)
O1i—Cd1—O2148.19 (7)C7—C6—C10119.6 (2)
N1i—Cd1—O2101.27 (7)C7—C6—C5132.1 (2)
N1—Cd1—O256.38 (7)C10—C6—C5108.3 (2)
O1—Cd1—O2i148.19 (7)C6—C7—C8116.8 (2)
O1i—Cd1—O2i94.62 (9)C6—C7—H7121.6
N1i—Cd1—O2i56.38 (7)C8—C7—H7121.6
N1—Cd1—O2i101.27 (7)C9—C8—C7120.0 (3)
O2—Cd1—O2i85.23 (11)C9—C8—H8120.0
C11—N1—C1118.1 (2)C7—C8—H8120.0
C11—N1—Cd1147.41 (17)N2—C9—C8124.0 (3)
C1—N1—Cd194.51 (14)N2—C9—H9118.0
C10—N2—C9115.1 (2)C8—C9—H9118.0
C1—O2—Cd193.31 (15)N2—C10—C6124.6 (2)
O2—C1—N1115.7 (2)N2—C10—C11127.3 (2)
O2—C1—C2124.3 (2)C6—C10—C11108.1 (2)
N1—C1—C2120.0 (2)N1—C11—C4124.2 (2)
C3—C2—C1120.8 (3)N1—C11—C10126.9 (2)
C3—C2—H2119.6C4—C11—C10108.9 (2)
C1—C2—H2119.6Cd1—O1—H1A109 (2)
C2—C3—C4118.2 (2)Cd1—O1—H1B120 (2)
C2—C3—H3120.9H1A—O1—H1B107 (3)
O1—Cd1—N1—C1193.5 (3)C3—C4—C5—C6−179.4 (3)
O1i—Cd1—N1—C11−9.3 (3)O3—C5—C6—C72.3 (5)
N1i—Cd1—N1—C11−139.1 (3)C4—C5—C6—C7−179.5 (3)
O2—Cd1—N1—C11179.0 (3)O3—C5—C6—C10−176.9 (3)
O2i—Cd1—N1—C11−104.6 (3)C4—C5—C6—C101.4 (3)
O1—Cd1—N1—C1−87.51 (16)C10—C6—C7—C80.9 (4)
O1i—Cd1—N1—C1169.70 (14)C5—C6—C7—C8−178.2 (3)
N1i—Cd1—N1—C139.89 (13)C6—C7—C8—C90.1 (4)
O2—Cd1—N1—C1−2.01 (13)C10—N2—C9—C80.3 (4)
O2i—Cd1—N1—C174.44 (15)C7—C8—C9—N2−0.7 (5)
O1—Cd1—O2—C1107.16 (15)C9—N2—C10—C60.7 (4)
O1i—Cd1—O2—C1−13.7 (2)C9—N2—C10—C11−179.8 (2)
N1i—Cd1—O2—C1−159.08 (14)C7—C6—C10—N2−1.3 (4)
N1—Cd1—O2—C12.17 (14)C5—C6—C10—N2178.0 (2)
O2i—Cd1—O2—C1−104.75 (16)C7—C6—C10—C11179.0 (2)
Cd1—O2—C1—N1−3.4 (2)C5—C6—C10—C11−1.7 (3)
Cd1—O2—C1—C2177.7 (2)C1—N1—C11—C4−0.2 (4)
C11—N1—C1—O2−177.1 (2)Cd1—N1—C11—C4178.7 (2)
Cd1—N1—C1—O23.5 (2)C1—N1—C11—C10−180.0 (2)
C11—N1—C1—C21.9 (3)Cd1—N1—C11—C10−1.1 (5)
Cd1—N1—C1—C2−177.5 (2)C3—C4—C11—N1−1.3 (4)
O2—C1—C2—C3176.7 (2)C5—C4—C11—N1179.7 (2)
N1—C1—C2—C3−2.2 (4)C3—C4—C11—C10178.6 (2)
C1—C2—C3—C40.7 (4)C5—C4—C11—C10−0.5 (3)
C2—C3—C4—C110.9 (4)N2—C10—C11—N11.6 (4)
C2—C3—C4—C5179.7 (3)C6—C10—C11—N1−178.8 (2)
C11—C4—C5—O3177.7 (3)N2—C10—C11—C4−178.3 (2)
C3—C4—C5—O3−1.2 (5)C6—C10—C11—C41.4 (3)
C11—C4—C5—C6−0.5 (3)
Symmetry codes: (i) −x+2, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N2i0.82 (2)2.02 (2)2.832 (3)172 (3)
O1—H1B···O2ii0.83 (2)1.86 (2)2.686 (3)170 (4)
C3—H3···O3iii0.932.483.351 (5)156
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) x, y+1, z; (iii) −x+3/2, −y−1/2, −z.
Table 1
Selected geometric parameters (Å, °) top
Cd1—O12.233 (2)Cd1—O22.410 (2)
Cd1—N12.3217 (19)
O1—Cd1—O1i101.59 (13)O1i—Cd1—O2148.19 (7)
O1—Cd1—N1i92.77 (7)N1i—Cd1—O2101.27 (7)
O1—Cd1—N1105.03 (8)N1—Cd1—O256.38 (7)
N1i—Cd1—N1151.82 (11)O2—Cd1—O2i85.23 (11)
O1—Cd1—O294.62 (9)
Symmetry codes: (i) −x+2, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···N2i0.82 (2)2.02 (2)2.832 (3)172 (3)
O1—H1B···O2ii0.83 (2)1.86 (2)2.686 (3)170 (4)
C3—H3···O3iii0.932.483.351 (5)156
Symmetry codes: (i) −x+2, y, −z+1/2; (ii) x, y+1, z; (iii) −x+3/2, −y−1/2, −z.
Acknowledgements top

The authors thank the Key Project of the Chinese Ministry of Education (grant No. 308008) and the Analysis and Testing Foundation of Northeast Normal University for financial support.

references
References top

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