
Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038457/fl2152sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038457/fl2152Isup2.hkl |
CCDC reference: 660235
1,8-diazafluoren-9-one was synthesized as previously reported (Siemeling & Scheppelmann, 2004). The title compound was crystallized by allowing slow evaporation of a dilute sulfuric acid solution (1 M) containing the compound. The crystals formed on the bottom of the beaker and were collected for analysis.
All H atoms were initially located in a difference Fourier map but were eventually placed in their geometrically idealized positions and constrained to ride on their parent atoms, with N—H = 0.88Å and C—H = 0.95 Å, and with Uiso(H) = 1.2eq(C,N).
The structure of the title compound, (I), is shown below. The molecule is of interest because the non-protonated form is used to make metal complexes in our laboratory. Some synthetic reactions need to be executed in acidic solutions, so a better understanding of the protonation behavior is useful for designing synthetic routes. Some monoprotonated forms have been reported (Balagopalakrishna et al., 1996), (Menon et al., 1994), (Ravikumar et al., 1995), (Zhang et al., 2003). The compound sits on a mirror plane in the orthorhombic space group Pnma. Each diazafluorenone ring has a 2+ charge which is balanced by the 2- charge of the sulfate group that is hydrogen bonded. Table 1 gives the bond distances for selected atoms and Figure 2 shows the placement of the bonds. The ketone group on the ring structure forms hydrogen bonds with the protons, but this could also be electrostatic attraction between the oxygen and nitrogen. The sulfate group forms two hydrogen bonds with the ring structure at a distance of 1.82 Å from the hydrogen atoms and 2.665 Å from the nitrogen atoms. The sulfate anion also forms hydrogen bonds with the hydrogen atoms on the ring. These distances are long and not included in the table but can be viewed in the cif file. The angles listed in Table 1 are obtained from the angle formed by the first three atoms listed in table. The angles formed by the S—O– –H(N) and C=O– –H(N) are slightly larger than the H—O—H angle of 109.5 found for water.
For related literature, see: Balagopalakrishna et al. (1996); Menon et al. (1994); Ravikumar et al. (1995); Siemeling & Scheppelmann (2004); Zhang et al. (2003).
Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2; data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXTL (Bruker, 2006); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.
C11H8N2O2+·SO42− | F(000) = 576 |
Mr = 280.25 | Dx = 1.673 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ac2n | Cell parameters from 2024 reflections |
a = 11.9016 (12) Å | θ = 3.1–25.5° |
b = 11.9344 (12) Å | µ = 0.31 mm−1 |
c = 7.8351 (7) Å | T = 150 K |
V = 1112.89 (19) Å3 | Block, colorless |
Z = 4 | 0.15 × 0.13 × 0.12 mm |
Bruker Kappa APEX II CCD area-detector diffractometer | 1140 independent reflections |
Radiation source: fine-focus sealed tube | 794 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.134 |
φ and ω scans | θmax = 26.0°, θmin = 3.1° |
Absorption correction: numerical (SADABS; Sheldrick, 1997) | h = −14→10 |
Tmin = 0.956, Tmax = 0.965 | k = −14→14 |
9704 measured reflections | l = −9→9 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0556P)2 + 0.4328P] where P = (Fo2 + 2Fc2)/3 |
1140 reflections | (Δ/σ)max < 0.001 |
94 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
C11H8N2O2+·SO42− | V = 1112.89 (19) Å3 |
Mr = 280.25 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 11.9016 (12) Å | µ = 0.31 mm−1 |
b = 11.9344 (12) Å | T = 150 K |
c = 7.8351 (7) Å | 0.15 × 0.13 × 0.12 mm |
Bruker Kappa APEX II CCD area-detector diffractometer | 1140 independent reflections |
Absorption correction: numerical (SADABS; Sheldrick, 1997) | 794 reflections with I > 2σ(I) |
Tmin = 0.956, Tmax = 0.965 | Rint = 0.134 |
9704 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.35 e Å−3 |
1140 reflections | Δρmin = −0.41 e Å−3 |
94 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7931 (3) | 0.3118 (2) | 0.0791 (4) | 0.0184 (7) | |
C2 | 0.7283 (3) | 0.4924 (3) | 0.0531 (4) | 0.0239 (8) | |
H2 | 0.6695 | 0.5427 | 0.0239 | 0.029* | |
C3 | 0.8294 (3) | 0.5351 (3) | 0.1087 (4) | 0.0254 (8) | |
H3 | 0.8394 | 0.6138 | 0.1182 | 0.031* | |
C4 | 0.9162 (3) | 0.4635 (3) | 0.1509 (4) | 0.0239 (8) | |
H4 | 0.9863 | 0.4914 | 0.1903 | 0.029* | |
C5 | 0.8977 (3) | 0.3494 (3) | 0.1336 (4) | 0.0204 (7) | |
C6 | 0.9715 (4) | 0.2500 | 0.1631 (5) | 0.0218 (10) | |
N1 | 0.7103 (2) | 0.3809 (2) | 0.0387 (3) | 0.0209 (6) | |
H1 | 0.6451 | 0.3549 | 0.0033 | 0.025* | |
O1 | 1.0703 (3) | 0.2500 | 0.2015 (4) | 0.0292 (8) | |
O2 | 0.6620 (3) | 0.7500 | 0.1629 (4) | 0.0324 (9) | |
O3 | 0.50345 (19) | 0.64879 (17) | 0.0518 (3) | 0.0260 (6) | |
O4 | 0.4856 (3) | 0.7500 | 0.3159 (4) | 0.0326 (9) | |
S1 | 0.54194 (10) | 0.7500 | 0.15386 (13) | 0.0199 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0169 (18) | 0.0198 (15) | 0.0186 (15) | 0.0004 (14) | 0.0038 (14) | 0.0017 (12) |
C2 | 0.025 (2) | 0.0187 (16) | 0.0277 (17) | −0.0010 (15) | 0.0020 (15) | −0.0002 (13) |
C3 | 0.029 (2) | 0.0190 (16) | 0.0287 (17) | −0.0034 (15) | 0.0040 (15) | −0.0045 (13) |
C4 | 0.022 (2) | 0.0264 (17) | 0.0236 (16) | −0.0079 (15) | 0.0034 (14) | −0.0059 (13) |
C5 | 0.0170 (19) | 0.0253 (16) | 0.0191 (15) | −0.0016 (15) | 0.0033 (13) | −0.0008 (12) |
C6 | 0.017 (3) | 0.032 (3) | 0.017 (2) | 0.000 | 0.0011 (19) | 0.000 |
N1 | 0.0183 (16) | 0.0207 (14) | 0.0238 (14) | −0.0024 (12) | −0.0011 (11) | −0.0010 (10) |
O1 | 0.021 (2) | 0.0406 (19) | 0.0264 (16) | 0.000 | −0.0040 (15) | 0.000 |
O2 | 0.016 (2) | 0.0286 (18) | 0.053 (2) | 0.000 | −0.0058 (15) | 0.000 |
O3 | 0.0276 (14) | 0.0200 (12) | 0.0304 (12) | −0.0006 (11) | −0.0048 (11) | −0.0035 (9) |
O4 | 0.034 (2) | 0.042 (2) | 0.0221 (16) | 0.000 | 0.0025 (15) | 0.000 |
S1 | 0.0160 (7) | 0.0192 (6) | 0.0246 (6) | 0.000 | −0.0022 (5) | 0.000 |
C1—N1 | 1.323 (4) | C4—H4 | 0.9500 |
C1—C5 | 1.390 (4) | C5—C6 | 1.494 (4) |
C1—C1i | 1.476 (6) | C6—O1 | 1.214 (5) |
C2—N1 | 1.352 (4) | C6—C5i | 1.494 (4) |
C2—C3 | 1.377 (5) | N1—H1 | 0.8800 |
C2—H2 | 0.9500 | O2—S1 | 1.430 (3) |
C3—C4 | 1.381 (5) | O3—S1 | 1.519 (2) |
C3—H3 | 0.9500 | O4—S1 | 1.436 (3) |
C4—C5 | 1.386 (4) | S1—O3ii | 1.519 (2) |
N1—C1—C5 | 122.7 (3) | C1—C5—C6 | 108.6 (3) |
N1—C1—C1i | 128.54 (17) | O1—C6—C5i | 127.45 (18) |
C5—C1—C1i | 108.80 (17) | O1—C6—C5 | 127.45 (18) |
N1—C2—C3 | 121.9 (3) | C5i—C6—C5 | 105.1 (4) |
N1—C2—H2 | 119.0 | C1—N1—C2 | 118.4 (3) |
C3—C2—H2 | 119.0 | C1—N1—H1 | 120.8 |
C2—C3—C4 | 120.0 (3) | C2—N1—H1 | 120.8 |
C2—C3—H3 | 120.0 | O2—S1—O4 | 115.0 (2) |
C4—C3—H3 | 120.0 | O2—S1—O3 | 109.11 (12) |
C3—C4—C5 | 117.7 (3) | O4—S1—O3 | 108.96 (12) |
C3—C4—H4 | 121.1 | O2—S1—O3ii | 109.11 (12) |
C5—C4—H4 | 121.1 | O4—S1—O3ii | 108.96 (12) |
C4—C5—C1 | 119.3 (3) | O3—S1—O3ii | 105.29 (17) |
C4—C5—C6 | 132.2 (3) |
Symmetry codes: (i) x, −y+1/2, z; (ii) x, −y+3/2, z. |
Experimental details
Crystal data | |
Chemical formula | C11H8N2O2+·SO42− |
Mr | 280.25 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 150 |
a, b, c (Å) | 11.9016 (12), 11.9344 (12), 7.8351 (7) |
V (Å3) | 1112.89 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.31 |
Crystal size (mm) | 0.15 × 0.13 × 0.12 |
Data collection | |
Diffractometer | Bruker Kappa APEX II CCD area-detector |
Absorption correction | Numerical (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.956, 0.965 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9704, 1140, 794 |
Rint | 0.134 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.138, 1.07 |
No. of reflections | 1140 |
No. of parameters | 94 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.41 |
Computer programs: APEX2 (Bruker, 2006), APEX2, SAINT (Bruker, 2006), SHELXTL (Bruker, 2006), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXTL.
Atoms | Distances (Å) | Angle (°) |
S—O···H—N(Ring) | 1.820 | 115.90 |
S—O···N(Ring) | 2.665 | 122.25 |
(Ring)C═O···H—N(Ring) | 2.777 | 121.14 |
(Ring)C═O···N(Ring) | 3.059 | 133.83 |
The structure of the title compound, (I), is shown below. The molecule is of interest because the non-protonated form is used to make metal complexes in our laboratory. Some synthetic reactions need to be executed in acidic solutions, so a better understanding of the protonation behavior is useful for designing synthetic routes. Some monoprotonated forms have been reported (Balagopalakrishna et al., 1996), (Menon et al., 1994), (Ravikumar et al., 1995), (Zhang et al., 2003). The compound sits on a mirror plane in the orthorhombic space group Pnma. Each diazafluorenone ring has a 2+ charge which is balanced by the 2- charge of the sulfate group that is hydrogen bonded. Table 1 gives the bond distances for selected atoms and Figure 2 shows the placement of the bonds. The ketone group on the ring structure forms hydrogen bonds with the protons, but this could also be electrostatic attraction between the oxygen and nitrogen. The sulfate group forms two hydrogen bonds with the ring structure at a distance of 1.82 Å from the hydrogen atoms and 2.665 Å from the nitrogen atoms. The sulfate anion also forms hydrogen bonds with the hydrogen atoms on the ring. These distances are long and not included in the table but can be viewed in the cif file. The angles listed in Table 1 are obtained from the angle formed by the first three atoms listed in table. The angles formed by the S—O– –H(N) and C=O– –H(N) are slightly larger than the H—O—H angle of 109.5 found for water.