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The title compound, C15H11N2+·HN2O6, crystallizes in the monoclinic space group C2/c with four mol­ecules in the unit cell. The planar 9-cyano-10-methyl­acridinium cations lie on crystallographic twofold axes and are arranged in layers, almost perpendicular to the ac plane, in such a way that neighbouring mol­ecules are positioned in a `head-to-tail' manner. These cations and the hydrogen dinitrate anions are linked through C—H...O interactions involving four of the six O atoms of the anion and the H atoms attached to the C atoms of the acridine moiety in ring positions 2 and 4. The H atom of the hydrogen dinitrate anion appears to be located on the centre of inversion relating two of the four O atoms engaged in the above-mentioned C—H...O interactions. In this way, columns of either anions or cations running along the c axis are held in place by the network of C—H...O interactions, forming a relatively compact crystal lattice.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004912/bm1487sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004912/bm1487Isup2.hkl
Contains datablock I

CCDC reference: 187939

Comment top

9-Cyano-10-methylacridinium salts (McCapra & Richardson, 1964), such as 9-carboxy-10-methylacridinium phenyl ester salts (Rak et al., 1999) or other 9-substituted-10-alkylacridinium salts (Dodeigne et al., 2000), can act as chemiluminescent or spectral indicators or as the chemiluminogenic fragments of chemiluminescent labels (Zomer et al., 1991). The possible applications of these compounds are principally dependent on the stability of their crystalline phases. The reasons for undertaking our present investigations were therefore, firstly, to investigate which 9-cyano-10-methylacridinium salts can be obtained in the crystalline state, secondly, to determine their structures and thirdly, to demonstrate to what extent structural features can influence their stability. We succeeded in crystallizing the title hydrogen dinitrate salt, (I), which is readily soluble in water and several organic solvents, and can thus be used in analytical and spectroscopic investigations. \sch

The stoichiometric unit of (I), is shown in Fig. 1. The cation of (I) is planar in the crystalline phase. Atoms C9 and N10, as well as the respective cyano group and methyl C atom attached to them, are arranged linearly along a crystallographic twofold axis (Table 1). The H atoms of the methyl group occupy two orientations, each with occupancy 0.5. This is typical of compounds in which the H atoms of the methyl group do not interact with the O atoms of the anions, unlike the 10-methylacridinium halides, where C—H interactions with anions fix the methyl group in one position (Storoniak et al., 2000). The central N1—O1···H1B···O1iii—N1iii moiety of the hydrogen dinitrate anion appears to be planar, as in other inorganic (Duke & Llewellyn, 1950; Faithful & Wallwork, 1967; Roziere et al., 1976) and organic (Al-Zamil et al., 1982; Roziere et al., 1979) compounds containing this anion [symmetry code: (iii) -x, -y, -z]. Please check added symmetry code. The other two O atoms of each nitrate are twisted out of this plane by 14.7 (2)°.

Compound (I) is a typical ionic compound in which electrostatic interactions between the ions are the main factor binding cations and anions in the lattice. As a result of these interactions, the lattice is relatively compact, and anions and cations are in contact with each other via O···H interactions (Table 2). The arrangement of the ions and the network of C—H···O interactions are shown in Fig. 2. It should be noted that the cations are arranged in layers, with the neighbouring molecules `head-to-tail'. These layers are linked through C—H···O interactions involving four O atoms of the hydrogen dinitrate anion and the H atoms attached to the C atoms of the acridine moiety in ring positions 2 or 4. One H atom seems to be located on a centre of inversion and participates in a very short hydrogen bond. The distance between the two O atoms of the two nitrate moieties involved in this interaction is 2.440 (4) Å and the H atom is located exactly at the midpoint of these two O atoms.

The effect of the strong hydrogen bond in the hydrogen dinitrate anion causes the bonds between the N and O atoms involved in it to be longer than the four remaining N—O bonds and the O—N—O valence angles to be inequivalent (Table 1). Another interesting feature is that the anions and cations form columns held in place by the network of C—H···O interactions. These multidirectional interactions undoubtedly stabilize the lattice and increase the attractiveness of the compound as an analytical indicator or a chemiluminogenic fragment of a label.

Experimental top

9-Cyano-10-methylacridinium hydrogen dinitrate was prepared by the oxidation of 9-cyano-10-methylacridan (Kaufmann & Albertini, 1909, 1911) with dilute nitric acid (McCapra & Richardson, 1964). Yellow crystals of (I) suitable for X-ray investigation were grown from a solution in water.

Refinement top

The H atom of the hydrogen nitrate was refined freely. Please check. The methyl H atoms attached to atom C16 were located from difference Fourier syntheses and refined as a rigid rotating group with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C). As C16 is located on a diad, the H atoms were refined in three unique positions with an occupancy factor of 0.5. Other H atoms attached to C atoms were placed geometrically and refined using a riding model, with Uiso(H) = 1.2Ueq(C) and C—H = 0.96 Å. Please clarify; according to the data in the CIF, they were all refined freely.

Computing details top

Data collection: KM-4 Software (Kuma Diffraction, 1989); cell refinement: KM-4 Software; data reduction: KM-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing the atom-labelling scheme and 50% probability displacement ellipsoids [symmetry codes: (i) -x, y, 1/2 - z; (iii) -x, -y, -z].
[Figure 2] Fig. 2. The packing diagram for (I) in the unit cell viewed along the b axis. Hydrogen bonds are represented by dashed lines.
9-Cyano-10-methylacridinium hydrogen dinitrate top
Crystal data top
C15H11N2+·HN2O6F(000) = 712
Mr = 344.29Dx = 1.507 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 50 reflections
a = 12.799 (4) Åθ = 6.0–24.0°
b = 10.015 (3) ŵ = 0.12 mm1
c = 13.168 (4) ÅT = 293 K
β = 115.96 (4)°Prism, green
V = 1517.6 (8) Å30.5 × 0.2 × 0.15 mm
Z = 4
Data collection top
Kuma KM-4
diffractometer
Rint = 0.000
Radiation source: fine-focus sealed tubeθmax = 29.0°, θmin = 2.7°
Graphite monochromatorh = 1715
θ/2θ scansk = 013
2003 measured reflectionsl = 1715
2003 independent reflections3 standard reflections every 200 reflections
1104 reflections with I > 2σ(I) intensity decay: 3.6%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.169H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.096P)2 + 0.22P]
where P = (Fo2 + 2Fc2)/3
2003 reflections(Δ/σ)max = 0.001
125 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C15H11N2+·HN2O6V = 1517.6 (8) Å3
Mr = 344.29Z = 4
Monoclinic, C2/cMo Kα radiation
a = 12.799 (4) ŵ = 0.12 mm1
b = 10.015 (3) ÅT = 293 K
c = 13.168 (4) Å0.5 × 0.2 × 0.15 mm
β = 115.96 (4)°
Data collection top
Kuma KM-4
diffractometer
Rint = 0.000
2003 measured reflections3 standard reflections every 200 reflections
2003 independent reflections intensity decay: 3.6%
1104 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.169H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.25 e Å3
2003 reflectionsΔρmin = 0.26 e Å3
125 parameters
Special details top

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) top
xyzUiso*/UeqOcc. (<1)
C10.11298 (16)0.6781 (2)0.45717 (15)0.0516 (5)
H1A0.109420.77390.457470.063 (6)*
C20.16584 (18)0.6095 (2)0.55404 (17)0.0616 (6)
H2A0.207130.65720.623510.086 (8)*
C30.16546 (19)0.4700 (2)0.55297 (18)0.0650 (6)
H3A0.202720.41820.620790.093 (8)*
C40.11164 (18)0.3993 (2)0.45533 (18)0.0580 (5)
H4A0.110710.30350.453510.074 (7)*
C90.00000.6776 (2)0.25000.0407 (5)
N100.00000.40130 (18)0.25000.0450 (5)
C110.05554 (14)0.60999 (16)0.35227 (14)0.0411 (4)
C120.05463 (15)0.46744 (16)0.35101 (15)0.0437 (4)
C150.00000.8218 (2)0.25000.0516 (6)
N20.00000.9351 (2)0.25000.0780 (9)
C160.00000.2535 (3)0.25000.0694 (9)
H16A0.00520.2216 (3)0.17920.104*0.50
H16B0.06540.2216 (3)0.26040.104*0.50
H16C0.07050.2216 (3)0.31040.104*0.50
N10.16168 (15)0.06181 (17)0.11855 (14)0.0541 (4)
O10.06814 (13)0.09328 (15)0.02957 (13)0.0674 (5)
O20.22574 (15)0.15292 (19)0.16909 (13)0.0796 (5)
O30.18071 (17)0.05459 (17)0.14531 (16)0.0817 (6)
H1B0.000 (4)0.000 (7)0.000 (6)0.105 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0509 (10)0.0533 (11)0.0519 (10)0.0047 (8)0.0238 (8)0.0059 (8)
C20.0564 (12)0.0773 (15)0.0483 (11)0.0046 (10)0.0203 (9)0.0022 (9)
C30.0552 (12)0.0822 (16)0.0526 (12)0.0059 (11)0.0189 (10)0.0191 (10)
C40.0572 (12)0.0482 (11)0.0680 (13)0.0049 (9)0.0269 (11)0.0161 (9)
C90.0434 (12)0.0329 (11)0.0509 (13)0.0000.0253 (11)0.000
N100.0443 (11)0.0284 (9)0.0606 (13)0.0000.0213 (10)0.000
C110.0405 (8)0.0372 (8)0.0482 (9)0.0020 (7)0.0219 (7)0.0011 (6)
C120.0396 (8)0.0380 (8)0.0539 (10)0.0001 (7)0.0207 (8)0.0047 (7)
C150.0669 (17)0.0399 (13)0.0543 (14)0.0000.0323 (13)0.000
N20.121 (3)0.0404 (14)0.091 (2)0.0000.063 (2)0.000
C160.0731 (19)0.0284 (11)0.091 (2)0.0000.0216 (17)0.000
N10.0527 (9)0.0604 (11)0.0475 (9)0.0005 (8)0.0203 (8)0.0026 (8)
O10.0599 (9)0.0544 (8)0.0662 (9)0.0058 (7)0.0075 (7)0.0108 (7)
O20.0743 (10)0.0881 (12)0.0672 (10)0.0266 (9)0.0224 (8)0.0163 (9)
O30.0793 (12)0.0695 (11)0.0798 (12)0.0193 (9)0.0195 (9)0.0137 (8)
Geometric parameters (Å, º) top
C9—C151.444 (3)C2—C31.397 (3)
N10—C161.480 (3)C3—H3A0.9598
C15—N21.135 (3)C3—C41.361 (3)
N1—O11.295 (2)C4—H4A0.9601
N1—O21.212 (2)C4—C121.417 (3)
N1—O31.211 (2)C9—C111.392 (2)
O1—H1B1.220 (2)N10—C121.372 (2)
C1—H1A0.9599C11—C121.428 (2)
C1—C21.343 (3)C16—H16C0.9600
C1—C111.423 (2)C16—H16A0.9600
C2—H2A0.9598C16—H16B0.9600
C11—C9—C15119.08 (10)H4A—C4—C3122.62
C12—N10—C16118.87 (10)H4A—C4—C12117.50
O1—N1—O2116.65 (17)C3—C4—C12119.88 (19)
O1—N1—O3119.07 (17)C9—C11—C1122.26 (16)
O2—N1—O3124.27 (19)C9—C11—C12118.47 (15)
N1—O1—H1B110.55 (13)C1—C11—C12119.27 (15)
H1A—C1—C2120.85N10—C12—C4122.35 (17)
H1A—C1—C11118.53N10—C12—C11119.48 (15)
C2—C1—C11120.53 (19)C4—C12—C11118.18 (16)
H2A—C2—C1119.26H16C—C16—H16A109.5
H2A—C2—C3120.37H16C—C16—H16B109.5
C1—C2—C3120.30 (19)H16A—C16—H16B109.5
H3A—C3—C4115.96H16C—C16—N10109.5
H3A—C3—C2122.20H16A—C16—N10109.5
C4—C3—C2121.84 (19)H16B—C16—N10109.5
C11i—C9—C11—C120.13 (11)C16—N10—C12—C40.36 (19)
C12i—N10—C12—C110.13 (11)C16—N10—C12—C11179.87 (11)
C11—C1—C2—C30.2 (3)C3—C4—C12—N10179.35 (17)
C1—C2—C3—C40.5 (3)C3—C4—C12—C110.2 (3)
C2—C3—C4—C120.4 (3)C9—C11—C12—N100.3 (2)
C15—C9—C11—C10.29 (18)C1—C11—C12—N10179.58 (14)
C15—C9—C11—C12179.87 (11)C9—C11—C12—C4179.79 (14)
C2—C1—C11—C9179.83 (16)C1—C11—C12—C40.1 (2)
C2—C1—C11—C120.0 (3)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2ii—H2Aii···O20.962.483.313 (3)145
C4—H4A···O1iii0.962.493.337 (3)147
O1—H1B···O1iv1.221.222.440 (4)180
Symmetry codes: (ii) x+1/2, y+1/2, z+1; (iii) x, y, z+1/2; (iv) x, y, z.

Experimental details

Crystal data
Chemical formulaC15H11N2+·HN2O6
Mr344.29
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)12.799 (4), 10.015 (3), 13.168 (4)
β (°) 115.96 (4)
V3)1517.6 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.5 × 0.2 × 0.15
Data collection
DiffractometerKuma KM-4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2003, 2003, 1104
Rint0.000
(sin θ/λ)max1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.169, 1.07
No. of reflections2003
No. of parameters125
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.25, 0.26

Computer programs: KM-4 Software (Kuma Diffraction, 1989), KM-4 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
C9—C151.444 (3)N1—O21.212 (2)
N10—C161.480 (3)N1—O31.211 (2)
C15—N21.135 (3)O1—H1B1.220 (2)
N1—O11.295 (2)
C11—C9—C15119.08 (10)O1—N1—O3119.07 (17)
C12—N10—C16118.87 (10)O2—N1—O3124.27 (19)
O1—N1—O2116.65 (17)N1—O1—H1B110.55 (13)
C11i—C9—C11—C120.13 (11)C12i—N10—C12—C110.13 (11)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2ii—H2Aii···O20.962.483.313 (3)145
C4—H4A···O1iii0.962.493.337 (3)147
O1—H1B···O1iv1.221.222.440 (4)180
Symmetry codes: (ii) x+1/2, y+1/2, z+1; (iii) x, y, z+1/2; (iv) x, y, z.
 

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