3,6-Diamino­acridinium perchlorate

The structure of the title compound, C₁₃H₁₂N₃⁺·ClO₄⁻, reveals a twofold axis through the ring N and para-C atoms; a twofold rotation axis also passes through the Cl atom. The structure of the organic fragment is similar to that of homologous heterocyclic systems. The organic cations and perchlorate anions self-assemble in the solid state through C—H...O and N—H...O hydrogen bonds, leading to a two-dimensional layer parallel to the (112) plane. The layers are stacked along the c axis through offset π–π inter­actions between cations from different layers (the distance between the planes through two cations is 3.35 Å), resulting in a three-dimensional supra­molecular architecture.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.051
• wR factor = 0.132
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT738_ALERT_1_B D-H..A  Calc    152.1(2), Rep   152.0(10) ......       5.00 su-Ra
              N1   -H1   -O1      1.555   1.555   1.555

Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2A    ...          ?

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Nitrogen containing heterocycles, along with aromatic amines, are valuable candidates for building supramolecular architectures (Berceanu et al., 2002 and Diop et al., 2002). The structural investigation of acridinium-3,6-diamine perchlorate, (C₁₃H₁₂N₃)⁺(ClO₄)^- (I), is a result of our constant interest in this field. The asymmetric unit of the title compound consists of two independent halves of each molecular ion. The remainder of the molecules are generated by twofold axes through atoms C7 and N1 for (C₁₃H₁₂N₃)⁺ and the Cl1 atom, bisecting the O—Cl—O angles, for (ClO₄)^- (Fig. 1). All metric data for the organic unit are consistent with the corresponding values found in homologous derivatives [cf. (C₁₃H₁₃N₃)Cl₂·2H₂O; (C₁₃H₁₂N₃)₂(SO₄)·3.5H₂O and C₁₃H₁₁N₃·H₂O: C—C = 1.32—1.45 Å, C—N = 1.33—1.39 Å, C—N—C = 118—123° (Obendorf et al., 1974; Jones & Neidle, 1975 and Achari & Neidle, 1976)]. The perchlorate unit is essentially tetrahedral.

The molecules associate in the solid state into a two-dimensional network via N—H···O and C—H···O hydrogen bonding (Fig. 2). Thus, each perchlorate unit links three organic units, which in turn is connected to three other perchlorates through the NH₂ group interacting with the O2 atoms from two ClO₄^- cations (Table 1).

The two-dimensional layers along the (112) plane are stacked in the third dimension due to off-set π-π interactions between organic molecules facing in alternating directions [distances between centroids: Cg1—Cg1^vi = 3.69 Å, Cg2—Cg2ⁱⁱⁱ = 3.72 Å, Cg1ⁱ—Cg1ⁱⁱⁱ = 3.69 Å, symmetry codes: (i) -x + 2, y, -z + 1/2; (iii) 2 - x, -y, -z; (iv) x, -y, z - 1/2; distance between the planes of two interacting cations 3.35 Å] (Fig. 3).

All these interactions lead to the formation of a three-dimensional supramolecular architecture built up by interlocking layers (Fig. 4).

Related literature

For similar structures, see: Obendorf et al. (1974); Jones & Neidle (1975); Achari & Neidle (1976). For related literature, see: Berceanu et al. (2002); Diop et al. (2002). For synthesis, see: Rus et al. (2001).

S2. Experimental

The title compound was obtained by decomposition of [FeL(ClO₄)₂(H₂O)₂](ClO₄), L = 4-(3-aminoacridine-6-imino)pentane-2-one, in 70% HClO₄ solution (Rus et al., 2001). Slow evaporation of the mother liquor at room temperature deposited the product as yellow crystals.

S3. Refinement

All hydrogen atoms were placed in calculated positions using a riding model, with C—H = 0.93–0.97 Å and U_iso= 1.2U_eq(C) for aryl H. The H atoms bonded to N1 and N2 were found in a difference map and refined with a restrained N—H distance of 0.86 (2), 0.85 (2) and 0.87 (2) Å, respectively.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures

	Fig. 1. : View of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x + 2, y, -z + 1/2].
	Fig. 2. : The hydrogen bonding (dashed lines) scheme in the title compound. [Symmetry codes: (i) -x + 2, y, -z + 1/2; (ii) -x + 3/2, y - 1/2, -z + 1/2].
	Fig. 3. : π-π interactions (dashed lines) between cations. [Symmetry codes: (i) -x + 2, y, -z + 1/2; (iii) 2 - x, -y, -z; (iv) x, -y, z - 1/2]. Cg1 is the centroid of the C1—C6 ring and Cg2 is the centroid of the C1C6C7C6^iC1^iN1 ring.
	Fig. 4. : Crystal packing of the title compound along the c axis. The hydrogen bonding is shown as dashed lines.

3,6-Diaminoacridinium perchlorate

Crystal data

C13H12N3^+·ClO4^−	F(000) = 640
Mr = 309.71	Dx = 1.538 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2203 reflections
a = 15.122 (3) Å	θ = 2.8–26.3°
b = 13.477 (3) Å	µ = 0.31 mm^−1
c = 6.6922 (13) Å	T = 297 K
β = 101.21 (3)°	Block, yellow
V = 1337.8 (5) Å^3	0.33 × 0.29 × 0.19 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1378 independent reflections
Radiation source: fine-focus sealed tube	1271 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SHELXTL; Bruker, 2001)	h = −18→18
Tmin = 0.906, Tmax = 0.934	k = −16→16
7044 measured reflections	l = −8→8

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0551P)^2 + 1.4184P] where P = (Fo^2 + 2Fc^2)/3
1378 reflections	(Δ/σ)max = 0.002
107 parameters	Δρmax = 0.29 e Å^−3
3 restraints	Δρmin = −0.26 e Å^−3

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
O1	1.07618 (16)	0.26928 (18)	0.3309 (4)	0.0941 (8)
Cl1	1.0000	0.32862 (5)	0.2500	0.0515 (3)
O2	0.98003 (15)	0.3883 (2)	0.4083 (4)	0.1039 (10)
H2B	0.6281 (14)	0.013 (2)	0.088 (4)	0.068 (9)*
H2A	0.6775 (19)	0.1098 (13)	0.086 (4)	0.058 (8)*
H1	1.0000	0.1045 (14)	0.2500	0.038 (8)*
C1	0.91822 (13)	−0.00693 (16)	0.2142 (3)	0.0332 (5)
C2	0.83806 (13)	0.04662 (16)	0.1780 (3)	0.0369 (5)
H2	0.8394	0.1156	0.1765	0.044*
C3	0.75599 (14)	−0.00306 (18)	0.1442 (3)	0.0409 (5)
C4	0.75544 (16)	−0.10858 (19)	0.1491 (3)	0.0482 (6)
H4	0.7007	−0.1421	0.1291	0.058*
C5	0.83282 (16)	−0.16078 (18)	0.1823 (3)	0.0472 (6)
H5	0.8305	−0.2297	0.1832	0.057*
C6	0.91832 (14)	−0.11245 (16)	0.2160 (3)	0.0379 (5)
C7	1.0000	−0.1620 (2)	0.2500	0.0422 (7)
H7	1.0000	−0.2310	0.2500	0.051*
N1	1.0000	0.04076 (17)	0.2500	0.0334 (5)
N2	0.67680 (14)	0.04645 (19)	0.1091 (3)	0.0555 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0980 (17)	0.0749 (15)	0.1176 (19)	0.0489 (13)	0.0411 (14)	0.0333 (13)
Cl1	0.0437 (5)	0.0335 (4)	0.0787 (6)	0.000	0.0151 (4)	0.000
O2	0.0599 (13)	0.1064 (18)	0.137 (2)	0.0192 (12)	−0.0019 (13)	−0.0666 (17)
C1	0.0377 (11)	0.0405 (11)	0.0216 (9)	−0.0026 (8)	0.0062 (7)	−0.0006 (7)
C2	0.0388 (11)	0.0419 (11)	0.0298 (10)	−0.0013 (9)	0.0062 (8)	0.0004 (8)
C3	0.0384 (11)	0.0574 (13)	0.0266 (10)	−0.0039 (9)	0.0058 (8)	−0.0011 (9)
C4	0.0441 (13)	0.0592 (14)	0.0411 (12)	−0.0167 (11)	0.0075 (10)	−0.0032 (11)
C5	0.0547 (14)	0.0437 (12)	0.0434 (12)	−0.0121 (10)	0.0100 (10)	−0.0017 (10)
C6	0.0442 (12)	0.0394 (11)	0.0297 (10)	−0.0043 (9)	0.0061 (8)	0.0001 (8)
C7	0.0581 (19)	0.0339 (15)	0.0350 (15)	0.000	0.0097 (13)	0.000
N1	0.0374 (13)	0.0303 (12)	0.0327 (12)	0.000	0.0072 (9)	0.000
N2	0.0354 (11)	0.0683 (16)	0.0608 (13)	−0.0036 (10)	0.0045 (9)	0.0007 (11)

Geometric parameters (Å, º)

O1—Cl1	1.420 (2)	C4—C5	1.346 (3)
Cl1—O2^i	1.409 (2)	C4—H4	0.9300
Cl1—O2	1.409 (2)	C5—C6	1.426 (3)
Cl1—O1^i	1.420 (2)	C5—H5	0.9300
C1—N1	1.373 (2)	C6—C7	1.384 (3)
C1—C2	1.391 (3)	C7—C6^i	1.384 (3)
C1—C6	1.422 (3)	C7—H7	0.9300
C2—C3	1.389 (3)	N1—C1^i	1.373 (2)
C2—H2	0.9300	N1—H1	0.859 (18)
C3—N2	1.351 (3)	N2—H2B	0.849 (17)
C3—C4	1.423 (3)	N2—H2A	0.868 (17)
Cl1—O1—H1	96.4 (2)	C5—C4—H4	119.4
O2^i—Cl1—O2	110.4 (3)	C3—C4—H4	119.4
O2^i—Cl1—O1	109.37 (14)	C4—C5—C6	121.3 (2)
O2—Cl1—O1	108.13 (15)	C4—C5—H5	119.3
O2^i—Cl1—O1^i	108.13 (15)	C6—C5—H5	119.3
O2—Cl1—O1^i	109.37 (14)	C7—C6—C1	118.9 (2)
O1—Cl1—O1^i	111.5 (2)	C7—C6—C5	123.9 (2)
N1—C1—C2	120.83 (19)	C1—C6—C5	117.1 (2)
N1—C1—C6	117.86 (19)	C6—C7—C6^i	122.3 (3)
C2—C1—C6	121.31 (18)	C6—C7—H7	118.9
C3—C2—C1	119.9 (2)	C6^i—C7—H7	118.9
C3—C2—H2	120.0	C1^i—N1—C1	124.2 (2)
C1—C2—H2	120.0	C1^i—N1—H1	117.92 (12)
N2—C3—C2	121.6 (2)	C1—N1—H1	117.91 (12)
N2—C3—C4	119.3 (2)	C3—N2—H2B	119 (2)
C2—C3—C4	119.1 (2)	C3—N2—H2A	118.4 (19)
C5—C4—C3	121.2 (2)	H2B—N2—H2A	122 (3)
H1—O1—Cl1—O2^i	−119.52 (15)	N1—C1—C6—C7	−1.1 (2)
H1—O1—Cl1—O2	120.25 (15)	C2—C1—C6—C7	179.14 (15)
H1—O1—Cl1—O1^i	0.001 (1)	N1—C1—C6—C5	178.86 (15)
N1—C1—C2—C3	−179.32 (15)	C2—C1—C6—C5	−0.9 (3)
C6—C1—C2—C3	0.4 (3)	C4—C5—C6—C7	−179.71 (18)
C1—C2—C3—N2	179.85 (19)	C4—C5—C6—C1	0.3 (3)
C1—C2—C3—C4	0.6 (3)	C1—C6—C7—C6^i	0.55 (12)
N2—C3—C4—C5	179.6 (2)	C5—C6—C7—C6^i	−179.4 (2)
C2—C3—C4—C5	−1.2 (3)	C2—C1—N1—C1^i	−179.68 (19)
C3—C4—C5—C6	0.7 (3)	C6—C1—N1—C1^i	0.55 (12)

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86 (2)	2.51 (2)	3.296 (3)	152 (1)
N1—H1···O1^i	0.86 (2)	2.51 (2)	3.296 (3)	152 (1)
C2—H2···O1^i	0.93	2.44	3.274 (3)	150
N2—H2B···O2^ii	0.85 (2)	2.35 (3)	3.174 (3)	164 (2)

Symmetry codes: (i) −x+2, y, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2.