N,N-Di­methyl-N'-phenyl­formamidinium perchlorate

The molecular structure of the title compound, C₉H₁₃N₂⁺·ClO₄⁻, consists of an N,N-di­methyl–N′-phenyl­formamidinium cation and a perchlorate anion. The latter forms five hydrogen bonds with three different formamidin­ium cations, using three O atoms. The cations and anions are linked through C—H...O and N—H...O hydrogen bonds, forming a ring; the centrosymmetrically related rings form a staircase via C—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.051
• wR factor = 0.153
• Data-to-parameter ratio = 18.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_728  Alert B D-H..A  Calc      136.62, Rep      134.00, Dev.      2.62 Deg.
                     C2   -H2   -O4      1.555   1.555   3.655


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 0 Alert Level C = Please check

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S1. Comment

There are considerable interests in the chemistry and structure of iminium salts, because of their importances in organic synthesis (Boehme & Viehe, 1976). The chromophore of visual pigments contain polyunsaturated iminium salts (Uhl & Abrahamson, 1981; Brige, 1981). The iminium salts exhibit optical properties and the position of the counterion plays in determining the optical properties of iminium cation (Arnaboldi et al., 1979).

The cation of the title compound, (I), is nearly planar and the dihedral angle between the phenyl ring and the Schiff base chain is 7.7 (1)°. The protonation occurs at N9, the positive charge is delocalized between N9 and N7 atoms, as evidenced from the N7—C8 [1.316 (3) Å] and C8═N9 [1.294 (3) Å]. This is confirmed by the planarity of the atoms C1, N7, C8, N9, C10 and C11 [maximum deviation is 0.031 (4) Å for C10]. The perchlorate anion accepts five hydrogen bonds from three different formamidinium cations using three O atoms. One of the perchlorate O atoms (O4) acts as an acceptor in three hydrogen bonds and this O atom is also characterized by an extended bond of 1.426 (2) Å. The cations and anions are linked through N7—H7···O4ⁱ and C8—H8···O3ⁱⁱ hydrogen bonds and form a ring, which is further reinforced by two C2—H2···O4ⁱ and C11—H11D···O4ⁱ hydrogen bonds. The centrosymmetrically related rings are linked via C11—H11E···O1ⁱⁱⁱ interactions and form a staircase, which runs parallel to b axis (see Table 2 for symmetry codes).

S2. Experimental

Anisole (0.05 mol) was dissolved in 6 ml DMF and kept under ice-cold condition. To this, 1.4 ml POCl₃ (0.035 ml) was added dropwise for 15 min with stirring. The reaction mixture was stirred at room temperature for 30 minutes and then at 353–363 K for 15 h. The reaction mixture was finally poured into crushed ice and treated with sodium perchlorate or dilute perchloric acid. The creamy yellow precipitate obtained was filtered, washed with water and dried. This crude product was recrystallized using CHCl₃ to give pure vinamidinium perchlorate.

S3. Refinement

The H atom on N7 was located in a difference Fourier map and refined, while all other H atoms were positioned geometrically and were allowed to ride on their attached atoms. One of the methyl group (C11) was found to be disordered; it was treated as an idealized disordered methyl group, with two positions rotated from each other by 60°, and the site-occupation factors fixed at 0.5.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT; data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997) and PLUTON (Spek, 1990); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

	Fig. 1. The molecular structure of title compound, (I), showing 35% probability displacement ellipsoids.
	Fig. 2. Part of the crystal packing of the title compound, showing hydrogen-bonded networks of cations and anions. Atoms marked with a dollar ($), hash (#) or asterisk (*) at the symmetry positions (1 − x, −y, −z), (1 − x, −y, 1 − z) and (1 − x, y − 1/2, 1/2 − z), respectively.

N,N-Dimethyl-N'-phenylformamidinium perchlorate

Crystal data

C9H13N2ClO4	F(000) = 520
Mr = 248.66	Dx = 1.433 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.8382 (2) Å	Cell parameters from 3903 reflections
b = 17.5688 (6) Å	θ = 2.3–28.3°
c = 9.1123 (2) Å	µ = 0.33 mm^−1
β = 113.269 (1)°	T = 293 K
V = 1152.77 (6) Å^3	Prism, pale yellow
Z = 4	0.28 × 0.16 × 0.12 mm

Data collection

Siemens SMART CCD area-detector diffractometer	2854 independent reflections
Radiation source: fine-focus sealed tube	1917 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 28.3°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −10→8
Tmin = 0.913, Tmax = 0.961	k = −15→23
7777 measured reflections	l = −11→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.0752P)^2 + 0.2933P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
2854 reflections	Δρmax = 0.34 e Å^−3
151 parameters	Δρmin = −0.22 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.007 (2)

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	Occ. (<1)
Cl1	0.75658 (8)	0.09207 (4)	0.40685 (6)	0.0505 (2)
O1	0.6675 (5)	0.16311 (15)	0.3667 (4)	0.1206 (11)
O2	0.9502 (3)	0.10162 (17)	0.4825 (3)	0.1099 (10)
O3	0.6889 (4)	0.04966 (17)	0.5051 (3)	0.1095 (10)
O4	0.7132 (3)	0.04853 (13)	0.2645 (2)	0.0815 (7)
C1	0.1972 (3)	0.04931 (12)	0.0399 (3)	0.0407 (5)
C2	0.1093 (3)	0.08289 (14)	−0.1084 (3)	0.0490 (6)
H2	0.1057	0.0581	−0.1997	0.059*
C3	0.0268 (4)	0.15331 (15)	−0.1204 (3)	0.0581 (7)
H3	−0.0322	0.1757	−0.2202	0.070*
C4	0.0309 (4)	0.19080 (14)	0.0139 (4)	0.0634 (7)
H4	−0.0216	0.2389	0.0056	0.076*
C5	0.1141 (4)	0.15589 (17)	0.1606 (4)	0.0689 (8)
H5	0.1141	0.1802	0.2513	0.083*
C6	0.1973 (4)	0.08558 (15)	0.1753 (3)	0.0590 (7)
H6	0.2530	0.0626	0.2749	0.071*
N7	0.2839 (3)	−0.02239 (11)	0.0462 (2)	0.0410 (4)
C8	0.3865 (3)	−0.05880 (13)	0.1778 (3)	0.0435 (5)
H8	0.4032	−0.0355	0.2742	0.052*
N9	0.4664 (3)	−0.12399 (11)	0.1854 (2)	0.0460 (5)
C10	0.5844 (5)	−0.1561 (2)	0.3408 (3)	0.0789 (10)
H10A	0.7117	−0.1552	0.3526	0.118*
H10B	0.5476	−0.2077	0.3473	0.118*
H10C	0.5714	−0.1265	0.4243	0.118*
C11	0.4510 (4)	−0.16781 (15)	0.0437 (3)	0.0565 (6)
H11A	0.5201	−0.2143	0.0764	0.085*	0.50
H11B	0.5000	−0.1384	−0.0196	0.085*	0.50
H11C	0.3229	−0.1794	−0.0184	0.085*	0.50
H11D	0.3752	−0.1404	−0.0508	0.085*	0.50
H11E	0.3953	−0.2163	0.0452	0.085*	0.50
H11F	0.5725	−0.1753	0.0440	0.085*	0.50
H7	0.273 (4)	−0.0405 (17)	−0.040 (4)	0.070 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0600 (4)	0.0554 (4)	0.0369 (3)	−0.0038 (3)	0.0200 (2)	−0.0073 (2)
O1	0.142 (2)	0.0674 (17)	0.136 (2)	0.0303 (16)	0.0374 (19)	−0.0123 (16)
O2	0.0655 (15)	0.136 (3)	0.105 (2)	−0.0195 (14)	0.0092 (13)	0.0016 (17)
O3	0.147 (2)	0.133 (2)	0.0808 (16)	−0.0242 (19)	0.0795 (18)	0.0046 (15)
O4	0.1266 (19)	0.0787 (15)	0.0445 (10)	−0.0073 (13)	0.0397 (12)	−0.0125 (10)
C1	0.0397 (11)	0.0372 (11)	0.0452 (11)	−0.0039 (9)	0.0168 (9)	−0.0001 (9)
C2	0.0534 (13)	0.0489 (14)	0.0467 (12)	−0.0012 (11)	0.0220 (11)	0.0059 (10)
C3	0.0562 (15)	0.0509 (14)	0.0653 (16)	0.0022 (12)	0.0222 (12)	0.0179 (13)
C4	0.0560 (15)	0.0378 (13)	0.095 (2)	0.0047 (11)	0.0284 (15)	0.0025 (14)
C5	0.0795 (19)	0.0547 (16)	0.0687 (18)	0.0066 (14)	0.0253 (15)	−0.0154 (14)
C6	0.0707 (17)	0.0539 (16)	0.0448 (13)	0.0096 (13)	0.0149 (12)	−0.0020 (11)
N7	0.0484 (10)	0.0391 (10)	0.0352 (9)	−0.0001 (8)	0.0163 (8)	0.0000 (8)
C8	0.0513 (13)	0.0445 (13)	0.0383 (11)	−0.0006 (10)	0.0216 (10)	0.0015 (9)
N9	0.0516 (11)	0.0445 (11)	0.0448 (10)	0.0055 (9)	0.0221 (8)	0.0074 (8)
C10	0.101 (2)	0.081 (2)	0.0570 (17)	0.0360 (19)	0.0327 (17)	0.0253 (15)
C11	0.0649 (16)	0.0470 (14)	0.0608 (15)	0.0006 (12)	0.0283 (13)	−0.0049 (11)

Geometric parameters (Å, º)

Cl1—O1	1.406 (3)	N7—C8	1.316 (3)
Cl1—O2	1.407 (2)	N7—H7	0.82 (3)
Cl1—O3	1.419 (2)	C8—N9	1.294 (3)
Cl1—O4	1.426 (2)	C8—H8	0.9300
C1—C2	1.383 (3)	N9—C10	1.465 (3)
C1—C6	1.388 (3)	N9—C11	1.466 (3)
C1—N7	1.422 (3)	C10—H10A	0.9600
C2—C3	1.380 (3)	C10—H10B	0.9600
C2—H2	0.9300	C10—H10C	0.9600
C3—C4	1.379 (4)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—C5	1.378 (4)	C11—H11C	0.9600
C4—H4	0.9300	C11—H11D	0.9600
C5—C6	1.378 (4)	C11—H11E	0.9600
C5—H5	0.9300	C11—H11F	0.9600
C6—H6	0.9300
O1—Cl1—O2	110.5 (2)	C8—N9—C10	120.0 (2)
O1—Cl1—O3	111.1 (2)	C8—N9—C11	123.2 (2)
O2—Cl1—O3	110.7 (2)	C10—N9—C11	116.7 (2)
O1—Cl1—O4	108.9 (2)	N9—C10—H10A	109.5
O2—Cl1—O4	109.5 (2)	N9—C10—H10B	109.5
O3—Cl1—O4	106.1 (2)	H10A—C10—H10B	109.5
C2—C1—C6	119.8 (2)	N9—C10—H10C	109.5
C2—C1—N7	117.6 (2)	H10A—C10—H10C	109.5
C6—C1—N7	122.6 (2)	H10B—C10—H10C	109.5
C3—C2—C1	119.8 (2)	N9—C11—H11A	109.5
C3—C2—H2	120.1	N9—C11—H11B	109.5
C1—C2—H2	120.1	H11A—C11—H11B	109.5
C2—C3—C4	120.8 (2)	N9—C11—H11C	109.5
C2—C3—H3	119.6	H11A—C11—H11C	109.5
C4—C3—H3	119.6	H11B—C11—H11C	109.5
C5—C4—C3	119.0 (2)	N9—C11—H11D	109.5
C5—C4—H4	120.5	H11A—C11—H11D	141.1
C3—C4—H4	120.5	H11B—C11—H11D	56.3
C4—C5—C6	121.1 (3)	H11C—C11—H11D	56.3
C4—C5—H5	119.4	N9—C11—H11E	109.5
C6—C5—H5	119.4	H11A—C11—H11E	56.3
C5—C6—C1	119.4 (2)	H11B—C11—H11E	141.1
C5—C6—H6	120.3	H11C—C11—H11E	56.3
C1—C6—H6	120.3	H11D—C11—H11E	109.5
C8—N7—C1	125.3 (2)	N9—C11—H11F	109.5
C8—N7—H7	119 (2)	H11A—C11—H11F	56.3
C1—N7—H7	116 (2)	H11B—C11—H11F	56.3
N9—C8—N7	126.0 (2)	H11C—C11—H11F	141.1
N9—C8—H8	117.0	H11D—C11—H11F	109.5
N7—C8—H8	117.0	H11E—C11—H11F	109.5
C6—C1—C2—C3	1.9 (4)	N7—C1—C6—C5	178.5 (2)
N7—C1—C2—C3	−178.5 (2)	C2—C1—N7—C8	173.9 (2)
C1—C2—C3—C4	0.0 (4)	C6—C1—N7—C8	−6.5 (4)
C2—C3—C4—C5	−1.9 (4)	C1—N7—C8—N9	−179.9 (2)
C3—C4—C5—C6	1.9 (4)	N7—C8—N9—C10	177.0 (2)
C4—C5—C6—C1	0.0 (4)	N7—C8—N9—C11	−0.7 (4)
C2—C1—C6—C5	−1.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11D···N7	0.96	2.47	2.875 (3)	105
N7—H7···O4^i	0.82 (3)	2.09 (3)	2.877 (3)	160 (3)
C2—H2···O4^i	0.93	2.56	3.295 (3)	134
C11—H11D···O4^i	0.96	2.41	3.329 (3)	160
C8—H8···O3^ii	0.93	2.40	3.174 (4)	140
C11—H11E···O1^iii	0.96	2.38	3.310 (4)	162

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