4,4,5,5-Tetra-methyl-2-(4-pyridinio)-2-imidazoline-1-oxyl-3-oxide perchlorate.

The crystal structure of the title compound, C(12)H(17)N(3)O(2) (+)·ClO(4) (-), consists of 4,4,5,5-tetra-methyl-2-(4-pyridinio)imidazoline-1-oxyl-3-oxide radical cations and perchlorate anions. Both the cation and the Cl atom of the anion are located on the same twofold rotation axis, and the crystal structure shows the average structure for the radical cation. The five-membered ring assumes a half-chair conformation. The cation links with the anion via N-H⋯O hydrogen bonding.

Related literature

For general background, see: Wang et al. (2004 ▶); Li et al. (2003 ▶); Kahn et al. (2000 ▶); Tsukahara et al. (2003 ▶); Fettouhi et al. (2003 ▶); Zhang et al. (2004 ▶); Fokin et al. (2004 ▶); Chang et al. (2009 ▶). For the synthesis, see: Ullman et al. (1970 ▶, 1972 ▶).

Experimental

Crystal data

C12H17N3O2 +·ClO4 −

M = 334.74

Orthorhombic,

a = 17.485 (4) Å

b = 11.854 (2) Å

c = 14.921 (2) Å

V = 3092.6 (10) Å3

Z = 8

Mo Kα radiation

μ = 0.28 mm−1

T = 273 K

0.33 × 0.26 × 0.23 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.915, T max = 0.930

3994 measured reflections

1204 independent reflections

1169 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.102

S = 1.06

1204 reflections

103 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.15 e Å−3

Absolute structure: Flack (1983 ▶), 457 Friedel pairs

Flack parameter: 0.12 (10)

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809013531/xu2504sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013531/xu2504Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H17N3O2+·ClO4−	F(000) = 1400
Mr = 334.74	Dx = 1.438 Mg m−3
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 2949 reflections
a = 17.485 (4) Å	θ = 2.3–29.0°
b = 11.854 (2) Å	µ = 0.28 mm−1
c = 14.921 (2) Å	T = 273 K
V = 3092.6 (10) Å3	Block, dark-purple
Z = 8	0.33 × 0.26 × 0.23 mm

Bruker SMART CCD area-detector diffractometer	1204 independent reflections
Radiation source: fine-focus sealed tube	1169 reflections with I > 2σ(I)
graphite	Rint = 0.016
φ and ω scans	θmax = 25.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→20
Tmin = 0.915, Tmax = 0.930	k = −11→14
3994 measured reflections	l = −15→18

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.033	w = 1/[σ2(Fo2) + (0.0762P)2 + 1.0334P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102	(Δ/σ)max < 0.001
S = 1.06	Δρmax = 0.27 e Å−3
1204 reflections	Δρmin = −0.15 e Å−3
103 parameters	Extinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0026 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 457 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.12 (10)

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
Cl1	0.0000	0.5000	0.05797 (7)	0.0787 (4)
O2	0.0203 (2)	0.4065 (5)	0.0039 (3)	0.1497 (15)
O3	0.06280 (15)	0.5281 (3)	0.1140 (2)	0.1055 (9)
N1	0.0000	0.5000	0.2971 (2)	0.0684 (10)
H1B	0.0000	0.5000	0.2395	0.082*
N2	0.05399 (9)	0.54721 (12)	0.62987 (12)	0.0399 (4)
C1	0.04640 (17)	0.5698 (2)	0.33929 (18)	0.0626 (6)
H1A	0.0785	0.6169	0.3067	0.075*
C2	0.04743 (13)	0.57302 (19)	0.43134 (16)	0.0520 (5)
H2A	0.0793	0.6232	0.4614	0.062*
C3	0.0000	0.5000	0.4789 (2)	0.0417 (6)
C4	0.0000	0.5000	0.5764 (2)	0.0379 (6)
C5	0.02991 (11)	0.54883 (16)	0.72622 (14)	0.0425 (5)
C6	0.09853 (14)	0.5301 (2)	0.78664 (19)	0.0630 (6)
H6A	0.1322	0.5939	0.7827	0.095*
H6B	0.1253	0.4634	0.7680	0.095*
H6C	0.0816	0.5213	0.8474	0.095*
C7	−0.00457 (14)	0.66478 (19)	0.74312 (19)	0.0616 (7)
H7A	0.0352	0.7206	0.7422	0.092*
H7B	−0.0293	0.6654	0.8006	0.092*
H7C	−0.0414	0.6815	0.6972	0.092*
O1	0.11652 (8)	0.59302 (15)	0.60418 (12)	0.0599 (5)

	U11	U22	U33	U12	U13	U23
Cl1	0.0631 (5)	0.1338 (9)	0.0392 (5)	−0.0116 (5)	0.000	0.000
O2	0.154 (3)	0.199 (4)	0.096 (3)	0.023 (3)	0.013 (2)	−0.053 (3)
O3	0.0789 (14)	0.167 (2)	0.0707 (17)	−0.0372 (15)	−0.0088 (13)	0.0105 (16)
N1	0.092 (2)	0.0776 (18)	0.0360 (17)	0.0404 (17)	0.000	0.000
N2	0.0356 (7)	0.0440 (7)	0.0400 (10)	−0.0075 (6)	−0.0005 (7)	−0.0002 (6)
C1	0.0729 (15)	0.0692 (14)	0.0457 (14)	0.0203 (11)	0.0104 (11)	0.0154 (11)
C2	0.0547 (12)	0.0570 (10)	0.0443 (13)	0.0068 (9)	0.0035 (9)	0.0088 (9)
C3	0.0394 (13)	0.0430 (12)	0.0425 (18)	0.0116 (10)	0.000	0.000
C4	0.0367 (12)	0.0376 (12)	0.0394 (18)	−0.0002 (9)	0.000	0.000
C5	0.0409 (10)	0.0499 (10)	0.0368 (11)	−0.0056 (9)	−0.0015 (9)	−0.0025 (8)
C6	0.0548 (12)	0.0865 (15)	0.0478 (15)	−0.0160 (12)	−0.0141 (11)	0.0046 (11)
C7	0.0683 (14)	0.0550 (11)	0.0614 (17)	−0.0014 (10)	0.0048 (12)	−0.0153 (10)
O1	0.0461 (7)	0.0784 (10)	0.0553 (11)	−0.0250 (7)	0.0047 (7)	0.0008 (8)

Cl1—O2i	1.416 (4)	C2—H2A	0.9300
Cl1—O2	1.416 (4)	C3—C2i	1.393 (3)
Cl1—O3	1.420 (3)	C3—C4	1.455 (4)
Cl1—O3i	1.420 (3)	C4—N2i	1.357 (2)
N1—C1	1.318 (4)	C5—C6	1.517 (3)
N1—C1i	1.318 (4)	C5—C7	1.522 (3)
N1—H1B	0.8600	C5—C5i	1.560 (4)
N2—O1	1.280 (2)	C6—H6A	0.9600
N2—C4	1.357 (2)	C6—H6B	0.9600
N2—C5	1.498 (3)	C6—H6C	0.9600
C1—C2	1.374 (4)	C7—H7A	0.9600
C1—H1A	0.9300	C7—H7B	0.9600
C2—C3	1.393 (3)	C7—H7C	0.9600
O2i—Cl1—O2	110.5 (5)	N2—C4—N2i	108.0 (3)
O2i—Cl1—O3	110.2 (3)	N2—C4—C3	126.01 (13)
O2—Cl1—O3	109.0 (2)	N2i—C4—C3	126.01 (13)
O2i—Cl1—O3i	109.0 (2)	N2—C5—C6	110.26 (18)
O2—Cl1—O3i	110.2 (3)	N2—C5—C7	106.37 (18)
O3—Cl1—O3i	107.9 (2)	C6—C5—C7	110.28 (19)
C1—N1—C1i	123.0 (3)	N2—C5—C5i	100.31 (10)
C1—N1—H1B	118.5	C6—C5—C5i	114.96 (17)
C1i—N1—H1B	118.5	C7—C5—C5i	113.9 (2)
O1—N2—C4	126.40 (18)	C5—C6—H6A	109.5
O1—N2—C5	121.47 (16)	C5—C6—H6B	109.5
C4—N2—C5	111.96 (16)	H6A—C6—H6B	109.5
N1—C1—C2	120.2 (3)	C5—C6—H6C	109.5
N1—C1—H1A	119.9	H6A—C6—H6C	109.5
C2—C1—H1A	119.9	H6B—C6—H6C	109.5
C1—C2—C3	118.9 (2)	C5—C7—H7A	109.5
C1—C2—H2A	120.5	C5—C7—H7B	109.5
C3—C2—H2A	120.5	H7A—C7—H7B	109.5
C2i—C3—C2	118.8 (3)	C5—C7—H7C	109.5
C2i—C3—C4	120.61 (16)	H7A—C7—H7C	109.5
C2—C3—C4	120.61 (16)	H7B—C7—H7C	109.5
C1i—N1—C1—C2	−0.68 (16)	C2—C3—C4—N2	−15.56 (13)
N1—C1—C2—C3	1.3 (3)	C2i—C3—C4—N2i	−15.56 (13)
C1—C2—C3—C2i	−0.65 (15)	C2—C3—C4—N2i	164.44 (13)
C1—C2—C3—C4	179.35 (15)	O1—N2—C5—C6	−39.6 (2)
O1—N2—C4—N2i	175.0 (2)	C4—N2—C5—C6	144.69 (16)
C5—N2—C4—N2i	−9.58 (9)	O1—N2—C5—C7	80.0 (2)
O1—N2—C4—C3	−5.0 (2)	C4—N2—C5—C7	−95.74 (16)
C5—N2—C4—C3	170.42 (9)	O1—N2—C5—C5i	−161.21 (18)
C2i—C3—C4—N2	164.44 (13)	C4—N2—C5—C5i	23.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.86	2.20	2.963 (4)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3	0.86	2.20	2.963 (4)	149