Literature DB >> 21580655

3,3'-Di-n-butyl-1,1'-(p-phenyl-ene-dimethyl-ene)diimidazolium bis-(hexa-fluoro-phosphate).

Rosenani A Haque, Abbas Washeel, S Fatimah Nasri, Chin Sing Yeap, Hoong-Kun Fun.

Abstract

The asymmetric unit of the title N-heterocyclic carbene compound, C(22)H(32)N(4) (2+)·2PF(6) (-), consists of one half of the N-heterocyclic carbene dication and one hexa-fluoro-phosphate anion. The dication lies across a crystallographic inversion center. The imidazole ring is twisted away from the central benzene ring, making a dihedral angle of 76.23 (6)°. The hexa-fluoro-phosphate anions link the cations into a three-dimensional network via inter-molecular C-H⋯F hydrogen bonds. A weak C-H⋯π inter-action further stabilizes the crystal structure.

Entities: CellLine Chemical Disease Gene

Year: 2010 PMID： 21580655 PMCID： PMC2983963 DOI： 10.1107/S1600536810008536

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For background to N-heterocyclic carbenes, see: Arduengo et al. (1991 ▶); Papini et al. (2008 ▶). For applications of N-heterocyclic carbene derivatives, see: Meyer et al. (2009 ▶); Barnard et al. (2004 ▶); Lin & Vasam (2007 ▶). For a related structure, see: Washeel et al. (2010 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C22H32N4 2+·2PF6 − M = 642.46 Monoclinic, a = 8.9802 (5) Å b = 17.8421 (10) Å c = 9.3637 (5) Å β = 113.233 (1)° V = 1378.64 (13) Å3 Z = 2 Mo Kα radiation μ = 0.26 mm−1 T = 100 K 0.37 × 0.25 × 0.20 mm

Data collection

Bruker APEX Duo CCD area detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.910, T max = 0.950 21938 measured reflections 5550 independent reflections 4750 reflections with I > 2σ(I) R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.036 wR(F 2) = 0.121 S = 1.10 5550 reflections 190 parameters H atoms treated by a mixture of independent and constrained refinement Δρmax = 0.52 e Å−3 Δρmin = −0.35 e Å−3 Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶). Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810008536/sj2739sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810008536/sj2739Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₂₂H₃₂N₄²⁺·2PF₆⁻	F(000) = 660
M_r = 642.46	D_x = 1.548 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8699 reflections
a = 8.9802 (5) Å	θ = 3.3–35.1°
b = 17.8421 (10) Å	µ = 0.26 mm⁻¹
c = 9.3637 (5) Å	T = 100 K
β = 113.233 (1)°	Block, colourless
V = 1378.64 (13) Å³	0.37 × 0.25 × 0.20 mm
Z = 2

Bruker APEX Duo CCD area detector diffractometer	5550 independent reflections
Radiation source: fine-focus sealed tube	4750 reflections with I > 2σ(I)
graphite	R_int = 0.027
φ and ω scans	θ_max = 34.0°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −12→14
T_min = 0.910, T_max = 0.950	k = −25→28
21938 measured reflections	l = −14→14

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0669P)² + 0.3404P] where P = (F_o² + 2F_c²)/3
5550 reflections	(Δ/σ)_max < 0.001
190 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	U_iso*/U_eq
P1	0.24993 (3)	0.644667 (14)	0.41525 (3)	0.01504 (7)
F1	0.17538 (13)	0.58756 (4)	0.27368 (9)	0.0377 (2)
F2	0.32152 (11)	0.70282 (5)	0.55641 (8)	0.03461 (19)
F3	0.40070 (10)	0.59059 (5)	0.49878 (11)	0.0363 (2)
F4	0.15300 (10)	0.60287 (5)	0.50374 (10)	0.03387 (18)
F5	0.34534 (10)	0.68616 (5)	0.32536 (10)	0.03212 (18)
F6	0.09980 (9)	0.70032 (5)	0.33174 (9)	0.02912 (16)
N1	−0.09308 (9)	−0.12292 (5)	0.43634 (9)	0.01428 (14)
N2	0.12122 (9)	−0.11365 (5)	0.38494 (10)	0.01434 (14)
C1	0.42820 (12)	−0.01546 (6)	0.34135 (11)	0.01608 (16)
C2	0.39498 (11)	−0.06136 (5)	0.44620 (11)	0.01435 (15)
C3	0.46724 (12)	−0.04565 (6)	0.60501 (11)	0.01585 (16)
C4	0.28430 (11)	−0.12854 (6)	0.38858 (12)	0.01716 (17)
H4A	0.2753	−0.1415	0.2849	0.021*
H4B	0.3314	−0.1710	0.4560	0.021*
C5	0.05423 (11)	−0.15095 (5)	0.46797 (11)	0.01380 (15)
H5A	0.1022	−0.1900	0.5365	0.017*
C6	0.01313 (13)	−0.05969 (6)	0.29775 (13)	0.01997 (18)
H6A	0.0295	−0.0256	0.2301	0.024*
C7	−0.12157 (12)	−0.06587 (6)	0.32955 (13)	0.01986 (18)
H7A	−0.2152	−0.0371	0.2873	0.024*
C8	−0.20778 (12)	−0.14960 (6)	0.50215 (12)	0.01732 (17)
H8A	−0.2538	−0.1069	0.5344	0.021*
H8B	−0.1501	−0.1799	0.5934	0.021*
C9	−0.34402 (11)	−0.19587 (6)	0.38501 (12)	0.01788 (17)
H9A	−0.4209	−0.2086	0.4304	0.021*
H9B	−0.4004	−0.1652	0.2940	0.021*
C10	−0.28848 (13)	−0.26785 (6)	0.33359 (13)	0.02143 (19)
H10A	−0.3792	−0.2892	0.2475	0.026*
H10B	−0.2049	−0.2557	0.2961	0.026*
C11	−0.22253 (16)	−0.32643 (7)	0.46144 (18)	0.0314 (3)
H11B	−0.1973	−0.3714	0.4194	0.047*
H11C	−0.3025	−0.3372	0.5028	0.047*
H11D	−0.1262	−0.3076	0.5428	0.047*
H1A	0.372 (2)	−0.0256 (10)	0.227 (2)	0.026 (4)*
H3A	0.447 (2)	−0.0786 (10)	0.671 (2)	0.025 (4)*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.01633 (12)	0.01343 (12)	0.01512 (11)	0.00062 (7)	0.00596 (9)	0.00052 (7)
F1	0.0666 (6)	0.0170 (3)	0.0251 (4)	−0.0065 (3)	0.0134 (4)	−0.0070 (3)
F2	0.0451 (5)	0.0276 (4)	0.0184 (3)	−0.0044 (3)	−0.0011 (3)	−0.0044 (3)
F3	0.0324 (4)	0.0346 (4)	0.0439 (5)	0.0182 (3)	0.0173 (3)	0.0191 (4)
F4	0.0300 (4)	0.0430 (5)	0.0339 (4)	−0.0048 (3)	0.0182 (3)	0.0085 (3)
F5	0.0322 (4)	0.0337 (4)	0.0369 (4)	−0.0006 (3)	0.0204 (3)	0.0123 (3)
F6	0.0231 (3)	0.0298 (4)	0.0278 (3)	0.0112 (3)	0.0029 (3)	0.0008 (3)
N1	0.0115 (3)	0.0145 (3)	0.0169 (3)	0.0003 (2)	0.0056 (3)	0.0004 (3)
N2	0.0127 (3)	0.0128 (3)	0.0185 (3)	−0.0015 (2)	0.0071 (3)	−0.0015 (3)
C1	0.0163 (4)	0.0168 (4)	0.0167 (4)	−0.0029 (3)	0.0081 (3)	−0.0029 (3)
C2	0.0125 (3)	0.0133 (4)	0.0192 (4)	−0.0020 (3)	0.0083 (3)	−0.0030 (3)
C3	0.0168 (4)	0.0158 (4)	0.0178 (4)	−0.0029 (3)	0.0099 (3)	−0.0010 (3)
C4	0.0147 (4)	0.0144 (4)	0.0258 (4)	−0.0035 (3)	0.0116 (3)	−0.0058 (3)
C5	0.0118 (3)	0.0133 (4)	0.0164 (4)	−0.0002 (3)	0.0056 (3)	−0.0003 (3)
C6	0.0180 (4)	0.0168 (4)	0.0248 (4)	−0.0006 (3)	0.0082 (3)	0.0057 (3)
C7	0.0156 (4)	0.0163 (4)	0.0265 (5)	0.0023 (3)	0.0070 (3)	0.0057 (3)
C8	0.0142 (4)	0.0214 (4)	0.0186 (4)	−0.0014 (3)	0.0089 (3)	−0.0021 (3)
C9	0.0124 (4)	0.0197 (4)	0.0218 (4)	−0.0007 (3)	0.0071 (3)	−0.0008 (3)
C10	0.0196 (4)	0.0212 (5)	0.0263 (5)	−0.0028 (3)	0.0121 (4)	−0.0044 (4)
C11	0.0290 (6)	0.0223 (5)	0.0447 (7)	0.0055 (4)	0.0166 (5)	0.0043 (5)

P1—F3	1.5939 (8)	C4—H4A	0.9700
P1—F1	1.5948 (8)	C4—H4B	0.9700
P1—F5	1.5999 (8)	C5—H5A	0.9300
P1—F2	1.6020 (8)	C6—C7	1.3595 (15)
P1—F4	1.6029 (8)	C6—H6A	0.9300
P1—F6	1.6073 (7)	C7—H7A	0.9300
N1—C5	1.3337 (12)	C8—C9	1.5241 (14)
N1—C7	1.3782 (13)	C8—H8A	0.9700
N1—C8	1.4725 (12)	C8—H8B	0.9700
N2—C5	1.3335 (12)	C9—C10	1.5229 (15)
N2—C6	1.3822 (13)	C9—H9A	0.9700
N2—C4	1.4755 (12)	C9—H9B	0.9700
C1—C3ⁱ	1.3966 (13)	C10—C11	1.5222 (17)
C1—C2	1.3981 (13)	C10—H10A	0.9700
C1—H1A	1.005 (17)	C10—H10B	0.9700
C2—C3	1.3964 (13)	C11—H11B	0.9600
C2—C4	1.5141 (13)	C11—H11C	0.9600
C3—C1ⁱ	1.3966 (13)	C11—H11D	0.9600
C3—H3A	0.925 (17)

F3—P1—F1	91.03 (5)	H4A—C4—H4B	107.9
F3—P1—F5	90.61 (5)	N2—C5—N1	108.63 (8)
F1—P1—F5	89.70 (5)	N2—C5—H5A	125.7
F3—P1—F2	90.02 (5)	N1—C5—H5A	125.7
F1—P1—F2	178.91 (5)	C7—C6—N2	107.00 (9)
F5—P1—F2	90.60 (5)	C7—C6—H6A	126.5
F3—P1—F4	89.66 (5)	N2—C6—H6A	126.5
F1—P1—F4	89.82 (5)	C6—C7—N1	106.99 (9)
F5—P1—F4	179.45 (5)	C6—C7—H7A	126.5
F2—P1—F4	89.87 (5)	N1—C7—H7A	126.5
F3—P1—F6	179.09 (5)	N1—C8—C9	111.68 (8)
F1—P1—F6	89.64 (5)	N1—C8—H8A	109.3
F5—P1—F6	88.78 (4)	C9—C8—H8A	109.3
F2—P1—F6	89.31 (4)	N1—C8—H8B	109.3
F4—P1—F6	90.95 (5)	C9—C8—H8B	109.3
C5—N1—C7	108.79 (8)	H8A—C8—H8B	107.9
C5—N1—C8	125.60 (8)	C10—C9—C8	114.48 (8)
C7—N1—C8	125.60 (8)	C10—C9—H9A	108.6
C5—N2—C6	108.59 (8)	C8—C9—H9A	108.6
C5—N2—C4	124.66 (8)	C10—C9—H9B	108.6
C6—N2—C4	126.75 (8)	C8—C9—H9B	108.6
C3ⁱ—C1—C2	120.28 (9)	H9A—C9—H9B	107.6
C3ⁱ—C1—H1A	120.5 (10)	C11—C10—C9	113.87 (9)
C2—C1—H1A	119.2 (10)	C11—C10—H10A	108.8
C3—C2—C1	119.47 (8)	C9—C10—H10A	108.8
C3—C2—C4	120.16 (9)	C11—C10—H10B	108.8
C1—C2—C4	120.36 (8)	C9—C10—H10B	108.8
C2—C3—C1ⁱ	120.25 (9)	H10A—C10—H10B	107.7
C2—C3—H3A	117.1 (11)	C10—C11—H11B	109.5
C1ⁱ—C3—H3A	122.5 (11)	C10—C11—H11C	109.5
N2—C4—C2	111.82 (8)	H11B—C11—H11C	109.5
N2—C4—H4A	109.3	C10—C11—H11D	109.5
C2—C4—H4A	109.3	H11B—C11—H11D	109.5
N2—C4—H4B	109.3	H11C—C11—H11D	109.5
C2—C4—H4B	109.3

C3ⁱ—C1—C2—C3	−0.02 (16)	C8—N1—C5—N2	178.85 (8)
C3ⁱ—C1—C2—C4	−178.77 (9)	C5—N2—C6—C7	−0.48 (12)
C1—C2—C3—C1ⁱ	0.02 (16)	C4—N2—C6—C7	179.81 (9)
C4—C2—C3—C1ⁱ	178.77 (9)	N2—C6—C7—N1	0.50 (12)
C5—N2—C4—C2	−118.10 (10)	C5—N1—C7—C6	−0.35 (12)
C6—N2—C4—C2	61.57 (13)	C8—N1—C7—C6	−179.15 (9)
C3—C2—C4—N2	78.63 (11)	C5—N1—C8—C9	−104.24 (11)
C1—C2—C4—N2	−102.63 (10)	C7—N1—C8—C9	74.36 (12)
C6—N2—C5—N1	0.26 (11)	N1—C8—C9—C10	63.05 (11)
C4—N2—C5—N1	179.98 (8)	C8—C9—C10—C11	67.80 (12)
C7—N1—C5—N2	0.05 (11)

Table 1. Hydrogen bond geometry (Å, °). Cg1 is centroids of benzene ring C1-C2-C3-C1A-C2A-C3A.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···F3ⁱⁱ	1.004 (17)	2.532 (18)	3.3945 (14)	143.8 (15)
C4—H4A···F4ⁱⁱ	0.97	2.52	3.3516 (14)	144
C4—H4B···F2ⁱⁱⁱ	0.97	2.45	3.3497 (14)	153
C7—H7A···F1^iv	0.93	2.36	2.8798 (13)	115
C8—H8B···F6^v	0.97	2.49	3.3537 (13)	148
C8—H8A···Cg1^vi	0.97	2.84	3.7376 (12)	154
C8—H8A···Cg1^vii	0.97	2.84	3.7376 (12)	154

Table 1

Hydrogen-bond geometry (Å, °)

Table 1 ▶. Hydrogen bond geometry (Å, °). Cg1 is the centroid of the C1–C3,C1A–C3A benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯F3ⁱ	1.004 (17)	2.532 (18)	3.3945 (14)	143.8 (15)
C4—H4A⋯F4ⁱ	0.97	2.52	3.3516 (14)	144
C4—H4B⋯F2ⁱⁱ	0.97	2.45	3.3497 (14)	153
C7—H7A⋯F1ⁱⁱⁱ	0.93	2.36	2.8798 (13)	115
C8—H8B⋯F6^iv	0.97	2.49	3.3537 (13)	148
C8—H8A⋯Cg1^v	0.97	2.84	3.7376 (12)	154
C8—H8A⋯Cg1^vi	0.97	2.84	3.7376 (12)	154

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

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1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Mitochondrial permeability transition induced by dinuclear gold(I)-carbene complexes: potential new antimitochondrial antitumour agents.

Authors: Peter J Barnard; Murray V Baker; Susan J Berners-Price; David A Day
Journal: J Inorg Biochem Date: 2004-10 Impact factor: 4.155

3. 3,5-Bis(3-methyl-imidazolium-1-ylmeth-yl)toluene bis-(hexa-fluoro-phosphate).

Authors: Abbas Washeel; Rosenani A Haque; Siang Guan Teoh; Chin Sing Yeap; Hoong-Kun Fun
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2010-02-06

4. Structure validation in chemical crystallography.

Authors: Anthony L Spek
Journal: Acta Crystallogr D Biol Crystallogr Date: 2009-01-20