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Acta Cryst. (2009). E65, m1359    [ doi:10.1107/S1600536809040148 ]

2-Carbamylpyridinium tetrachloridoferrate(III)

A. Nielsen, C. J. McKenzie and A. D. Bond

Abstract top

The title compound, (C6H7N2O)[FeCl4], contains two carbamylpyridinium (picolinamidinium) cations, which are linked into chains by N+-H...O hydrogen bonds formed between protonated pyridyl N atoms and carbonyl groups. Tetrachloridoferrate(III) anions lie between these chains, accepting N-H...Cl hydrogen bonds from both H atoms of the picolinamidium -NH2 group.

Comment top

Picolinamidium cations are present in two other structures in the Cambridge Structural Database. One structure (refcode: EYIXAL; Uçar et al., 2004) includes squarate anions, C4HO4-, and contains planar picolinadinium:squarate layers in which all three N—H donors in picolinadinium form hydrogen bonds to squarate. The other (refcode: POVZEG; Gotoh et al., 2009) contains chloranilate anions, C6HCl2O4-, in which all three N—H donors in picolinadinium form hydrogen bonds to chloranilate.

Related literature top

For related structures containing picolinamidium cations, see: Uçar et al. (2004); Gotoh et al. (2009).

Experimental top

Picolinamide (35 mg, 28 mmol) was dissolved in acetonitrile (2.75 ml) and anhydrous FeCl3 (46 mg, 28 mmol) trimethylamine-N-oxide (32 mg, 28 mmol) and concentrated hydrochloric acid (0.2 ml) were added. After one week, a few milligrams of the title compound were deposited as yellow crystals.

Refinement top

H atoms bound to C atoms were placed in idealized positions with C—H = 0.95 Å and refined as riding with Uiso(H) = 1.2Ueq(C). H atoms bound to N were located in difference Fourier maps and refined with isotropic displacement parameters. The distances N2—H21 and N2—H22 were restrained to a common refined value, with an s.u. of 0.01 Å, and atom H1 was refined without restraint.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure with displacement ellipsoids shown at 50% probability for non-H atoms.
[Figure 2] Fig. 2. Picolinamidium cations linked into chains along the b axis by N+—H···O hydrogen bonds.
[Figure 3] Fig. 3. Unit-cell contents projected along the b axis, showing FeCl4- anions between the hydrogen-bonded chains of picolinamidium cations.
2-Carbamylpyridinium tetrachloridoferrate(III) top
Crystal data top
(C6H7N2O)[FeCl4]F(000) = 636
Mr = 320.79Dx = 1.813 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 8949 reflections
a = 13.5252 (8) Åθ = 2.2–28.1°
b = 6.1704 (3) ŵ = 2.16 mm−1
c = 14.1165 (7) ÅT = 180 K
β = 93.853 (2)°Block, yellow
V = 1175.44 (11) Å30.40 × 0.30 × 0.20 mm
Z = 4
Data collection top
Bruker–Nonius X8 APEXII CCD
diffractometer		2808 independent reflections
Radiation source: fine-focus sealed tube2420 reflections with I > 2σ(I)
graphiteRint = 0.024
Thin–slice ω and φ scansθmax = 28.3°, θmin = 3.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −17→15
Tmin = 0.484, Tmax = 0.672k = −7→8
15093 measured reflectionsl = −16→18
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)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.049H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0236P)2 + 0.2718P]
where P = (Fo2 + 2Fc2)/3
2808 reflections(Δ/σ)max = 0.002
140 parametersΔρmax = 0.26 e Å−3
2 restraintsΔρmin = −0.23 e Å−3
Crystal data top
(C6H7N2O)[FeCl4]V = 1175.44 (11) Å3
Mr = 320.79Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.5252 (8) ŵ = 2.16 mm−1
b = 6.1704 (3) ÅT = 180 K
c = 14.1165 (7) Å0.40 × 0.30 × 0.20 mm
β = 93.853 (2)°
Data collection top
Bruker–Nonius X8 APEXII CCD
diffractometer		2808 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2420 reflections with I > 2σ(I)
Tmin = 0.484, Tmax = 0.672Rint = 0.024
15093 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.020H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.049Δρmax = 0.26 e Å−3
S = 1.05Δρmin = −0.23 e Å−3
2808 reflectionsAbsolute structure: ?
140 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
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*/Ueq
O10.68522 (7)1.05039 (17)0.72326 (8)0.0328 (2)
N10.62577 (9)0.68301 (19)0.79936 (8)0.0223 (2)
H10.6851 (13)0.703 (3)0.7851 (11)0.029 (4)*
N20.53208 (10)1.1233 (2)0.65734 (10)0.0332 (3)
H210.5522 (13)1.219 (3)0.6233 (12)0.044 (5)*
H220.4739 (11)1.081 (3)0.6457 (13)0.045 (5)*
C10.59653 (10)1.0119 (2)0.71214 (10)0.0236 (3)
C20.55609 (10)0.8255 (2)0.76671 (9)0.0201 (3)
C30.45980 (10)0.7950 (2)0.78930 (9)0.0229 (3)
H3A0.40950.89390.76740.027*
C40.43698 (10)0.6185 (2)0.84436 (10)0.0251 (3)
H4A0.37070.59660.86080.030*
C50.51019 (11)0.4743 (2)0.87552 (10)0.0279 (3)
H5A0.49480.35230.91280.034*
C60.60612 (11)0.5101 (2)0.85165 (10)0.0266 (3)
H6A0.65760.41280.87220.032*
Fe10.283137 (14)0.53471 (3)0.540664 (13)0.02141 (7)
Cl10.38209 (3)0.39866 (6)0.43917 (3)0.04193 (11)
Cl20.30476 (3)0.37620 (6)0.67908 (2)0.02817 (9)
Cl30.31100 (3)0.88308 (6)0.55199 (3)0.03815 (10)
Cl40.12782 (3)0.49004 (7)0.48904 (3)0.03714 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0187 (5)0.0355 (6)0.0441 (6)−0.0075 (4)0.0024 (5)0.0018 (5)
N10.0161 (6)0.0268 (6)0.0242 (6)−0.0002 (5)0.0030 (5)−0.0048 (5)
N20.0235 (7)0.0325 (7)0.0440 (8)−0.0003 (6)0.0041 (6)0.0106 (6)
C10.0208 (7)0.0231 (7)0.0276 (7)−0.0014 (5)0.0058 (6)−0.0055 (6)
C20.0186 (6)0.0224 (6)0.0194 (6)−0.0013 (5)0.0007 (5)−0.0066 (5)
C30.0181 (7)0.0290 (7)0.0212 (7)−0.0001 (5)−0.0002 (5)−0.0062 (6)
C40.0195 (7)0.0341 (8)0.0221 (7)−0.0061 (6)0.0048 (6)−0.0083 (6)
C50.0337 (8)0.0273 (7)0.0232 (7)−0.0047 (6)0.0050 (6)−0.0023 (6)
C60.0286 (8)0.0259 (7)0.0250 (7)0.0032 (6)−0.0001 (6)−0.0015 (6)
Fe10.02269 (12)0.01900 (10)0.02251 (11)−0.00276 (7)0.00133 (8)−0.00228 (8)
Cl10.0585 (3)0.03076 (19)0.0393 (2)0.00053 (18)0.0235 (2)−0.00672 (16)
Cl20.03014 (19)0.03054 (18)0.02317 (18)−0.00099 (14)−0.00311 (14)−0.00080 (14)
Cl30.0468 (2)0.01959 (17)0.0481 (2)−0.00492 (15)0.00358 (19)−0.00486 (16)
Cl40.0283 (2)0.0439 (2)0.0376 (2)−0.00929 (16)−0.00973 (16)0.01353 (17)
Geometric parameters (Å, °) top
O1—C11.2225 (17)C3—H3A0.950
N1—C61.3341 (19)C4—C51.381 (2)
N1—C21.3473 (18)C4—H4A0.950
N1—H10.85 (2)C5—C61.380 (2)
N2—C11.319 (2)C5—H5A0.950
N2—H210.82 (1)C6—H6A0.950
N2—H220.84 (1)Fe1—Cl32.1863 (4)
C1—C21.5073 (19)Fe1—Cl22.1870 (4)
C2—C31.3744 (18)Fe1—Cl12.1923 (4)
C3—C41.385 (2)Fe1—Cl42.1941 (4)
C6—N1—C2123.39 (13)C5—C4—C3120.23 (13)
C6—N1—H1118.4 (11)C5—C4—H4A119.9
C2—N1—H1118.2 (11)C3—C4—H4A119.9
C1—N2—H21119.2 (13)C6—C5—C4119.00 (13)
C1—N2—H22121.9 (13)C6—C5—H5A120.5
H21—N2—H22117.1 (19)C4—C5—H5A120.5
O1—C1—N2125.32 (14)N1—C6—C5119.25 (14)
O1—C1—C2117.99 (13)N1—C6—H6A120.4
N2—C1—C2116.68 (12)C5—C6—H6A120.4
N1—C2—C3118.90 (13)Cl3—Fe1—Cl2111.243 (17)
N1—C2—C1113.78 (12)Cl3—Fe1—Cl1108.329 (17)
C3—C2—C1127.24 (12)Cl2—Fe1—Cl1111.207 (17)
C2—C3—C4119.22 (13)Cl3—Fe1—Cl4107.713 (18)
C2—C3—H3A120.4Cl2—Fe1—Cl4107.946 (16)
C4—C3—H3A120.4Cl1—Fe1—Cl4110.350 (19)
C6—N1—C2—C31.15 (19)N1—C2—C3—C4−0.38 (19)
C6—N1—C2—C1178.00 (12)C1—C2—C3—C4−176.75 (13)
O1—C1—C2—N1−19.00 (18)C2—C3—C4—C5−0.5 (2)
N2—C1—C2—N1162.32 (12)C3—C4—C5—C60.6 (2)
O1—C1—C2—C3157.53 (14)C2—N1—C6—C5−1.0 (2)
N2—C1—C2—C3−21.1 (2)C4—C5—C6—N10.1 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.85 (2)2.00 (2)2.7234 (16)142 (2)
N2—H22···Cl30.84 (1)2.78 (2)3.5710 (15)160 (2)
N2—H21···Cl1ii0.82 (1)2.69 (2)3.4811 (14)163 (2)
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.85 (2)2.00 (2)2.7234 (16)142 (2)
N2—H22···Cl30.84 (1)2.78 (2)3.5710 (15)160 (2)
N2—H21···Cl1ii0.82 (1)2.69 (2)3.4811 (14)163 (2)
Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) −x+1, −y+2, −z+1.
Acknowledgements top

We are grateful to the Danish Natural Sciences Research Council and the Carlsberg Foundation for provision of the X-ray equipment.

references
References top

Bruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.

Gotoh, K., Nagoshi, H. & Ishida, H. (2009). Acta Cryst. C65, o273–o277.

Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Uçar, İ., Bulut, A., Yeşilel, O. Z. & Büyükgüngör, O. (2004). Acta Cryst. C60, o585–o588.