2-Carbamylpyridinium tetra­chlorido­ferrate(III)

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

doi:10.1107/S1600536809040148

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1359

https://doi.org/10.1107/S1600536809040148

Open

access

2-Carbamylpyridinium tetrachloridoferrate(III)

Anne Nielsen,^a Christine J. McKenzie ^a and Andrew D. Bond ^a ^*

^aUniversity of Southern Denmark, Department of Physics and Chemistry, Campusvej 55, 5230 Odense M, Denmark
^*Correspondence e-mail: adb@chem.sdu.dk

(Received 29 September 2009; accepted 1 October 2009; online 17 October 2009)

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.

Related literature

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

Experimental

Crystal data

(C₆H₇N₂O)[FeCl₄]
M_r = 320.79
Monoclinic, P 2₁ /n
a = 13.5252 (8) Å
b = 6.1704 (3) Å
c = 14.1165 (7) Å
β = 93.853 (2)°
V = 1175.44 (11) Å³
Z = 4
Mo Kα radiation
μ = 2.16 mm⁻¹
T = 180 K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.484, T_max = 0.672
15093 measured reflections
2808 independent reflections
2420 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.020
wR(F²) = 0.049
S = 1.05
2808 reflections
140 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.85 (2)	2.00 (2)	2.7234 (16)	142 (2)
N2—H22⋯Cl3	0.84 (1)	2.78 (2)	3.5710 (15)	160 (2)
N2—H21⋯Cl1ⁱⁱ	0.82 (1)	2.69 (2)	3.4811 (14)	163 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2003 ); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809040148/zq2012sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040148/zq2012Isup2.hkl

checkCIF report

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.

Structure description top

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

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

	Fig. 1. Molecular structure with displacement ellipsoids shown at 50% probability for non-H atoms.
	Fig. 2. Picolinamidium cations linked into chains along the b axis by N⁺—H···O hydrogen bonds.
	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
M_r = 320.79	D_x = 1.813 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8949 reflections
a = 13.5252 (8) Å	θ = 2.2–28.1°
b = 6.1704 (3) Å	µ = 2.16 mm⁻¹
c = 14.1165 (7) Å	T = 180 K
β = 93.853 (2)°	Block, yellow
V = 1175.44 (11) Å³	0.40 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker–Nonius X8 APEXII CCD diffractometer	2808 independent reflections
Radiation source: fine-focus sealed tube	2420 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
Thin–slice ω and φ scans	θ_max = 28.3°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→15
T_min = 0.484, T_max = 0.672	k = −7→8
15093 measured reflections	l = −16→18

Refinement top

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)] = 0.020	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0236P)² + 0.2718P] where P = (F_o² + 2F_c²)/3
2808 reflections	(Δ/σ)_max = 0.002
140 parameters	Δρ_max = 0.26 e Å⁻³
2 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

(C₆H₇N₂O)[FeCl₄]	V = 1175.44 (11) Å³
M_r = 320.79	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.5252 (8) Å	µ = 2.16 mm⁻¹
b = 6.1704 (3) Å	T = 180 K
c = 14.1165 (7) Å	0.40 × 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)
T_min = 0.484, T_max = 0.672	R_int = 0.024
15093 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.020	2 restraints
wR(F²) = 0.049	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.26 e Å⁻³
2808 reflections	Δρ_min = −0.23 e Å⁻³
140 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.68522 (7)	1.05039 (17)	0.72326 (8)	0.0328 (2)
N1	0.62577 (9)	0.68301 (19)	0.79936 (8)	0.0223 (2)
H1	0.6851 (13)	0.703 (3)	0.7851 (11)	0.029 (4)*
N2	0.53208 (10)	1.1233 (2)	0.65734 (10)	0.0332 (3)
H21	0.5522 (13)	1.219 (3)	0.6233 (12)	0.044 (5)*
H22	0.4739 (11)	1.081 (3)	0.6457 (13)	0.045 (5)*
C1	0.59653 (10)	1.0119 (2)	0.71214 (10)	0.0236 (3)
C2	0.55609 (10)	0.8255 (2)	0.76671 (9)	0.0201 (3)
C3	0.45980 (10)	0.7950 (2)	0.78930 (9)	0.0229 (3)
H3A	0.4095	0.8939	0.7674	0.027*
C4	0.43698 (10)	0.6185 (2)	0.84436 (10)	0.0251 (3)
H4A	0.3707	0.5966	0.8608	0.030*
C5	0.51019 (11)	0.4743 (2)	0.87552 (10)	0.0279 (3)
H5A	0.4948	0.3523	0.9128	0.034*
C6	0.60612 (11)	0.5101 (2)	0.85165 (10)	0.0266 (3)
H6A	0.6576	0.4128	0.8722	0.032*
Fe1	0.283137 (14)	0.53471 (3)	0.540664 (13)	0.02141 (7)
Cl1	0.38209 (3)	0.39866 (6)	0.43917 (3)	0.04193 (11)
Cl2	0.30476 (3)	0.37620 (6)	0.67908 (2)	0.02817 (9)
Cl3	0.31100 (3)	0.88308 (6)	0.55199 (3)	0.03815 (10)
Cl4	0.12782 (3)	0.49004 (7)	0.48904 (3)	0.03714 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0187 (5)	0.0355 (6)	0.0441 (6)	−0.0075 (4)	0.0024 (5)	0.0018 (5)
N1	0.0161 (6)	0.0268 (6)	0.0242 (6)	−0.0002 (5)	0.0030 (5)	−0.0048 (5)
N2	0.0235 (7)	0.0325 (7)	0.0440 (8)	−0.0003 (6)	0.0041 (6)	0.0106 (6)
C1	0.0208 (7)	0.0231 (7)	0.0276 (7)	−0.0014 (5)	0.0058 (6)	−0.0055 (6)
C2	0.0186 (6)	0.0224 (6)	0.0194 (6)	−0.0013 (5)	0.0007 (5)	−0.0066 (5)
C3	0.0181 (7)	0.0290 (7)	0.0212 (7)	−0.0001 (5)	−0.0002 (5)	−0.0062 (6)
C4	0.0195 (7)	0.0341 (8)	0.0221 (7)	−0.0061 (6)	0.0048 (6)	−0.0083 (6)
C5	0.0337 (8)	0.0273 (7)	0.0232 (7)	−0.0047 (6)	0.0050 (6)	−0.0023 (6)
C6	0.0286 (8)	0.0259 (7)	0.0250 (7)	0.0032 (6)	−0.0001 (6)	−0.0015 (6)
Fe1	0.02269 (12)	0.01900 (10)	0.02251 (11)	−0.00276 (7)	0.00133 (8)	−0.00228 (8)
Cl1	0.0585 (3)	0.03076 (19)	0.0393 (2)	0.00053 (18)	0.0235 (2)	−0.00672 (16)
Cl2	0.03014 (19)	0.03054 (18)	0.02317 (18)	−0.00099 (14)	−0.00311 (14)	−0.00080 (14)
Cl3	0.0468 (2)	0.01959 (17)	0.0481 (2)	−0.00492 (15)	0.00358 (19)	−0.00486 (16)
Cl4	0.0283 (2)	0.0439 (2)	0.0376 (2)	−0.00929 (16)	−0.00973 (16)	0.01353 (17)

Geometric parameters (Å, º) top

O1—C1	1.2225 (17)	C3—H3A	0.950
N1—C6	1.3341 (19)	C4—C5	1.381 (2)
N1—C2	1.3473 (18)	C4—H4A	0.950
N1—H1	0.85 (2)	C5—C6	1.380 (2)
N2—C1	1.319 (2)	C5—H5A	0.950
N2—H21	0.82 (1)	C6—H6A	0.950
N2—H22	0.84 (1)	Fe1—Cl3	2.1863 (4)
C1—C2	1.5073 (19)	Fe1—Cl2	2.1870 (4)
C2—C3	1.3744 (18)	Fe1—Cl1	2.1923 (4)
C3—C4	1.385 (2)	Fe1—Cl4	2.1941 (4)

C6—N1—C2	123.39 (13)	C5—C4—C3	120.23 (13)
C6—N1—H1	118.4 (11)	C5—C4—H4A	119.9
C2—N1—H1	118.2 (11)	C3—C4—H4A	119.9
C1—N2—H21	119.2 (13)	C6—C5—C4	119.00 (13)
C1—N2—H22	121.9 (13)	C6—C5—H5A	120.5
H21—N2—H22	117.1 (19)	C4—C5—H5A	120.5
O1—C1—N2	125.32 (14)	N1—C6—C5	119.25 (14)
O1—C1—C2	117.99 (13)	N1—C6—H6A	120.4
N2—C1—C2	116.68 (12)	C5—C6—H6A	120.4
N1—C2—C3	118.90 (13)	Cl3—Fe1—Cl2	111.243 (17)
N1—C2—C1	113.78 (12)	Cl3—Fe1—Cl1	108.329 (17)
C3—C2—C1	127.24 (12)	Cl2—Fe1—Cl1	111.207 (17)
C2—C3—C4	119.22 (13)	Cl3—Fe1—Cl4	107.713 (18)
C2—C3—H3A	120.4	Cl2—Fe1—Cl4	107.946 (16)
C4—C3—H3A	120.4	Cl1—Fe1—Cl4	110.350 (19)

C6—N1—C2—C3	1.15 (19)	N1—C2—C3—C4	−0.38 (19)
C6—N1—C2—C1	178.00 (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—N1	162.32 (12)	C3—C4—C5—C6	0.6 (2)
O1—C1—C2—C3	157.53 (14)	C2—N1—C6—C5	−1.0 (2)
N2—C1—C2—C3	−21.1 (2)	C4—C5—C6—N1	0.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85 (2)	2.00 (2)	2.7234 (16)	142 (2)
N2—H22···Cl3	0.84 (1)	2.78 (2)	3.5710 (15)	160 (2)
N2—H21···Cl1ⁱⁱ	0.82 (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.

Experimental details

Crystal data
Chemical formula	(C₆H₇N₂O)[FeCl₄]
M_r	320.79
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	180
a, b, c (Å)	13.5252 (8), 6.1704 (3), 14.1165 (7)
β (°)	93.853 (2)
V (Å³)	1175.44 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.16
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker–Nonius X8 APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.484, 0.672
No. of measured, independent and observed [I > 2σ(I)] reflections	15093, 2808, 2420
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.020, 0.049, 1.05
No. of reflections	2808
No. of parameters	140
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.85 (2)	2.00 (2)	2.7234 (16)	142 (2)
N2—H22···Cl3	0.84 (1)	2.78 (2)	3.5710 (15)	160 (2)
N2—H21···Cl1ⁱⁱ	0.82 (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

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

References

Bruker (2003). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gotoh, K., Nagoshi, H. & Ishida, H. (2009). Acta Cryst. C65, o273–o277. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Uçar, İ., Bulut, A., Yeşilel, O. Z. & Büyükgüngör, O. (2004). Acta Cryst. C60, o585–o588. Web of Science CSD CrossRef IUCr Journals Google Scholar