1′-Acetyl­ferrocene-1-carbonitrile

In the title compound, [Fe(C₆H₄N)(C₇H₇O)], the two cyclo­penta­dienyl rings are nearly parallel, making a dihedral angle of 2.3 (1) Å, and are almost eclipsed as viewed down the normal to each ring. In the crystal structure, the mol­ecules are stacked along the b axis, with a short distance of 3.749 (1) Å between the centroids of the cyclo­penta­dienyl rings of neighbouring mol­ecules. Weak inter­molecular C—H...N and C—H...O hydrogen bonds link these stacks into two-dimensional sheets parallel to the bc plane.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.082
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C8     -   C13    ...       1.43 Ang.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C7
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4     ..  N1      ..       2.72 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9     ..  N1      ..       2.73 Ang.

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1         (3)       3.79

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

Ferrocenes are well known class of organometallic compounds and the wealth of its derivatives is described in literature. Ferrocene compounds are widely used in homogenous catalysis, organic or organometallic synthesis and in material science. In last three years, utilization of ferrocene derivatives in drying of oxidizable paints has been investigated, and it was observed that ferrocenes bearing electron-withdrawing substituents showed the highest activity in drying processes Šťáva et al., 2007). In the framework of investigation of ferrocene derivatives we prepared, spectroscopically characterized the title compound (I) and determined its molecular structure in the solid state.

Figure 1 shows typical sandwich structure of (I) with cyclopentadienyl ligands being very close to be eclipsed. The dihedral angle between a ring carbon, the two ring centroids and the carbon atom of opposite ring varies from 6.9 (2) to 8.2 (2)°. The exocyclic bond lengths C8—C13 and C1—C6 of 1.429 (3) Å and 1.466 (3) Å, respectively, are very close to those found in cyanoferrocene [1.432 (6) Å, (Bell et al., 1996)] and diacetylferrocene [1.747 (8) Å, 1.768 (8) Å (Palenik, 1970)]. The interatomic distances and angles in the molecule of (I) are comparable to those observed for similar ferrocene derivatives, the principial interest lies in the intermolecular interactions.

The ring Cp2 of molecule at (x, y, z) is nearly coplanar with ring Cp1 of the molecule at (x, 1 + y, z) with dihedral angle of 2.3 (1)°. The distance between the centriods of Cp rings was found to be 3.749 (1) Å indicating significant intermolecular π···π interaction between neighboring molecules of (I) along b axis.. Atom N1 in the molecule at (x, y, z) acts as hydrogen-bond acceptor from cyclopentadienyl carbon atoms C4 and C9 of the molecule at (2 - x, 1 - y, 1 - z), i.e. (i), with C···N distances of 3.411 (3) and 3.464 (3) Å, respectively. Simultaneously, N1ⁱ atom serves as hydrogen-bond acceptor from atoms C4 and C9 of molecule at (x, y, z) generating molecular pairs connected by four C—H···N hydrogen bonds. Thus each nitrogen atom exhibits trigonal coordination; an angle H4ⁱ···N1···H9ⁱ was found to be 73°. Oxygen atom O1 of acetyl group also participates in intermolecular interactions, being hydrogen-bond acceptor from atom C11 of the molecule at (2 - x, - y, - z). Reversely, atom C11 in the molecule at (x, y, z) acts as donor to the oxygen atom of the molecule at (2 - x, - y, - z). Figure 2 depicts three molecules of (I) interconnected by weak hydrogen bonds.

The interplay of π···π stacking and weak hydrogen bonds is responsible for the observed structure giving two-dimensional sheets parallel to bc-plane

Related literature

Transition metal complexes bearing a strongly electron-withdrawing cyano group at the cyclopentadienyl ring are relatively sparse and only three related structures have been published previously: (η⁵-cyanocyclopentadienyl)-(η⁴-tetraphenylcyclobutadiene)cobalt (Villa et al., 1974), (η⁵-cyanocyclopentadienyl)dicarbonylnitrosylchromium (Rogers et al., 1988) and cyanoferrocene (Bell et al., 1996). For related literature dealing with acetyl- and cyano-substituted ferrocenes, see: Nesmeyanov et al. (1962); Palenik (1970); Šťáva et al. (2007).

S2. Experimental

The title compound (I) was synthesized by direct cyanation of acetylferrocene following published procedure (Nesmeyanov et al., 1962). Melting point, IR, Raman and NMR spectra confirmed identity and purity of prepared compound. Crystals of (I) suitable for X-ray diffraction analysis were grown by sublimation in sealed ampoule at 0.1 Pa and 353 K.

S3. Refinement

All H atoms were positioned geometrically and refined as riding on their parent C atoms, with C—H = 0.93 Å, U_iso(H) = 1.2Ueq(C) and C—H = 0.96 Å, U_iso(H) = 1.5Ueq(C) for cyclopentadienyl and methyl H atoms, respectively.

Computing details

Data collection: COLLECT (Hooft, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. ORTEP view of the title compound (I) with displacement ellipsoids drawn at the 50% probability.
	Fig. 2. A view of three molecules of (I) linked by weak C—H···N and C—H···O hydrogen bonds (dashed lines). H atoms not involved in contacts have been omitted. [Symmetry codes: (i) 2 - x, 1 - y, 1 - z; (ii) 2 - x, - y, - z]

1'-Acetylferrocene-1-carbonitrile

Crystal data

[Fe(C6H4N)(C7H7O)]	Z = 2
Mr = 253.08	F(000) = 260
Triclinic, P1	Dx = 1.609 Mg m^−3
Hall symbol: -P 1	Melting point: 370 K
a = 5.7610 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.8431 (5) Å	Cell parameters from 7054 reflections
c = 14.1940 (14) Å	θ = 1–27.5°
α = 99.264 (7)°	µ = 1.42 mm^−1
β = 99.666 (6)°	T = 150 K
γ = 104.277 (7)°	Plate, red
V = 522.45 (8) Å^3	0.16 × 0.10 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD area-detector diffractometer	2383 independent reflections
Radiation source: fine-focus sealed tube	2151 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.7°
φ and ω scans to fill the Ewald sphere	h = −7→7
Absorption correction: integration (Gaussian; Coppens et al., 1970)	k = −8→8
Tmin = 0.801, Tmax = 0.931	l = −18→18
6982 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0403P)^2 + 0.3168P] where P = (Fo^2 + 2Fc^2)/3
2383 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.59 e Å^−3

Special details

Experimental. Melting point: 370–371 K. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 2.40 (s, 3H), 4.40 (s, 2H), 4.62 (s, 4H), 4.87 (s, 2H). ¹³C NMR (CDCl₃, δ, p.p.m.): 27.9, 53.9, 71.8, 72.4, 73.2, 74.5, 81.3, 118.9, 200.9. Uv-Vis (cyclohexane, maxima at nm): 447, 350s h, 314s h. IR (KBr disc, cm^-1): 3121 (m), 3104 (m), 3092 (m), 3078 (s), 2925 (m), 2856 (m), 2231 (versus), 1655 (versus), 1455 (s), 1400 (m), 1375 (s), 1356 (m), 1279 (versus), 1235 (m), 1117 (m), 1069 (w), 1039 (m), 966 (w), 917 (m), 896 (m), 854 (w), 833 (s), 667 (w), 623 (m), 556 (s), 527 (s), 512 (m), 483 (s). Raman (quartz capillary, cm^-1): 3122 (m), 3108 (s), 3092 (w), 3077 (m), 2925 (m), 2232 (versus), 1654 (versus), 1457 (w), 1446 (m), 1401 (w), 1378 (w), 1283 (m), 1234 (s), 1119 (m), 1077 (m), 1042 (m), 1034 (m), 917 (w), 673 (m), 641 (m), 625 (w), 555 (w), 527 (w), 483 (w), 358 (m), 314 (versus), 218 (m), 186 (m), 115 (m).

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
Fe1	0.92112 (5)	0.18493 (4)	0.26947 (2)	0.01257 (10)
C12	1.0895 (4)	0.4420 (3)	0.22364 (15)	0.0183 (4)
H12	1.2460	0.4734	0.2108	0.022*
O1	1.1803 (3)	−0.1467 (3)	0.09502 (12)	0.0281 (4)
C4	0.8082 (4)	−0.0211 (3)	0.35489 (16)	0.0192 (4)
H4	0.7015	−0.0130	0.3969	0.023*
C7	0.7473 (4)	−0.2488 (4)	0.03850 (17)	0.0277 (5)
H7A	0.7866	−0.2852	−0.0239	0.042*
H7B	0.6589	−0.1471	0.0362	0.042*
H7C	0.6478	−0.3693	0.0537	0.042*
C1	0.9600 (4)	−0.0971 (3)	0.21714 (15)	0.0151 (4)
C9	0.7666 (4)	0.4179 (3)	0.30431 (15)	0.0180 (4)
H9	0.6772	0.4308	0.3526	0.022*
C10	0.6706 (4)	0.3170 (3)	0.20418 (15)	0.0184 (4)
H10	0.5061	0.2521	0.1757	0.022*
C5	0.7397 (4)	−0.1180 (3)	0.25418 (15)	0.0163 (4)
H5	0.5806	−0.1833	0.2185	0.020*
C3	1.0686 (4)	0.0617 (3)	0.38067 (15)	0.0191 (4)
H3	1.1604	0.1340	0.4422	0.023*
C11	0.8676 (4)	0.3322 (3)	0.15519 (15)	0.0184 (4)
H11	0.8538	0.2791	0.0893	0.022*
C2	1.1633 (4)	0.0151 (3)	0.29684 (15)	0.0171 (4)
H2	1.3279	0.0508	0.2937	0.021*
C6	0.9806 (4)	−0.1621 (3)	0.11602 (15)	0.0184 (4)
N1	1.3441 (4)	0.6917 (3)	0.47474 (15)	0.0311 (5)
C8	1.0275 (4)	0.4956 (3)	0.31641 (15)	0.0173 (4)
C13	1.2006 (4)	0.6036 (3)	0.40509 (16)	0.0212 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.01291 (15)	0.01076 (16)	0.01458 (16)	0.00420 (11)	0.00143 (10)	0.00445 (10)
C12	0.0214 (10)	0.0129 (9)	0.0237 (11)	0.0062 (8)	0.0075 (8)	0.0078 (8)
O1	0.0228 (8)	0.0363 (10)	0.0250 (8)	0.0086 (7)	0.0077 (7)	0.0026 (7)
C4	0.0236 (11)	0.0160 (10)	0.0217 (10)	0.0069 (8)	0.0075 (8)	0.0101 (8)
C7	0.0257 (12)	0.0293 (12)	0.0219 (11)	0.0039 (10)	−0.0006 (9)	0.0000 (9)
C1	0.0154 (9)	0.0094 (9)	0.0209 (10)	0.0044 (7)	0.0026 (8)	0.0044 (8)
C9	0.0213 (10)	0.0159 (10)	0.0208 (10)	0.0099 (8)	0.0059 (8)	0.0063 (8)
C10	0.0165 (10)	0.0178 (10)	0.0224 (11)	0.0082 (8)	0.0001 (8)	0.0073 (8)
C5	0.0155 (9)	0.0111 (9)	0.0219 (10)	0.0021 (7)	0.0027 (8)	0.0061 (8)
C3	0.0251 (11)	0.0162 (10)	0.0169 (10)	0.0087 (8)	−0.0003 (8)	0.0067 (8)
C11	0.0248 (11)	0.0165 (10)	0.0169 (10)	0.0086 (8)	0.0037 (8)	0.0083 (8)
C2	0.0145 (9)	0.0149 (10)	0.0237 (10)	0.0067 (8)	0.0014 (8)	0.0077 (8)
C6	0.0212 (10)	0.0130 (9)	0.0196 (10)	0.0037 (8)	0.0027 (8)	0.0034 (8)
N1	0.0316 (11)	0.0258 (11)	0.0293 (11)	0.0040 (9)	−0.0009 (9)	0.0010 (9)
C8	0.0202 (10)	0.0121 (9)	0.0199 (10)	0.0054 (8)	0.0032 (8)	0.0039 (8)
C13	0.0244 (11)	0.0134 (10)	0.0254 (11)	0.0052 (9)	0.0049 (9)	0.0039 (8)

Geometric parameters (Å, º)

Fe1—C8	2.026 (2)	C7—H7A	0.9600
Fe1—C1	2.0332 (19)	C7—H7B	0.9600
Fe1—C5	2.036 (2)	C7—H7C	0.9600
Fe1—C9	2.042 (2)	C1—C5	1.438 (3)
Fe1—C12	2.049 (2)	C1—C2	1.440 (3)
Fe1—C2	2.052 (2)	C1—C6	1.466 (3)
Fe1—C10	2.055 (2)	C9—C10	1.426 (3)
Fe1—C4	2.060 (2)	C9—C8	1.436 (3)
Fe1—C11	2.062 (2)	C9—H9	0.9300
Fe1—C3	2.063 (2)	C10—C11	1.419 (3)
C12—C11	1.420 (3)	C10—H10	0.9300
C12—C8	1.436 (3)	C5—H5	0.9300
C12—H12	0.9300	C3—C2	1.413 (3)
O1—C6	1.221 (3)	C3—H3	0.9300
C4—C5	1.419 (3)	C11—H11	0.9300
C4—C3	1.426 (3)	C2—H2	0.9300
C4—H4	0.9300	N1—C13	1.145 (3)
C7—C6	1.506 (3)	C8—C13	1.429 (3)
C8—Fe1—C1	156.37 (9)	C6—C7—H7B	109.5
C8—Fe1—C5	160.78 (8)	H7A—C7—H7B	109.5
C1—Fe1—C5	41.38 (8)	C6—C7—H7C	109.5
C8—Fe1—C9	41.34 (8)	H7A—C7—H7C	109.5
C1—Fe1—C9	161.58 (8)	H7B—C7—H7C	109.5
C5—Fe1—C9	122.75 (8)	C5—C1—C2	107.46 (18)
C8—Fe1—C12	41.27 (8)	C5—C1—C6	127.67 (18)
C1—Fe1—C12	121.50 (8)	C2—C1—C6	124.73 (18)
C5—Fe1—C12	155.76 (9)	C5—C1—Fe1	69.43 (11)
C9—Fe1—C12	69.39 (8)	C2—C1—Fe1	70.06 (11)
C8—Fe1—C2	120.61 (8)	C6—C1—Fe1	122.50 (14)
C1—Fe1—C2	41.27 (8)	C10—C9—C8	107.00 (18)
C5—Fe1—C2	69.15 (8)	C10—C9—Fe1	70.11 (12)
C9—Fe1—C2	154.11 (9)	C8—C9—Fe1	68.71 (11)
C12—Fe1—C2	109.65 (8)	C10—C9—H9	126.5
C8—Fe1—C10	68.63 (8)	C8—C9—H9	126.5
C1—Fe1—C10	125.75 (8)	Fe1—C9—H9	126.2
C5—Fe1—C10	106.12 (8)	C11—C10—C9	108.71 (18)
C9—Fe1—C10	40.74 (8)	C11—C10—Fe1	70.12 (11)
C12—Fe1—C10	68.34 (8)	C9—C10—Fe1	69.15 (11)
C2—Fe1—C10	164.69 (9)	C11—C10—H10	125.6
C8—Fe1—C4	124.28 (9)	C9—C10—H10	125.6
C1—Fe1—C4	68.66 (8)	Fe1—C10—H10	126.7
C5—Fe1—C4	40.54 (8)	C4—C5—C1	107.80 (18)
C9—Fe1—C4	104.96 (8)	C4—C5—Fe1	70.63 (12)
C12—Fe1—C4	163.19 (9)	C1—C5—Fe1	69.19 (11)
C2—Fe1—C4	68.14 (8)	C4—C5—H5	126.1
C10—Fe1—C4	118.35 (9)	C1—C5—H5	126.1
C8—Fe1—C11	68.51 (8)	Fe1—C5—H5	125.7
C1—Fe1—C11	109.10 (8)	C2—C3—C4	108.44 (18)
C5—Fe1—C11	120.23 (8)	C2—C3—Fe1	69.49 (11)
C9—Fe1—C11	68.56 (8)	C4—C3—Fe1	69.65 (11)
C12—Fe1—C11	40.41 (8)	C2—C3—H3	125.8
C2—Fe1—C11	128.46 (9)	C4—C3—H3	125.8
C10—Fe1—C11	40.31 (8)	Fe1—C3—H3	126.7
C4—Fe1—C11	153.79 (9)	C10—C11—C12	108.58 (18)
C8—Fe1—C3	107.35 (8)	C10—C11—Fe1	69.56 (11)
C1—Fe1—C3	68.57 (8)	C12—C11—Fe1	69.28 (11)
C5—Fe1—C3	68.50 (8)	C10—C11—H11	125.7
C9—Fe1—C3	118.52 (9)	C12—C11—H11	125.7
C12—Fe1—C3	127.16 (9)	Fe1—C11—H11	127.0
C2—Fe1—C3	40.17 (8)	C3—C2—C1	107.97 (18)
C10—Fe1—C3	153.12 (9)	C3—C2—Fe1	70.34 (12)
C4—Fe1—C3	40.48 (8)	C1—C2—Fe1	68.68 (11)
C11—Fe1—C3	165.04 (9)	C3—C2—H2	126.0
C11—C12—C8	107.36 (18)	C1—C2—H2	126.0
C11—C12—Fe1	70.31 (11)	Fe1—C2—H2	126.5
C8—C12—Fe1	68.50 (11)	O1—C6—C1	121.19 (19)
C11—C12—H12	126.3	O1—C6—C7	120.82 (19)
C8—C12—H12	126.3	C1—C6—C7	117.99 (18)
Fe1—C12—H12	126.4	C13—C8—C9	126.81 (19)
C5—C4—C3	108.33 (19)	C13—C8—C12	124.83 (19)
C5—C4—Fe1	68.83 (11)	C9—C8—C12	108.35 (18)
C3—C4—Fe1	69.87 (12)	C13—C8—Fe1	124.42 (15)
C5—C4—H4	125.8	C9—C8—Fe1	69.95 (11)
C3—C4—H4	125.8	C12—C8—Fe1	70.23 (11)
Fe1—C4—H4	127.0	N1—C13—C8	178.1 (2)
C6—C7—H7A	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···N1^i	0.93	2.72	3.411 (3)	132
C9—H9···N1^i	0.93	2.73	3.463 (3)	137
C11—H11···O1^ii	0.93	2.59	3.514 (3)	178

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