N,N-Di­methyl-N'-(o-fluoro­benzoyl)­hydrazide

The title di­methyl­hydrazide o-FC₆H₄C(O)NHNMe₂, or C₉H₁₁FN₂O, is compared structurally both with other aroyl hydrazides, ArC(O)NHNH₂, and with related tri­methyl­ammonio yl­ides, Me₃N(+)-N(-)C(O)Ar.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.045
• wR factor = 0.116
• Data-to-parameter ratio = 14.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

The title compound, (I), was prepared as a precurser to the corresponding trimethylammonio-stabilized nitrogen ylide Me₃N(+)—N(-)—C(O)C₆H₄—F-o. Its structure was determined in the course of an investigation into the ability of nitrogen ylides to act as ligands with transition metals (Morris et al., 2003).

The presence of the ortho-fluoro substituent causes (I) to adopt a conformation (Fig. 1) which precludes conjugation across the C6—C7 bond [C1—C6—C7—N1 = 122.5 (2)°]. Possibly as a result, the C6—C7 bond [1.509 (2) Å] is 0.02 Å longer than the database average value obtained by Orpen et al. (1992) for such bonds, whereas all other bond lengths in (I) agree within 0.008 Å with appropriate average values from the Cambridge Structural Database (Allen, 2002). Phenylhydrazides, in general, adopt much flatter conformations than that found in (I). For example, in PhC(O)NHNH₂, (II), the C(Ph)—C(Ph)—C(O)—N torsion angle is 30° (Kallel et al., 1992), while in o-HOC₆H₄C(O)NHNH₂, (III), the corresponding angle is only 3° (Mikenda et al., 1993). In (I), the C6—C7—N1—N2 torsion angle is 175.9 (1)°. Corresponding values in other hydrazides are almost invariably close to 180°; the only exception we are aware of is provided by Ph(CO)NMeNMe₂, where this torsion angle is only 8.5° (Knapp et al., 1981), presumably for steric reasons. In (I), the N—N distance [1.420 (2) Å] and C—N—N angle [119.8 (1)°] are typical of hydrazides, such as (II) and (III), whereas in the closely related Me₃N(+)—N(-)C(O)Ar ylides, the N—N distances are longer and the C—N—N angles more acute, e.g. 1.470 (3) Å and 114.2 (3)° when Ar = Ph (Cameron et al., 1972), and 1.474 (1) Å and 174.8 (1)° when Ar = p-Cl–C₆H₄ (Morris et al., 2003). QUEST and CONQUEST search programs were used with Version 5.24 of the Cambridge Structural Database (Allen, 2002) to obtain some torsion angles not given by the original authors.

Glide-plane-related molecules connected by N—H···O hydrogen bonds (Fig. 2) form stacks which run parallel to the b axis. These stacks pack so that alternate layers parallel to (001) contain, respectively, aromatic rings and terminal NMe₂ groups, as can be seen by viewing the contents of the unit cell in projection down the a axis (Fig. 3). As expected (Glusker et al., 1994), the F atoms do not participate in the hydrogen bonding.

The atomic U^ij values are moderately well reproduced by a TLS analysis (Schomacher & Trueblood, 1968): R₂ = (ΣΔU²/ΣU²)^1/2 = 0.10; they also pass the Hirshfeld (1976) rigid-bond test, the worst discrepancy being ΔU = 0.0018 (12) Ų for C4—C5.

S2. Experimental

The title compound was prepared by the method of Smith et al. (1968).

S3. Refinement

All H atoms were initially located from difference syntheses. The H atom bonded to N1 was freely refined. Other H atoms were positioned geometrically and refined with riding constraints, assuming C—H bond lengths of 0.93 and 0.96 Å, respectively, for sp² and sp³ C atoms. In the case of each of the two methyl groups, a single orientation parameter was also refined.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. View of (I), shown with 50% probability displacement ellipsoids.
	Fig. 2. Part of a stack of hydrogen-bonded molecules related by the b-glide plane normal to the a axis. The direction of view is down the a axis and b runs from left to right in the plane of the drawing.
	Fig. 3. The unit-cell contents, viewed in projection down the a axis.

(I)

Crystal data

C9H11FN2O	F(000) = 768
Mr = 182.2	Dx = 1.303 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1794 reflections
a = 11.8503 (5) Å	θ = 2.9–26.0°
b = 7.8530 (3) Å	µ = 0.10 mm^−1
c = 19.9630 (9) Å	T = 100 K
V = 1857.77 (13) Å^3	Needle, colourless
Z = 8	0.40 × 0.05 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer	Rint = 0.057
thick–slices ω and ϕ scans	θmax = 25.9°, θmin = 3.3°
6796 measured reflections	h = −14→14
1797 independent reflections	k = −9→9
1491 reflections with I > 2σ(I)	l = −24→24

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.045	w = 1/[σ^2(Fo^2) + (0.048P)^2 + 0.85P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.116	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.23 e Å^−3
1797 reflections	Δρmin = −0.25 e Å^−3
124 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.04440 (14)	0.0364 (2)	0.31315 (8)	0.0242 (4)
C2	0.01463 (14)	−0.0441 (2)	0.25446 (9)	0.0275 (4)
H2	−0.056	−0.0942	0.2495	0.033*
C3	0.09321 (15)	−0.0482 (2)	0.20276 (8)	0.0285 (4)
H3	0.0747	−0.0992	0.1622	0.034*
C4	0.19926 (15)	0.0235 (2)	0.21152 (9)	0.0283 (4)
H4	0.2516	0.0203	0.1768	0.034*
C5	0.22732 (14)	0.0997 (2)	0.27185 (8)	0.0252 (4)
H5	0.2992	0.145	0.2777	0.03*
C6	0.14924 (13)	0.1093 (2)	0.32376 (8)	0.0217 (4)
C7	0.17407 (14)	0.2139 (2)	0.38546 (8)	0.0220 (4)
C8	0.25331 (19)	0.1700 (3)	0.53962 (9)	0.0384 (5)
H8A	0.1723	0.1678	0.5382	0.058*
H8B	0.2776	0.2334	0.5781	0.058*
H8C	0.2815	0.0556	0.5425	0.058*
C9	0.41985 (17)	0.2554 (3)	0.47847 (10)	0.0395 (5)
H9A	0.4488	0.1415	0.4814	0.059*
H9B	0.4462	0.3206	0.5161	0.059*
H9C	0.4456	0.3073	0.4377	0.059*
F1	−0.03368 (8)	0.04377 (14)	0.36335 (5)	0.0329 (3)
N1	0.26030 (13)	0.15704 (18)	0.42201 (7)	0.0253 (3)
H1	0.2893 (17)	0.051 (3)	0.4152 (10)	0.034 (5)*
N2	0.29666 (13)	0.25077 (19)	0.47890 (7)	0.0273 (4)
O1	0.11979 (10)	0.34444 (15)	0.39699 (6)	0.0279 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0200 (8)	0.0247 (8)	0.0278 (9)	0.0017 (7)	0.0018 (7)	−0.0009 (7)
C2	0.0199 (8)	0.0294 (9)	0.0332 (9)	−0.0004 (7)	−0.0047 (7)	−0.0045 (7)
C3	0.0281 (9)	0.0311 (9)	0.0263 (9)	0.0038 (8)	−0.0055 (7)	−0.0055 (7)
C4	0.0265 (9)	0.0326 (9)	0.0260 (9)	0.0013 (7)	0.0021 (7)	0.0004 (7)
C5	0.0203 (8)	0.0273 (9)	0.0280 (8)	−0.0017 (7)	−0.0012 (7)	0.0005 (7)
C6	0.0208 (8)	0.0195 (8)	0.0248 (8)	0.0015 (6)	−0.0028 (7)	0.0013 (6)
C7	0.0211 (8)	0.0210 (8)	0.0239 (8)	−0.0026 (6)	0.0004 (6)	0.0020 (6)
C8	0.0498 (12)	0.0378 (10)	0.0275 (9)	−0.0050 (9)	−0.0023 (9)	−0.0040 (8)
C9	0.0332 (10)	0.0449 (11)	0.0405 (11)	−0.0068 (9)	−0.0097 (9)	−0.0056 (9)
F1	0.0235 (5)	0.0414 (6)	0.0338 (6)	−0.0067 (5)	0.0068 (4)	−0.0083 (4)
N1	0.0301 (8)	0.0192 (7)	0.0267 (7)	0.0030 (6)	−0.0073 (6)	−0.0043 (6)
N2	0.0313 (8)	0.0252 (7)	0.0254 (7)	0.0001 (7)	−0.0088 (6)	−0.0043 (6)
O1	0.0256 (6)	0.0250 (6)	0.0331 (7)	0.0028 (5)	−0.0046 (5)	−0.0053 (5)

Geometric parameters (Å, º)

C1—F1	1.3653 (19)	C7—O1	1.232 (2)
C1—C2	1.377 (2)	C7—N1	1.333 (2)
C1—C6	1.384 (2)	C8—N2	1.462 (2)
C2—C3	1.390 (3)	C8—H8A	0.96
C2—H2	0.93	C8—H8B	0.96
C3—C4	1.388 (3)	C8—H8C	0.96
C3—H3	0.93	C9—N2	1.460 (2)
C4—C5	1.385 (2)	C9—H9A	0.96
C4—H4	0.93	C9—H9B	0.96
C5—C6	1.391 (2)	C9—H9C	0.96
C5—H5	0.93	N1—N2	1.4202 (19)
C6—C7	1.509 (2)	N1—H1	0.91 (2)
F1—C1—C2	118.06 (15)	N1—C7—C6	114.46 (14)
F1—C1—C6	118.58 (14)	N2—C8—H8A	109.5
C2—C1—C6	123.36 (16)	N2—C8—H8B	109.5
C1—C2—C3	118.07 (16)	H8A—C8—H8B	109.5
C1—C2—H2	121	N2—C8—H8C	109.5
C3—C2—H2	121	H8A—C8—H8C	109.5
C4—C3—C2	120.23 (16)	H8B—C8—H8C	109.5
C4—C3—H3	119.9	N2—C9—H9A	109.5
C2—C3—H3	119.9	N2—C9—H9B	109.5
C5—C4—C3	120.13 (16)	H9A—C9—H9B	109.5
C5—C4—H4	119.9	N2—C9—H9C	109.5
C3—C4—H4	119.9	H9A—C9—H9C	109.5
C4—C5—C6	120.75 (16)	H9B—C9—H9C	109.5
C4—C5—H5	119.6	C7—N1—N2	119.79 (14)
C6—C5—H5	119.6	C7—N1—H1	120.9 (13)
C1—C6—C5	117.42 (15)	N2—N1—H1	118.6 (13)
C1—C6—C7	121.66 (15)	N1—N2—C9	108.16 (14)
C5—C6—C7	120.50 (14)	N1—N2—C8	109.36 (14)
O1—C7—N1	125.22 (15)	C9—N2—C8	111.54 (15)
O1—C7—C6	120.24 (14)
F1—C1—C2—C3	178.55 (15)	C4—C5—C6—C7	−171.20 (15)
C6—C1—C2—C3	−1.7 (3)	C1—C6—C7—O1	−60.7 (2)
C1—C2—C3—C4	1.6 (3)	C5—C6—C7—O1	111.73 (18)
C2—C3—C4—C5	−0.1 (3)	C1—C6—C7—N1	122.50 (17)
C3—C4—C5—C6	−1.6 (3)	C5—C6—C7—N1	−65.1 (2)
F1—C1—C6—C5	179.89 (14)	O1—C7—N1—N2	−0.7 (3)
C2—C1—C6—C5	0.1 (2)	C6—C7—N1—N2	175.91 (14)
F1—C1—C6—C7	−7.5 (2)	C7—N1—N2—C9	−136.70 (17)
C2—C1—C6—C7	172.74 (15)	C7—N1—N2—C8	101.65 (18)
C4—C5—C6—C1	1.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.91 (2)	1.98 (2)	2.8801 (19)	168.8 (19)

Symmetry code: (i) −x+1/2, y−1/2, z.