N-(Trimethyl­silyl)pyridine-3-carbox­amide

Gilg, K.; Klüfers, P.

doi:10.1107/S1600536807059478

N-(Trimethylsilyl)pyridine-3-carboxamide

The title compound, C₉H₁₄N₂OSi, crystallizes with two molecules of different conformation in the asymmetric unit. As the main intermolecular interactions, C—H

O and N—H

O hydrogen bonds connect the individual molecules into chains along [100]. While N—H donors connect to O-atom acceptors, the potential pyridine N-atom acceptors obviously are of minor importance: one of them accepts a hydrogen bond of a pyridylic C—H function, and the other one does not establish any interactions within a `sum of the van der Waals radii plus 0.2 Å' criterion. In addition, there are π–π stacking interactions between pyridyl rings (centroid–centroid distance = 3.615 Å).

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059478/bt2620sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059478/bt2620Isup2.hkl Contains datablock I

CCDC reference: 672981

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Key indicators

Single-crystal X-ray study
T = 200 K
Mean (C-C) = 0.003 Å
R factor = 0.052
wR factor = 0.126
Data-to-parameter ratio = 21.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Si1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Si2

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound, silylated nicotineamide, is a building block for the synthesis of coenzymes of the NAD family. In contrast to the results presented by Franchetti et al. (2004), numerous variations of the reaction conditions always yielded the mono- instead of the bis-silyl derivative of nicotineamide. In order to verify Si-NMR-spectroscopic hints on monosilylation, the product was crystallized and structurally characterized.

In the crystal structure, two molecules with a different orientation of the pyridine-N atoms with respect to the amide function are stacked at right angles. The strongest intermolecular interactions are N–H···O hydrogen bonds (Fig. 1), the O acceptor thus being the stronger one compared with the potential pyridine-N acceptor. The latter acts as an acceptor in a weak C–H···N interaction, which, together with supporting π-stacking, connects two N–H···O-connected chains along [100] to double chains (Fig. 2).

Related literature top

The title compound was prepared according to a published procedure for the bis(trimethylsilyl) derivative (Franchetti et al., 2004).

Experimental top

The title compound was prepared in analogy to a published procedure (Franchetti et al., 2004) upon reaction of nicotineamide with chlorotrimethylsilane in boiling hexamethyldisilazane. Crystals suitable for X-ray analysis were obtained within one day after slowly cooling down the reaction mixture.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and anisotropic displacement ellipsoids (drawn at 40% probability level. Intermolecular N–H···O hydrogen bonds are drawn as yellow bars.
	Fig. 2. Two N–H···O-connected chains. The main interactions are C–H···N bonds (green bars) and pyridyl–pyridyl π-stacking (top middle and bottom middle of the figure).

N-(Trimethylsilyl)pyridine-3-carboxamide top

Crystal data top

C₉H₁₄N₂OSi	Z = 4
M_r = 194.31	F(000) = 416
Triclinic, P1	D_x = 1.149 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.9550 (3) Å	Cell parameters from 3640 reflections
b = 11.0928 (4) Å	θ = 3.1–27.5°
c = 11.2096 (4) Å	µ = 0.18 mm⁻¹
α = 80.5113 (14)°	T = 200 K
β = 82.6627 (13)°	Needle, colourless
γ = 67.2202 (19)°	0.18 × 0.06 × 0.03 mm
V = 1122.91 (7) Å³

Data collection top

KappaCCD diffractometer	3244 reflections with I > 2σ(I)
Radiation source: rotating anode	R_int = 0.030
MONTEL, graded multilayered X-ray optics monochromator	θ_max = 27.5°, θ_min = 3.3°
ϕ/ω–scan	h = −12→12
7682 measured reflections	k = −14→12
5073 independent reflections	l = −13→14

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.126	Only H-atom displacement parameters refined
S = 1.01	w = 1/[σ²(F_o²) + (0.0385P)² + 0.342P] where P = (F_o² + 2F_c²)/3
5073 reflections	(Δ/σ)_max < 0.001
237 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₉H₁₄N₂OSi	γ = 67.2202 (19)°
M_r = 194.31	V = 1122.91 (7) Å³
Triclinic, P1	Z = 4
a = 9.9550 (3) Å	Mo Kα radiation
b = 11.0928 (4) Å	µ = 0.18 mm⁻¹
c = 11.2096 (4) Å	T = 200 K
α = 80.5113 (14)°	0.18 × 0.06 × 0.03 mm
β = 82.6627 (13)°

Data collection top

KappaCCD diffractometer	3244 reflections with I > 2σ(I)
7682 measured reflections	R_int = 0.030
5073 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.126	Only H-atom displacement parameters refined
S = 1.01	Δρ_max = 0.20 e Å⁻³
5073 reflections	Δρ_min = −0.24 e Å⁻³
237 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Si1	0.70081 (7)	0.07672 (6)	0.13501 (6)	0.04635 (18)
Si2	0.15496 (6)	0.20555 (7)	0.41313 (6)	0.04568 (18)
O1	0.42748 (15)	0.31010 (16)	0.16768 (15)	0.0530 (4)
O2	−0.05206 (15)	0.23814 (16)	0.23110 (14)	0.0519 (4)
N1	0.6058 (2)	0.5495 (2)	0.3814 (2)	0.0594 (6)
N2	0.66665 (17)	0.22227 (17)	0.19744 (16)	0.0436 (4)
H721	0.7404	0.2323	0.2246	0.056 (2)*
N3	−0.0520 (3)	0.3866 (2)	−0.1337 (2)	0.0665 (6)
N4	0.15327 (17)	0.26542 (17)	0.25745 (15)	0.0384 (4)
H741	0.2223	0.2940	0.2244	0.056 (2)*
C1	0.6209 (2)	0.4456 (2)	0.3272 (2)	0.0500 (6)
H1	0.7110	0.3723	0.3325	0.056 (2)*
C2	0.5146 (2)	0.4372 (2)	0.26416 (19)	0.0392 (5)
C3	0.3823 (2)	0.5446 (2)	0.2575 (2)	0.0504 (6)
H3	0.3052	0.5434	0.2163	0.056 (2)*
C4	0.3658 (3)	0.6531 (2)	0.3123 (2)	0.0560 (6)
H4	0.2775	0.7285	0.3080	0.056 (2)*
C5	0.4783 (3)	0.6506 (2)	0.3727 (2)	0.0555 (6)
H5	0.4645	0.7254	0.4106	0.056 (2)*
C6	0.5334 (2)	0.3194 (2)	0.20598 (19)	0.0411 (5)
C7	0.8928 (3)	−0.0263 (3)	0.1667 (3)	0.0643 (7)
H71	0.9013	−0.0455	0.2545	0.116 (3)*
H72	0.9561	0.0212	0.1304	0.116 (3)*
H73	0.9226	−0.1090	0.1319	0.116 (3)*
C8	0.6801 (3)	0.1152 (3)	−0.0291 (3)	0.0777 (9)
H81	0.5780	0.1699	−0.0437	0.116 (3)*
H82	0.7087	0.0331	−0.0648	0.116 (3)*
H83	0.7427	0.1630	−0.0663	0.116 (3)*
C9	0.5745 (3)	−0.0029 (3)	0.2113 (3)	0.0724 (8)
H91	0.5881	−0.0228	0.2984	0.116 (3)*
H92	0.5949	−0.0848	0.1775	0.116 (3)*
H93	0.4735	0.0568	0.1983	0.116 (3)*
C10	−0.0537 (2)	0.3488 (2)	−0.0142 (2)	0.0526 (6)
H10	−0.1427	0.3475	0.0270	0.056 (2)*
C11	0.0669 (2)	0.3113 (2)	0.05355 (18)	0.0383 (5)
C12	0.1957 (2)	0.3146 (2)	−0.0080 (2)	0.0466 (5)
H12	0.2807	0.2914	0.0345	0.056 (2)*
C13	0.1991 (3)	0.3517 (3)	−0.1311 (2)	0.0589 (6)
H13	0.2869	0.3524	−0.1752	0.056 (2)*
C14	0.0738 (3)	0.3878 (2)	−0.1894 (2)	0.0640 (7)
H14	0.0770	0.4152	−0.2742	0.056 (2)*
C15	0.0515 (2)	0.2697 (2)	0.18614 (19)	0.0381 (5)
C16	0.1900 (3)	0.0272 (3)	0.4290 (3)	0.0713 (8)
H161	0.2827	−0.0184	0.3845	0.116 (3)*
H162	0.1106	0.0146	0.3958	0.116 (3)*
H163	0.1951	−0.0088	0.5149	0.116 (3)*
C17	0.3083 (3)	0.2331 (3)	0.4661 (2)	0.0678 (7)
H171	0.2875	0.3279	0.4570	0.116 (3)*
H172	0.3984	0.1893	0.4177	0.116 (3)*
H173	0.3201	0.1967	0.5516	0.116 (3)*
C18	−0.0187 (3)	0.2966 (3)	0.4963 (2)	0.0765 (9)
H181	−0.0342	0.3904	0.4864	0.116 (3)*
H182	−0.0141	0.2620	0.5826	0.116 (3)*
H183	−0.0997	0.2857	0.4640	0.116 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0443 (3)	0.0472 (4)	0.0531 (4)	−0.0208 (3)	−0.0041 (3)	−0.0118 (3)
Si2	0.0445 (3)	0.0535 (4)	0.0421 (4)	−0.0217 (3)	−0.0064 (3)	−0.0035 (3)
O1	0.0354 (8)	0.0616 (11)	0.0699 (11)	−0.0227 (7)	−0.0111 (7)	−0.0124 (8)
O2	0.0333 (8)	0.0691 (11)	0.0613 (10)	−0.0260 (7)	−0.0024 (7)	−0.0133 (8)
N1	0.0482 (11)	0.0602 (14)	0.0773 (15)	−0.0230 (10)	0.0032 (10)	−0.0287 (11)
N2	0.0330 (9)	0.0456 (11)	0.0584 (12)	−0.0181 (8)	−0.0070 (8)	−0.0120 (9)
N3	0.0791 (16)	0.0530 (14)	0.0612 (15)	−0.0072 (11)	−0.0350 (12)	−0.0109 (11)
N4	0.0328 (8)	0.0492 (11)	0.0400 (10)	−0.0219 (8)	−0.0061 (7)	−0.0049 (8)
C1	0.0351 (11)	0.0513 (14)	0.0667 (15)	−0.0160 (10)	−0.0003 (10)	−0.0190 (12)
C2	0.0328 (10)	0.0418 (12)	0.0448 (12)	−0.0179 (9)	0.0018 (8)	−0.0038 (9)
C3	0.0406 (12)	0.0540 (15)	0.0517 (14)	−0.0135 (10)	−0.0066 (10)	−0.0013 (11)
C4	0.0543 (14)	0.0454 (14)	0.0564 (15)	−0.0077 (11)	0.0042 (12)	−0.0081 (12)
C5	0.0574 (15)	0.0522 (15)	0.0613 (16)	−0.0245 (12)	0.0078 (12)	−0.0181 (12)
C6	0.0320 (10)	0.0475 (13)	0.0475 (13)	−0.0200 (9)	−0.0024 (9)	−0.0031 (10)
C7	0.0514 (14)	0.0542 (16)	0.0832 (19)	−0.0107 (12)	−0.0054 (13)	−0.0195 (14)
C8	0.082 (2)	0.095 (2)	0.0586 (17)	−0.0306 (17)	−0.0094 (14)	−0.0191 (16)
C9	0.0713 (17)	0.0576 (17)	0.098 (2)	−0.0358 (14)	0.0067 (15)	−0.0151 (15)
C10	0.0473 (13)	0.0516 (14)	0.0590 (16)	−0.0110 (11)	−0.0187 (11)	−0.0148 (12)
C11	0.0364 (10)	0.0363 (12)	0.0435 (12)	−0.0101 (9)	−0.0096 (9)	−0.0122 (9)
C12	0.0468 (12)	0.0511 (14)	0.0445 (13)	−0.0184 (10)	−0.0063 (10)	−0.0104 (11)
C13	0.0734 (17)	0.0567 (16)	0.0459 (14)	−0.0233 (13)	0.0030 (12)	−0.0121 (12)
C14	0.097 (2)	0.0452 (15)	0.0425 (14)	−0.0141 (14)	−0.0152 (14)	−0.0091 (11)
C15	0.0285 (10)	0.0399 (12)	0.0480 (12)	−0.0114 (8)	−0.0065 (8)	−0.0120 (9)
C16	0.0840 (19)	0.0589 (18)	0.0745 (19)	−0.0346 (15)	−0.0060 (15)	0.0026 (14)
C17	0.0763 (18)	0.088 (2)	0.0530 (15)	−0.0437 (16)	−0.0251 (13)	0.0016 (14)
C18	0.0653 (17)	0.101 (2)	0.0498 (16)	−0.0157 (16)	0.0027 (13)	−0.0176 (16)

Geometric parameters (Å, º) top

Si1—N2	1.7604 (18)	C7—H71	0.9800
Si1—C8	1.838 (3)	C7—H72	0.9800
Si1—C9	1.852 (3)	C7—H73	0.9800
Si1—C7	1.853 (2)	C8—H81	0.9800
Si2—N4	1.7617 (18)	C8—H82	0.9800
Si2—C18	1.851 (3)	C8—H83	0.9800
Si2—C17	1.852 (2)	C9—H91	0.9800
Si2—C16	1.852 (3)	C9—H92	0.9800
O1—C6	1.234 (2)	C9—H93	0.9800
O2—C15	1.237 (2)	C10—C11	1.390 (3)
N1—C5	1.331 (3)	C10—H10	0.9500
N1—C1	1.339 (3)	C11—C12	1.387 (3)
N2—C6	1.351 (3)	C11—C15	1.489 (3)
N2—H721	0.8800	C12—C13	1.374 (3)
N3—C14	1.330 (4)	C12—H12	0.9500
N3—C10	1.336 (3)	C13—C14	1.370 (4)
N4—C15	1.350 (2)	C13—H13	0.9500
N4—H741	0.8800	C14—H14	0.9500
C1—C2	1.384 (3)	C16—H161	0.9800
C1—H1	0.9500	C16—H162	0.9800
C2—C3	1.392 (3)	C16—H163	0.9800
C2—C6	1.493 (3)	C17—H171	0.9800
C3—C4	1.385 (3)	C17—H172	0.9800
C3—H3	0.9500	C17—H173	0.9800
C4—C5	1.369 (3)	C18—H181	0.9800
C4—H4	0.9500	C18—H182	0.9800
C5—H5	0.9500	C18—H183	0.9800

N2—Si1—C8	109.72 (12)	H81—C8—H82	109.5
N2—Si1—C9	109.61 (11)	Si1—C8—H83	109.5
C8—Si1—C9	111.13 (14)	H81—C8—H83	109.5
N2—Si1—C7	103.89 (10)	H82—C8—H83	109.5
C8—Si1—C7	110.88 (13)	Si1—C9—H91	109.5
C9—Si1—C7	111.36 (14)	Si1—C9—H92	109.5
N4—Si2—C18	111.29 (11)	H91—C9—H92	109.5
N4—Si2—C17	104.79 (10)	Si1—C9—H93	109.5
C18—Si2—C17	110.26 (14)	H91—C9—H93	109.5
N4—Si2—C16	108.14 (11)	H92—C9—H93	109.5
C18—Si2—C16	111.33 (14)	N3—C10—C11	124.0 (2)
C17—Si2—C16	110.82 (13)	N3—C10—H10	118.0
C5—N1—C1	116.3 (2)	C11—C10—H10	118.0
C6—N2—Si1	123.55 (14)	C12—C11—C10	117.2 (2)
C6—N2—H721	118.2	C12—C11—C15	123.86 (18)
Si1—N2—H721	118.2	C10—C11—C15	119.0 (2)
C14—N3—C10	116.9 (2)	C13—C12—C11	119.2 (2)
C15—N4—Si2	123.40 (14)	C13—C12—H12	120.4
C15—N4—H741	118.3	C11—C12—H12	120.4
Si2—N4—H741	118.3	C14—C13—C12	119.0 (2)
N1—C1—C2	124.7 (2)	C14—C13—H13	120.5
N1—C1—H1	117.6	C12—C13—H13	120.5
C2—C1—H1	117.6	N3—C14—C13	123.6 (2)
C1—C2—C3	117.4 (2)	N3—C14—H14	118.2
C1—C2—C6	123.68 (19)	C13—C14—H14	118.2
C3—C2—C6	118.94 (19)	O2—C15—N4	119.9 (2)
C4—C3—C2	118.4 (2)	O2—C15—C11	120.82 (17)
C4—C3—H3	120.8	N4—C15—C11	119.24 (17)
C2—C3—H3	120.8	Si2—C16—H161	109.5
C5—C4—C3	119.2 (2)	Si2—C16—H162	109.5
C5—C4—H4	120.4	H161—C16—H162	109.5
C3—C4—H4	120.4	Si2—C16—H163	109.5
N1—C5—C4	123.9 (2)	H161—C16—H163	109.5
N1—C5—H5	118.0	H162—C16—H163	109.5
C4—C5—H5	118.0	Si2—C17—H171	109.5
O1—C6—N2	120.3 (2)	Si2—C17—H172	109.5
O1—C6—C2	120.15 (18)	H171—C17—H172	109.5
N2—C6—C2	119.52 (17)	Si2—C17—H173	109.5
Si1—C7—H71	109.5	H171—C17—H173	109.5
Si1—C7—H72	109.5	H172—C17—H173	109.5
H71—C7—H72	109.5	Si2—C18—H181	109.5
Si1—C7—H73	109.5	Si2—C18—H182	109.5
H71—C7—H73	109.5	H181—C18—H182	109.5
H72—C7—H73	109.5	Si2—C18—H183	109.5
Si1—C8—H81	109.5	H181—C18—H183	109.5
Si1—C8—H82	109.5	H182—C18—H183	109.5

C8—Si1—N2—C6	68.8 (2)	C3—C2—C6—O1	−10.0 (3)
C9—Si1—N2—C6	−53.5 (2)	C1—C2—C6—N2	−10.2 (3)
C7—Si1—N2—C6	−172.58 (18)	C3—C2—C6—N2	171.14 (19)
C18—Si2—N4—C15	−57.1 (2)	C14—N3—C10—C11	−0.1 (4)
C17—Si2—N4—C15	−176.31 (17)	N3—C10—C11—C12	0.4 (3)
C16—Si2—N4—C15	65.44 (19)	N3—C10—C11—C15	−179.3 (2)
C5—N1—C1—C2	0.1 (4)	C10—C11—C12—C13	−1.1 (3)
N1—C1—C2—C3	−0.5 (4)	C15—C11—C12—C13	178.5 (2)
N1—C1—C2—C6	−179.2 (2)	C11—C12—C13—C14	1.6 (3)
C1—C2—C3—C4	0.9 (3)	C10—N3—C14—C13	0.6 (4)
C6—C2—C3—C4	179.7 (2)	C12—C13—C14—N3	−1.4 (4)
C2—C3—C4—C5	−1.1 (3)	Si2—N4—C15—O2	4.5 (3)
C1—N1—C5—C4	−0.3 (4)	Si2—N4—C15—C11	−174.82 (14)
C3—C4—C5—N1	0.9 (4)	C12—C11—C15—O2	−162.3 (2)
Si1—N2—C6—O1	−0.9 (3)	C10—C11—C15—O2	17.3 (3)
Si1—N2—C6—C2	177.98 (15)	C12—C11—C15—N4	17.0 (3)
C1—C2—C6—O1	168.7 (2)	C10—C11—C15—N4	−163.37 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H721···O2ⁱ	0.88	2.10	2.948 (2)	161
N4—H741···O1	0.88	2.13	2.982 (2)	164
C12—H12···O1	0.95	2.30	3.201 (3)	157
C1—H1···O2ⁱ	0.95	2.49	3.343 (3)	149
C3—H3···N3ⁱⁱ	0.95	2.58	3.492 (4)	161

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

Experimental details

Crystal data
Chemical formula	C₉H₁₄N₂OSi
M_r	194.31
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	9.9550 (3), 11.0928 (4), 11.2096 (4)
α, β, γ (°)	80.5113 (14), 82.6627 (13), 67.2202 (19)
V (Å³)	1122.91 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.18 × 0.06 × 0.03

Data collection
Diffractometer	KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7682, 5073, 3244
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.126, 1.01
No. of reflections	5073
No. of parameters	237
H-atom treatment	Only H-atom displacement parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.24

Computer programs: COLLECT (Nonius, 2000), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996).