A new key intermediate in the synthesis of 6-oxo­piperidine-2-carboxyl­ate derivatives

The relative stereochemistry of methyl 6-oxo-5-(5-phenyl­tetrazol-2-yl)­piperidine-2-carboxyl­ate, C₁₄H₁₅N₅O₃, has been determined. It confirms the cis configuration of the piperidine ring as well as the position of the substituent on the tetrazole ring. The packing of the mol­ecules is influenced by N—H...O and C—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.044
• wR factor = 0.108
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

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Alert level C
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ....        C13

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 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
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
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   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: KappaCCD Server Software (Nonius, 1998); data reduction: DENZO (Otwinowski & Miror, 1997); 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) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: WinGX (Farugia, 1999).

6-oxo-5-(5-phenyltetrazol-2-yl)piperidine-2-carboxylate

Crystal data

C14H15N5O3	Z = 4
Mr = 301.31	F(000) = 632
Monoclinic, P21/c	Dx = 1.356 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71069 Å
a = 12.7980 (6) Å	µ = 0.10 mm^−1
b = 10.8334 (3) Å	T = 296 K
c = 10.9142 (3) Å	Needle, colourless
β = 102.796 (1)°	0.1 × 0.08 × 0.05 mm
V = 1475.63 (9) Å^3

Data collection

Nonius KappaCCD diffractometer	1777 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 25.0°, θmin = 3.8°
ω scans	h = −15→14
5170 measured reflections	k = 0→12
2563 independent reflections	l = 0→12

Refinement

Refinement on F^2	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0438P)^2 + 0.1856P] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.044	(Δ/σ)max = 0.001
wR(F^2) = 0.108	Δρmax = 0.16 e Å^−3
S = 1.04	Δρmin = −0.15 e Å^−3
2563 reflections	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
204 parameters	Extinction coefficient: 0.026 (4)
0 restraints

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
N1	0.52361 (14)	0.15788 (16)	0.06580 (15)	0.0462 (5)
H1N	0.5552 (19)	0.097 (2)	0.032 (2)	0.076 (8)*
N2	0.29820 (13)	0.18081 (13)	0.21242 (13)	0.0378 (4)
N3	0.19857 (13)	0.14531 (14)	0.16191 (13)	0.0416 (4)
N4	0.24570 (14)	0.10269 (16)	0.36540 (14)	0.0518 (5)
N5	0.32864 (14)	0.15610 (15)	0.33375 (14)	0.0487 (5)
O1	0.76028 (12)	0.28508 (14)	0.24956 (13)	0.0665 (5)
O2	0.65052 (14)	0.15029 (16)	0.30919 (15)	0.0822 (6)
O3	0.38084 (12)	0.03380 (13)	0.05594 (13)	0.0579 (4)
C1	0.59129 (16)	0.26183 (17)	0.11582 (16)	0.0445 (5)
H1	0.6323	0.2865	0.0539	0.053*
C2	0.42661 (16)	0.13289 (18)	0.08577 (16)	0.0407 (5)
C3	0.36943 (15)	0.23592 (16)	0.14012 (15)	0.0393 (5)
H3	0.3240	0.2790	0.0689	0.047*
C4	0.44307 (17)	0.33169 (17)	0.21531 (19)	0.0510 (6)
H4A	0.4798	0.2971	0.2952	0.061*
H4B	0.4018	0.4025	0.2316	0.061*
C5	0.52385 (18)	0.37085 (18)	0.1399 (2)	0.0541 (6)
H5A	0.5702	0.4343	0.1855	0.065*
H5B	0.4864	0.4055	0.0604	0.065*
C6	0.16740 (16)	0.09652 (16)	0.25988 (16)	0.0404 (5)
C7	0.06222 (16)	0.04183 (17)	0.25248 (17)	0.0448 (5)
C8	0.0422 (2)	−0.0313 (2)	0.34883 (19)	0.0605 (6)
H8	0.0957	−0.0438	0.4207	0.073*
C9	−0.0567 (2)	−0.0855 (2)	0.3385 (2)	0.0747 (7)
H9	−0.0695	−0.1345	0.4036	0.090*
C10	−0.1362 (2)	−0.0680 (2)	0.2333 (3)	0.0740 (7)
H10	−0.2027	−0.1051	0.2270	0.089*
C11	−0.11774 (19)	0.0041 (2)	0.1370 (2)	0.0663 (7)
H11	−0.1717	0.0161	0.0655	0.080*
C12	−0.01924 (18)	0.0589 (2)	0.14638 (19)	0.0571 (6)
H12	−0.0071	0.1079	0.0809	0.068*
C13	0.66901 (17)	0.22383 (19)	0.23538 (18)	0.0483 (5)
C14	0.8408 (2)	0.2597 (2)	0.3625 (2)	0.0866 (9)
H14A	0.9030	0.3093	0.3632	0.130*
H14B	0.8601	0.1739	0.3644	0.130*
H14C	0.8127	0.2789	0.4349	0.130*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0395 (11)	0.0531 (11)	0.0485 (9)	−0.0062 (9)	0.0151 (8)	−0.0137 (8)
N2	0.0363 (10)	0.0424 (9)	0.0343 (8)	0.0044 (7)	0.0068 (7)	−0.0022 (6)
N3	0.0382 (11)	0.0476 (10)	0.0385 (8)	−0.0007 (8)	0.0076 (7)	−0.0027 (7)
N4	0.0505 (12)	0.0628 (11)	0.0415 (9)	−0.0051 (9)	0.0090 (8)	0.0044 (8)
N5	0.0476 (11)	0.0584 (11)	0.0382 (9)	0.0005 (9)	0.0055 (8)	0.0018 (7)
O1	0.0529 (11)	0.0703 (10)	0.0679 (9)	−0.0196 (8)	−0.0050 (7)	0.0094 (8)
O2	0.0743 (13)	0.0927 (13)	0.0733 (11)	−0.0205 (10)	0.0026 (9)	0.0309 (9)
O3	0.0467 (10)	0.0556 (9)	0.0762 (10)	−0.0121 (7)	0.0238 (7)	−0.0268 (7)
C1	0.0434 (13)	0.0492 (12)	0.0422 (10)	−0.0108 (10)	0.0122 (9)	−0.0003 (9)
C2	0.0382 (13)	0.0473 (12)	0.0367 (10)	−0.0011 (10)	0.0086 (8)	−0.0056 (8)
C3	0.0389 (12)	0.0416 (11)	0.0381 (9)	0.0005 (9)	0.0099 (8)	0.0022 (8)
C4	0.0519 (14)	0.0400 (11)	0.0636 (13)	−0.0007 (10)	0.0186 (11)	−0.0099 (9)
C5	0.0575 (15)	0.0416 (12)	0.0619 (12)	−0.0061 (10)	0.0105 (11)	0.0039 (9)
C6	0.0444 (13)	0.0401 (10)	0.0374 (10)	0.0023 (9)	0.0103 (9)	−0.0022 (8)
C7	0.0475 (14)	0.0432 (11)	0.0465 (11)	−0.0038 (10)	0.0162 (10)	−0.0043 (9)
C8	0.0666 (17)	0.0591 (14)	0.0573 (13)	−0.0082 (12)	0.0173 (11)	0.0074 (10)
C9	0.084 (2)	0.0669 (16)	0.0809 (17)	−0.0203 (15)	0.0339 (16)	0.0103 (13)
C10	0.0661 (19)	0.0659 (16)	0.0950 (19)	−0.0236 (14)	0.0285 (16)	−0.0046 (14)
C11	0.0482 (16)	0.0754 (16)	0.0726 (15)	−0.0137 (13)	0.0078 (12)	−0.0067 (12)
C12	0.0527 (15)	0.0653 (14)	0.0538 (13)	−0.0100 (12)	0.0131 (11)	0.0010 (10)
C13	0.0460 (14)	0.0471 (12)	0.0521 (12)	−0.0073 (10)	0.0112 (10)	0.0003 (10)
C14	0.0674 (19)	0.0917 (19)	0.0819 (16)	−0.0154 (15)	−0.0240 (14)	0.0081 (14)

Geometric parameters (Å, º)

N1—C2	1.335 (2)	C4—H4A	0.9700
N1—C1	1.452 (2)	C4—H4B	0.9700
N1—H1N	0.89 (2)	C5—H5A	0.9700
N2—N5	1.3224 (19)	C5—H5B	0.9700
N2—N3	1.329 (2)	C6—C7	1.456 (3)
N2—C3	1.459 (2)	C7—C8	1.385 (3)
N3—C6	1.331 (2)	C7—C12	1.388 (3)
N4—N5	1.320 (2)	C8—C9	1.377 (3)
N4—C6	1.350 (2)	C8—H8	0.9300
O1—C13	1.322 (2)	C9—C10	1.369 (3)
O1—C14	1.447 (3)	C9—H9	0.9300
O2—C13	1.193 (2)	C10—C11	1.371 (3)
O3—C2	1.232 (2)	C10—H10	0.9300
C1—C13	1.512 (3)	C11—C12	1.377 (3)
C1—C5	1.520 (3)	C11—H11	0.9300
C1—H1	0.9800	C12—H12	0.9300
C2—C3	1.525 (3)	C14—H14A	0.9600
C3—C4	1.515 (2)	C14—H14B	0.9600
C3—H3	0.9800	C14—H14C	0.9600
C4—C5	1.517 (3)
C2—N1—C1	126.51 (17)	C4—C5—H5B	109.4
C2—N1—H1N	116.2 (16)	C1—C5—H5B	109.4
C1—N1—H1N	115.9 (16)	H5A—C5—H5B	108.0
N5—N2—N3	113.55 (15)	N3—C6—N4	111.57 (17)
N5—N2—C3	122.94 (15)	N3—C6—C7	123.70 (16)
N3—N2—C3	123.44 (13)	N4—C6—C7	124.72 (16)
N2—N3—C6	102.27 (14)	C8—C7—C12	118.6 (2)
N5—N4—C6	106.64 (15)	C8—C7—C6	120.97 (19)
N4—N5—N2	105.97 (15)	C12—C7—C6	120.41 (17)
C13—O1—C14	116.62 (17)	C9—C8—C7	120.2 (2)
N1—C1—C13	109.70 (15)	C9—C8—H8	119.9
N1—C1—C5	110.71 (17)	C7—C8—H8	119.9
C13—C1—C5	110.63 (15)	C10—C9—C8	120.6 (2)
N1—C1—H1	108.6	C10—C9—H9	119.7
C13—C1—H1	108.6	C8—C9—H9	119.7
C5—C1—H1	108.6	C9—C10—C11	120.0 (2)
O3—C2—N1	122.59 (17)	C9—C10—H10	120.0
O3—C2—C3	119.98 (17)	C11—C10—H10	120.0
N1—C2—C3	117.31 (17)	C10—C11—C12	120.0 (2)
N2—C3—C4	112.06 (14)	C10—C11—H11	120.0
N2—C3—C2	108.78 (14)	C12—C11—H11	120.0
C4—C3—C2	114.67 (16)	C11—C12—C7	120.7 (2)
N2—C3—H3	107.0	C11—C12—H12	119.6
C4—C3—H3	107.0	C7—C12—H12	119.6
C2—C3—H3	107.0	O2—C13—O1	123.92 (19)
C3—C4—C5	108.33 (16)	O2—C13—C1	124.99 (19)
C3—C4—H4A	110.0	O1—C13—C1	111.07 (17)
C5—C4—H4A	110.0	O1—C14—H14A	109.5
C3—C4—H4B	110.0	O1—C14—H14B	109.5
C5—C4—H4B	110.0	H14A—C14—H14B	109.5
H4A—C4—H4B	108.4	O1—C14—H14C	109.5
C4—C5—C1	110.97 (16)	H14A—C14—H14C	109.5
C4—C5—H5A	109.4	H14B—C14—H14C	109.5
C1—C5—H5A	109.4
N5—N2—N3—C6	0.22 (19)	N2—N3—C6—N4	0.02 (19)
C3—N2—N3—C6	177.19 (15)	N2—N3—C6—C7	−179.08 (16)
C6—N4—N5—N2	0.37 (19)	N5—N4—C6—N3	−0.3 (2)
N3—N2—N5—N4	−0.39 (19)	N5—N4—C6—C7	178.84 (17)
C3—N2—N5—N4	−177.37 (15)	N3—C6—C7—C8	165.45 (18)
C2—N1—C1—C13	94.6 (2)	N4—C6—C7—C8	−13.5 (3)
C2—N1—C1—C5	−27.7 (2)	N3—C6—C7—C12	−12.5 (3)
C1—N1—C2—O3	−168.83 (17)	N4—C6—C7—C12	168.56 (18)
C1—N1—C2—C3	15.1 (3)	C12—C7—C8—C9	0.0 (3)
N5—N2—C3—C4	−37.4 (2)	C6—C7—C8—C9	−177.9 (2)
N3—N2—C3—C4	145.91 (16)	C7—C8—C9—C10	0.1 (4)
N5—N2—C3—C2	90.43 (18)	C8—C9—C10—C11	−0.1 (4)
N3—N2—C3—C2	−86.25 (19)	C9—C10—C11—C12	0.0 (4)
O3—C2—C3—N2	32.4 (2)	C10—C11—C12—C7	0.1 (3)
N1—C2—C3—N2	−151.41 (16)	C8—C7—C12—C11	−0.1 (3)
O3—C2—C3—C4	158.79 (17)	C6—C7—C12—C11	177.84 (19)
N1—C2—C3—C4	−25.1 (2)	C14—O1—C13—O2	−0.2 (3)
N2—C3—C4—C5	172.31 (15)	C14—O1—C13—C1	178.35 (18)
C2—C3—C4—C5	47.7 (2)	N1—C1—C13—O2	−32.8 (3)
C3—C4—C5—C1	−61.0 (2)	C5—C1—C13—O2	89.6 (2)
N1—C1—C5—C4	50.0 (2)	N1—C1—C13—O1	148.64 (17)
C13—C1—C5—C4	−71.8 (2)	C5—C1—C13—O1	−88.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3^i	0.90 (2)	1.99 (2)	2.880 (2)	175
C3—H3···N4^ii	0.98	2.57	3.528 (2)	167

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