tert-Butyl 4-(2-diazo-acet-yl)piperazine-1-carboxyl-ate.

The title crystal structure, C(11)H(18)N(4)O(3), is the first diazo-acetamide in which the diazo-acetyl group is attached to an N atom. The piperazine ring is in a chair form and hence the mol-ecule has an extended conformation. Both ring N atoms are bonded in an essentially planar configuration with the sum of the C-N-C angles being 359.8 (2) and 357.7 (2)°. In the crystal structure, the O atom of the diazo-acetyl group accepts two H atoms from C-H donors, thus generating chains of weak hydrogen-bonded R(2) (1)(7) rings.

Related literature

For the only other reported synthesis of a diazo­acetamide in the Chemical Abstracts Service (CAS, American Chemical Society, 2008 ▶) with a 1,4-diaza six-membered ring, see: Mickelson et al. (1996 ▶). For other diazo­acetamides, see: Ouihia et al. (1993 ▶). For related structures, see: Fenlon et al. (2007 ▶); Wang et al. (2006 ▶); Miller et al. (1991 ▶). For synthetic details, see: Kaupang (2010 ▶); Toma et al. (2007 ▶). For n class="Chemical">hydrogen-bond graph-set notation, see: Bernstein et al. (1995 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C11H18N4O3

M = 254.29

Monoclinic,

a = 14.654 (10) Å

b = 10.548 (7) Å

c = 8.553 (6) Å

β = 91.122 (6)°

V = 1321.8 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 105 K

0.55 × 0.42 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.870, T max = 0.992

7308 measured reflections

2692 independent reflections

2111 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.103

S = 1.03

2692 reflections

169 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.17 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810016211/lh5033sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810016211/lh5033Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C11H18N4O3	F(000) = 544
Mr = 254.29	Dx = 1.278 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.654 (10) Å	Cell parameters from 2404 reflections
b = 10.548 (7) Å	θ = 2.4–26.4°
c = 8.553 (6) Å	µ = 0.10 mm−1
β = 91.122 (6)°	T = 105 K
V = 1321.8 (15) Å3	Plate, yellow
Z = 4	0.55 × 0.42 × 0.08 mm

Bruker APEXII CCD diffractometer	2692 independent reflections
Radiation source: fine-focus sealed tube	2111 reflections with I > 2σ(I)
graphite	Rint = 0.041
Detector resolution: 8.3 pixels mm-1	θmax = 26.4°, θmin = 2.4°
Three sets of frames each taken over 0.3° ω rotation with 20 s exposure time. Detector set at 2θ = 26°, crystal–to–detector distance 6.00 cm. scans	h = −17→18
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −10→13
Tmin = 0.870, Tmax = 0.992	l = −10→10
7308 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0463P)2 + 0.1671P] where P = (Fo2 + 2Fc2)/3
2692 reflections	(Δ/σ)max = 0.001
169 parameters	Δρmax = 0.17 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Experimental. Crystallized from dichloromethane and n-pentane.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections.

	x	y	z	Uiso*/Ueq
O1	0.02567 (7)	0.20344 (9)	0.19361 (12)	0.0353 (3)
O2	0.38950 (6)	0.35633 (9)	0.62995 (11)	0.0296 (2)
O3	0.33388 (6)	0.55670 (8)	0.64091 (11)	0.0294 (2)
N1	−0.14125 (10)	0.34028 (15)	−0.00383 (19)	0.0562 (4)
N2	−0.08817 (8)	0.37402 (12)	0.08229 (16)	0.0377 (3)
N3	0.10933 (7)	0.34931 (10)	0.32642 (14)	0.0293 (3)
N4	0.27460 (8)	0.42179 (11)	0.46913 (15)	0.0350 (3)
C1	−0.02502 (10)	0.41229 (14)	0.18201 (17)	0.0324 (3)
H1	−0.0254 (10)	0.4999 (17)	0.2058 (19)	0.039*
C2	0.03721 (9)	0.31392 (13)	0.23569 (16)	0.0276 (3)
C3	0.11676 (9)	0.47080 (12)	0.40835 (18)	0.0301 (3)
H31	0.0971	0.4604	0.5177	0.036*
H32	0.0760	0.5337	0.3568	0.036*
C4	0.17261 (10)	0.25284 (13)	0.38538 (18)	0.0317 (3)
H41	0.1681	0.1763	0.3188	0.038*
H42	0.1561	0.2287	0.4931	0.038*
C5	0.21342 (9)	0.51824 (13)	0.40729 (18)	0.0322 (3)
H51	0.2304	0.5397	0.2990	0.039*
H52	0.2188	0.5960	0.4717	0.039*
C6	0.26896 (10)	0.30251 (13)	0.38538 (19)	0.0349 (4)
H61	0.3104	0.2399	0.4357	0.042*
H62	0.2886	0.3150	0.2763	0.042*
C7	0.33775 (9)	0.43825 (12)	0.58409 (16)	0.0259 (3)
C8	0.39795 (9)	0.59837 (13)	0.76528 (15)	0.0275 (3)
C9	0.36780 (11)	0.73381 (14)	0.79087 (18)	0.0387 (4)
H91	0.3721	0.7811	0.6927	0.058*
H92	0.4073	0.7734	0.8707	0.058*
H93	0.3045	0.7346	0.8258	0.058*
C10	0.49473 (10)	0.59327 (15)	0.70952 (17)	0.0354 (4)
H101	0.4989	0.6386	0.6099	0.053*
H102	0.5129	0.5047	0.6951	0.053*
H103	0.5354	0.6333	0.7873	0.053*
C11	0.38403 (10)	0.52052 (14)	0.91124 (17)	0.0351 (4)
H111	0.3190	0.5190	0.9358	0.053*
H112	0.4186	0.5583	0.9987	0.053*
H113	0.4055	0.4337	0.8939	0.053*

	U11	U22	U33	U12	U13	U23
O1	0.0331 (6)	0.0239 (5)	0.0487 (6)	−0.0044 (4)	−0.0025 (5)	−0.0072 (5)
O2	0.0298 (5)	0.0242 (5)	0.0348 (5)	0.0047 (4)	−0.0017 (4)	0.0004 (4)
O3	0.0326 (5)	0.0217 (5)	0.0336 (5)	0.0019 (4)	−0.0074 (4)	−0.0042 (4)
N1	0.0446 (8)	0.0565 (10)	0.0665 (10)	−0.0058 (7)	−0.0207 (8)	−0.0054 (8)
N2	0.0320 (7)	0.0341 (7)	0.0469 (8)	−0.0010 (5)	−0.0060 (6)	−0.0007 (6)
N3	0.0279 (6)	0.0200 (6)	0.0398 (7)	0.0018 (5)	−0.0042 (5)	−0.0041 (5)
N4	0.0304 (6)	0.0239 (6)	0.0503 (8)	0.0057 (5)	−0.0125 (6)	−0.0096 (5)
C1	0.0297 (8)	0.0281 (8)	0.0390 (8)	−0.0023 (6)	−0.0063 (6)	−0.0020 (6)
C2	0.0257 (7)	0.0241 (7)	0.0332 (7)	−0.0038 (5)	0.0042 (6)	−0.0018 (6)
C3	0.0324 (8)	0.0204 (7)	0.0373 (8)	0.0039 (6)	−0.0050 (6)	−0.0041 (6)
C4	0.0342 (8)	0.0202 (7)	0.0406 (8)	0.0031 (6)	−0.0035 (6)	−0.0040 (6)
C5	0.0341 (8)	0.0224 (7)	0.0396 (8)	−0.0002 (6)	−0.0089 (6)	−0.0014 (6)
C6	0.0325 (8)	0.0264 (7)	0.0455 (9)	0.0053 (6)	−0.0054 (7)	−0.0121 (6)
C7	0.0241 (7)	0.0237 (7)	0.0300 (7)	−0.0013 (5)	0.0030 (5)	−0.0008 (6)
C8	0.0314 (7)	0.0259 (7)	0.0249 (7)	−0.0041 (6)	−0.0037 (6)	−0.0013 (5)
C9	0.0523 (10)	0.0268 (8)	0.0367 (8)	−0.0006 (7)	−0.0048 (7)	−0.0049 (6)
C10	0.0346 (8)	0.0390 (8)	0.0325 (8)	−0.0078 (7)	−0.0006 (6)	0.0005 (6)
C11	0.0398 (8)	0.0354 (8)	0.0302 (8)	−0.0032 (7)	0.0025 (6)	0.0019 (6)

O1—C2	1.2303 (17)	C4—H41	0.9900
O2—C7	1.2099 (16)	C4—H42	0.9900
O3—C7	1.3422 (17)	C5—H51	0.9900
O3—C8	1.4722 (16)	C5—H52	0.9900
N1—N2	1.1189 (18)	C6—H61	0.9900
N2—C1	1.3099 (19)	C6—H62	0.9900
N3—C2	1.3515 (18)	C8—C10	1.506 (2)
N3—C4	1.4600 (18)	C8—C11	1.511 (2)
N3—C3	1.4635 (18)	C8—C9	1.513 (2)
N4—C7	1.3483 (18)	C9—H91	0.9800
N4—C5	1.4490 (18)	C9—H92	0.9800
N4—C6	1.4494 (19)	C9—H93	0.9800
C1—C2	1.450 (2)	C10—H101	0.9800
C1—H1	0.946 (17)	C10—H102	0.9800
C3—C5	1.503 (2)	C10—H103	0.9800
C3—H31	0.9900	C11—H111	0.9800
C3—H32	0.9900	C11—H112	0.9800
C4—C6	1.506 (2)	C11—H113	0.9800
C7—O3—C8	120.57 (10)	N4—C6—H61	109.6
N1—N2—C1	179.04 (18)	C4—C6—H61	109.6
C2—N3—C4	119.35 (12)	N4—C6—H62	109.6
C2—N3—C3	124.53 (11)	C4—C6—H62	109.6
C4—N3—C3	113.83 (11)	H61—C6—H62	108.1
C7—N4—C5	125.93 (12)	O2—C7—O3	125.31 (12)
C7—N4—C6	120.26 (11)	O2—C7—N4	124.15 (13)
C5—N4—C6	113.59 (12)	O3—C7—N4	110.52 (11)
N2—C1—C2	114.68 (13)	O3—C8—C10	110.59 (12)
N2—C1—H1	115.7 (9)	O3—C8—C11	109.89 (11)
C2—C1—H1	129.6 (9)	C10—C8—C11	112.67 (12)
O1—C2—N3	122.08 (12)	O3—C8—C9	101.68 (11)
O1—C2—C1	120.21 (13)	C10—C8—C9	111.04 (12)
N3—C2—C1	117.64 (12)	C11—C8—C9	110.43 (13)
N3—C3—C5	110.49 (12)	C8—C9—H91	109.5
N3—C3—H31	109.6	C8—C9—H92	109.5
C5—C3—H31	109.6	H91—C9—H92	109.5
N3—C3—H32	109.6	C8—C9—H93	109.5
C5—C3—H32	109.6	H91—C9—H93	109.5
H31—C3—H32	108.1	H92—C9—H93	109.5
N3—C4—C6	110.29 (12)	C8—C10—H101	109.5
N3—C4—H41	109.6	C8—C10—H102	109.5
C6—C4—H41	109.6	H101—C10—H102	109.5
N3—C4—H42	109.6	C8—C10—H103	109.5
C6—C4—H42	109.6	H101—C10—H103	109.5
H41—C4—H42	108.1	H102—C10—H103	109.5
N4—C5—C3	109.92 (12)	C8—C11—H111	109.5
N4—C5—H51	109.7	C8—C11—H112	109.5
C3—C5—H51	109.7	H111—C11—H112	109.5
N4—C5—H52	109.7	C8—C11—H113	109.5
C3—C5—H52	109.7	H111—C11—H113	109.5
H51—C5—H52	108.2	H112—C11—H113	109.5
N4—C6—C4	110.27 (12)
C4—N3—C2—O1	−4.1 (2)	C7—N4—C6—C4	128.14 (15)
C3—N3—C2—O1	−165.84 (14)	C5—N4—C6—C4	−57.04 (17)
C4—N3—C2—C1	178.83 (13)	N3—C4—C6—N4	53.39 (17)
C3—N3—C2—C1	17.1 (2)	C8—O3—C7—O2	2.4 (2)
N2—C1—C2—O1	−3.6 (2)	C8—O3—C7—N4	−178.51 (11)
N2—C1—C2—N3	173.55 (13)	C5—N4—C7—O2	−177.86 (14)
C2—N3—C3—C5	−143.07 (14)	C6—N4—C7—O2	−3.7 (2)
C4—N3—C3—C5	54.32 (16)	C5—N4—C7—O3	3.0 (2)
C2—N3—C4—C6	142.52 (13)	C6—N4—C7—O3	177.17 (13)
C3—N3—C4—C6	−53.89 (17)	C7—O3—C8—C10	62.39 (16)
C7—N4—C5—C3	−128.35 (15)	C7—O3—C8—C11	−62.62 (16)
C6—N4—C5—C3	57.18 (17)	C7—O3—C8—C9	−179.61 (12)
N3—C3—C5—N4	−53.86 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1i	0.946 (17)	2.313 (18)	3.250 (3)	170.6 (14)
C3—H32···O1i	0.99	2.36	3.327 (3)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1i	0.946 (17)	2.313 (18)	3.250 (3)	170.6 (14)
C3—H32⋯O1i	0.99	2.36	3.327 (3)	164

Symmetry code: (i) .