rac-1-(Furan-2-ylmeth-yl)-N-nitro-5-(oxolan-2-ylmeth-yl)-1,3,5-triazinan-2-imine.

In the title compound C(13)H(19)N(5)O(4), which belongs to the insecticidally active neonicotinoid group of compounds, the triazane ring exhibits a half-chair conformation. The large discrepancy between the two nitro O-N-N bond angles [116.1 (2) and 123.98 (19)°] may be attributed to intra-molecular N-H⋯O hydrogen bonding involving one of the nitro O atoms as the acceptor. The delocalization of the electrons extends as far as the nitro group, forming coplanar π-electron networks. In the crystal, inversion dimers lined by pairs of N-H⋯O hydrogen bonds occur.

Related literature

For general background to neonicotinoids, see: Kagabu et al. (2005 ▶); Peter & Ralf (2008 ▶); Riley & Merz (2007 ▶); Tian et al. (2007 ▶); Tomizawa et al. (2000 ▶). For the synthesis, see: Zhu et al. (2010 ▶).

Experimental

Crystal data

C13H19N5O4

M = 309.33

Monoclinic,

a = 11.1898 (12) Å

b = 9.262 (1) Å

c = 14.4863 (15) Å

β = 99.276 (2)°

V = 1481.7 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 298 K

0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

9196 measured reflections

2902 independent reflections

2615 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.164

S = 1.18

2902 reflections

202 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.21 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810036561/zs2064sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036561/zs2064Isup2.hkl

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

C13H19N5O4	F(000) = 656
Mr = 309.33	Dx = 1.387 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4051 reflections
a = 11.1898 (12) Å	θ = 2.5–28.3°
b = 9.262 (1) Å	µ = 0.11 mm−1
c = 14.4863 (15) Å	T = 298 K
β = 99.276 (2)°	Block, colorless
V = 1481.7 (3) Å3	0.16 × 0.12 × 0.10 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2615 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
graphite	θmax = 26.0°, θmin = 2.1°
φ and ω scans	h = −12→13
9196 measured reflections	k = −9→11
2902 independent reflections	l = −17→17

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ2(Fo2) + (0.0599P)2 + 0.7103P] where P = (Fo2 + 2Fc2)/3
2902 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.1890 (2)	1.0871 (3)	−0.01634 (16)	0.0487 (6)
H1	0.1262	1.0589	−0.0684	0.058*
C2	0.2996 (3)	1.1394 (3)	−0.0536 (2)	0.0696 (8)
H2A	0.3568	1.0614	−0.0561	0.084*
H2B	0.2777	1.1802	−0.1157	0.084*
C3	0.3511 (3)	1.2516 (4)	0.0146 (2)	0.0736 (9)
H3A	0.3924	1.3257	−0.0156	0.088*
H3B	0.4078	1.2094	0.0651	0.088*
C4	0.2436 (3)	1.3124 (3)	0.0502 (2)	0.0615 (7)
H4A	0.2630	1.3307	0.1169	0.074*
H4B	0.2191	1.4027	0.0188	0.074*
C5	0.2134 (2)	0.9639 (3)	0.05245 (16)	0.0473 (6)
H5A	0.2792	0.9902	0.1017	0.057*
H5B	0.1420	0.9468	0.0809	0.057*
C6	0.1429 (2)	0.7399 (3)	−0.02488 (15)	0.0482 (6)
H6A	0.1663	0.6655	−0.0656	0.058*
H6B	0.0791	0.7970	−0.0608	0.058*
C7	0.16647 (19)	0.6493 (2)	0.13610 (15)	0.0382 (5)
C8	0.3341 (2)	0.7465 (3)	0.06578 (16)	0.0476 (6)
H8A	0.4025	0.8074	0.0900	0.057*
H8B	0.3630	0.6705	0.0290	0.057*
C9	0.3679 (2)	0.6694 (3)	0.23428 (16)	0.0532 (6)
H9A	0.3267	0.6217	0.2798	0.064*
H9B	0.3899	0.7657	0.2574	0.064*
C10	0.4795 (2)	0.5882 (3)	0.22556 (16)	0.0482 (6)
C11	0.5939 (2)	0.6300 (3)	0.23025 (18)	0.0540 (6)
H11	0.6233	0.7234	0.2408	0.065*
C12	0.6623 (2)	0.5070 (4)	0.2163 (2)	0.0693 (8)
H12	0.7454	0.5036	0.2161	0.083*
C13	0.5869 (3)	0.3982 (4)	0.2035 (3)	0.0808 (10)
H13	0.6081	0.3034	0.1925	0.097*
N1	0.24528 (17)	0.8309 (2)	0.00685 (12)	0.0440 (5)
N2	0.09726 (18)	0.6721 (2)	0.05406 (13)	0.0434 (5)
H2	0.024 (2)	0.659 (3)	0.0503 (18)	0.052*
N3	0.28447 (16)	0.6810 (2)	0.14521 (12)	0.0442 (5)
N4	0.13154 (16)	0.5958 (2)	0.21520 (13)	0.0463 (5)
N5	0.01557 (17)	0.5609 (2)	0.21385 (14)	0.0486 (5)
O1	0.14841 (15)	1.20885 (19)	0.03162 (12)	0.0540 (5)
O2	0.47092 (18)	0.4451 (2)	0.20884 (18)	0.0799 (7)
O3	−0.06477 (17)	0.5800 (3)	0.14598 (15)	0.0902 (8)
O4	−0.00984 (17)	0.5099 (2)	0.28658 (14)	0.0709 (6)

	U11	U22	U33	U12	U13	U23
C1	0.0558 (14)	0.0487 (14)	0.0407 (12)	−0.0013 (11)	0.0050 (10)	0.0002 (10)
C2	0.092 (2)	0.0565 (17)	0.0706 (18)	−0.0087 (16)	0.0424 (17)	0.0028 (14)
C3	0.0628 (17)	0.078 (2)	0.084 (2)	−0.0169 (16)	0.0242 (16)	−0.0094 (17)
C4	0.0651 (17)	0.0516 (16)	0.0669 (17)	−0.0046 (13)	0.0075 (13)	−0.0092 (13)
C5	0.0543 (14)	0.0514 (14)	0.0384 (11)	−0.0023 (11)	0.0141 (10)	0.0002 (10)
C6	0.0558 (14)	0.0530 (14)	0.0361 (11)	0.0010 (11)	0.0086 (10)	−0.0008 (10)
C7	0.0385 (11)	0.0360 (11)	0.0409 (11)	0.0031 (9)	0.0088 (9)	−0.0005 (9)
C8	0.0448 (12)	0.0543 (14)	0.0470 (12)	0.0011 (11)	0.0175 (10)	0.0064 (11)
C9	0.0432 (13)	0.0758 (18)	0.0407 (12)	−0.0032 (12)	0.0072 (10)	0.0061 (12)
C10	0.0418 (12)	0.0613 (16)	0.0393 (11)	−0.0063 (11)	0.0004 (9)	0.0113 (11)
C11	0.0406 (12)	0.0648 (16)	0.0580 (14)	−0.0129 (12)	0.0121 (11)	0.0088 (12)
C12	0.0416 (14)	0.093 (2)	0.0730 (18)	0.0042 (15)	0.0090 (13)	0.0168 (17)
C13	0.0614 (18)	0.069 (2)	0.108 (3)	0.0143 (17)	0.0027 (17)	0.0073 (19)
N1	0.0493 (11)	0.0454 (11)	0.0393 (9)	0.0019 (9)	0.0125 (8)	0.0025 (8)
N2	0.0386 (10)	0.0493 (12)	0.0416 (10)	−0.0025 (9)	0.0046 (8)	0.0033 (8)
N3	0.0370 (10)	0.0562 (12)	0.0403 (10)	0.0008 (8)	0.0091 (8)	0.0102 (8)
N4	0.0369 (10)	0.0568 (12)	0.0465 (10)	−0.0022 (9)	0.0099 (8)	0.0112 (9)
N5	0.0423 (11)	0.0519 (12)	0.0523 (12)	−0.0010 (9)	0.0101 (9)	0.0095 (9)
O1	0.0495 (10)	0.0493 (10)	0.0636 (11)	0.0033 (8)	0.0104 (8)	−0.0040 (8)
O2	0.0524 (12)	0.0665 (14)	0.1163 (19)	−0.0084 (10)	−0.0001 (11)	0.0061 (12)
O3	0.0461 (11)	0.154 (2)	0.0675 (13)	−0.0258 (13)	0.0006 (10)	0.0314 (14)
O4	0.0549 (11)	0.0947 (16)	0.0677 (12)	−0.0047 (10)	0.0235 (9)	0.0345 (11)

C1—O1	1.436 (3)	C7—N4	1.362 (3)
C1—C2	1.508 (4)	C8—N1	1.433 (3)
C1—C5	1.510 (3)	C8—N3	1.485 (3)
C1—H1	0.9800	C8—H8A	0.9700
C2—C3	1.485 (4)	C8—H8B	0.9700
C2—H2A	0.9700	C9—N3	1.469 (3)
C2—H2B	0.9700	C9—C10	1.481 (3)
C3—C4	1.494 (4)	C9—H9A	0.9700
C3—H3A	0.9700	C9—H9B	0.9700
C3—H3B	0.9700	C10—C11	1.329 (3)
C4—O1	1.426 (3)	C10—O2	1.348 (3)
C4—H4A	0.9700	C11—C12	1.405 (4)
C4—H4B	0.9700	C11—H11	0.9300
C5—N1	1.469 (3)	C12—C13	1.309 (4)
C5—H5A	0.9700	C12—H12	0.9300
C5—H5B	0.9700	C13—O2	1.382 (4)
C6—N1	1.436 (3)	C13—H13	0.9300
C6—N2	1.467 (3)	N2—H2	0.82 (3)
C6—H6A	0.9700	N4—N5	1.335 (3)
C6—H6B	0.9700	N5—O4	1.229 (3)
C7—N2	1.327 (3)	N5—O3	1.233 (3)
C7—N3	1.338 (3)
O1—C1—C2	105.2 (2)	N1—C8—N3	111.98 (18)
O1—C1—C5	108.15 (18)	N1—C8—H8A	109.2
C2—C1—C5	114.1 (2)	N3—C8—H8A	109.2
O1—C1—H1	109.7	N1—C8—H8B	109.2
C2—C1—H1	109.7	N3—C8—H8B	109.2
C5—C1—H1	109.7	H8A—C8—H8B	107.9
C3—C2—C1	103.8 (2)	N3—C9—C10	112.8 (2)
C3—C2—H2A	111.0	N3—C9—H9A	109.0
C1—C2—H2A	111.0	C10—C9—H9A	109.0
C3—C2—H2B	111.0	N3—C9—H9B	109.0
C1—C2—H2B	111.0	C10—C9—H9B	109.0
H2A—C2—H2B	109.0	H9A—C9—H9B	107.8
C2—C3—C4	104.2 (2)	C11—C10—O2	109.6 (2)
C2—C3—H3A	110.9	C11—C10—C9	131.8 (3)
C4—C3—H3A	110.9	O2—C10—C9	118.6 (2)
C2—C3—H3B	110.9	C10—C11—C12	107.4 (3)
C4—C3—H3B	110.9	C10—C11—H11	126.3
H3A—C3—H3B	108.9	C12—C11—H11	126.3
O1—C4—C3	107.4 (2)	C13—C12—C11	106.9 (3)
O1—C4—H4A	110.2	C13—C12—H12	126.6
C3—C4—H4A	110.2	C11—C12—H12	126.6
O1—C4—H4B	110.2	C12—C13—O2	109.9 (3)
C3—C4—H4B	110.2	C12—C13—H13	125.1
H4A—C4—H4B	108.5	O2—C13—H13	125.1
N1—C5—C1	111.59 (18)	C8—N1—C6	108.15 (19)
N1—C5—H5A	109.3	C8—N1—C5	112.63 (19)
C1—C5—H5A	109.3	C6—N1—C5	113.40 (19)
N1—C5—H5B	109.3	C7—N2—C6	122.69 (19)
C1—C5—H5B	109.3	C7—N2—H2	117.9 (18)
H5A—C5—H5B	108.0	C6—N2—H2	118.7 (18)
N1—C6—N2	111.20 (18)	C7—N3—C9	123.22 (18)
N1—C6—H6A	109.4	C7—N3—C8	119.94 (18)
N2—C6—H6A	109.4	C9—N3—C8	116.49 (18)
N1—C6—H6B	109.4	N5—N4—C7	119.09 (19)
N2—C6—H6B	109.4	O4—N5—O3	119.9 (2)
H6A—C6—H6B	108.0	O4—N5—N4	116.1 (2)
N2—C7—N3	118.54 (19)	O3—N5—N4	123.98 (19)
N2—C7—N4	127.3 (2)	C4—O1—C1	109.54 (19)
N3—C7—N4	114.15 (19)	C10—O2—C13	106.2 (2)
O1—C1—C2—C3	29.5 (3)	N1—C6—N2—C7	−25.4 (3)
C5—C1—C2—C3	−88.8 (3)	N2—C7—N3—C9	175.7 (2)
C1—C2—C3—C4	−30.1 (3)	N4—C7—N3—C9	−4.3 (3)
C2—C3—C4—O1	20.2 (3)	N2—C7—N3—C8	2.8 (3)
O1—C1—C5—N1	175.01 (18)	N4—C7—N3—C8	−177.2 (2)
C2—C1—C5—N1	−68.3 (3)	C10—C9—N3—C7	130.5 (2)
N3—C9—C10—C11	110.1 (3)	C10—C9—N3—C8	−56.4 (3)
N3—C9—C10—O2	−69.1 (3)	N1—C8—N3—C7	28.7 (3)
O2—C10—C11—C12	−0.3 (3)	N1—C8—N3—C9	−144.7 (2)
C9—C10—C11—C12	−179.6 (2)	N2—C7—N4—N5	−0.1 (4)
C10—C11—C12—C13	0.3 (3)	N3—C7—N4—N5	179.9 (2)
C11—C12—C13—O2	−0.2 (4)	C7—N4—N5—O4	178.3 (2)
N3—C8—N1—C6	−56.5 (3)	C7—N4—N5—O3	−3.5 (4)
N3—C8—N1—C5	69.6 (2)	C3—C4—O1—C1	−1.6 (3)
N2—C6—N1—C8	54.5 (2)	C2—C1—O1—C4	−17.4 (3)
N2—C6—N1—C5	−71.2 (2)	C5—C1—O1—C4	104.8 (2)
C1—C5—N1—C8	144.4 (2)	C11—C10—O2—C13	0.2 (3)
C1—C5—N1—C6	−92.4 (2)	C9—C10—O2—C13	179.6 (2)
N3—C7—N2—C6	−4.4 (3)	C12—C13—O2—C10	0.0 (4)
N4—C7—N2—C6	175.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3	0.82 (3)	1.97 (3)	2.563 (3)	128 (2)
N2—H2···O1i	0.82 (3)	2.43 (3)	3.035 (3)	132 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3	0.82 (3)	1.97 (3)	2.563 (3)	128 (2)
N2—H2⋯O1i	0.82 (3)	2.43 (3)	3.035 (3)	132 (2)

Symmetry code: (i) .