1-[(6-Chloro-pyridin-3-yl)meth-yl]-10-nitro-1,2,3,5,6,7,8,9-octa-hydro-5,9-methano-imidazo[1,2-a]azocin-5-ol.

In the title compound, C16H19ClN4O3, the cyclo-hexane ring displays a chair formation and the tetra-hydro-pyridine ring displays an envelope conformation with the methyl-ene C atom as the flap; the imidazolidine ring also displays an envelope conformation with a methyl-ene C atom as the flap. In the crystal, O-H⋯N hydrogen bonds between hy-droxy groups and pyridine rings link inversion-related mol-ecules into dimers. Weak C-H⋯O hydrogen bonds further link the dimers into supra-molecular chains running along the c axis.

Related literature

For background to the title compound, see: Jeschkel & Nauen (2008 ▶). For the synthesis, see: Tian et al. (2007 ▶).

Experimental

Crystal data

C16H19ClN4O3

M = 350.80

Monoclinic,

a = 13.3975 (14) Å

b = 18.7124 (18) Å

c = 6.5721 (8) Å

β = 97.897 (10)°

V = 1632.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 296 K

0.38 × 0.24 × 0.23 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.93, T max = 0.94

7705 measured reflections

2921 independent reflections

1727 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.071

wR(F 2) = 0.217

S = 1.05

2921 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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 datablock(s) I, global. DOI: 10.1107/S1600536813014402/xu5695sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813014402/xu5695Isup2.hkl

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

C16H19ClN4O3	F(000) = 736
Mr = 350.80	Dx = 1.428 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1166 reflections
a = 13.3975 (14) Å	θ = 2.6–25.2°
b = 18.7124 (18) Å	µ = 0.26 mm−1
c = 6.5721 (8) Å	T = 296 K
β = 97.897 (10)°	Prism, colourless
V = 1632.0 (3) Å3	0.38 × 0.24 × 0.23 mm
Z = 4

Bruker APEXII diffractometer	2921 independent reflections
Radiation source: fine-focus sealed tube	1727 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 16.03 pixels mm-1	θmax = 25.2°, θmin = 2.7°
φ and ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −21→22
Tmin = 0.93, Tmax = 0.94	l = −7→6
7705 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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.217	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.1042P)2 + 0.1363P] where P = (Fo2 + 2Fc2)/3
2921 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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. 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 > 2sigma(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
Cl1	−0.41200 (9)	0.65584 (9)	0.0781 (3)	0.0997 (6)
N1	0.1452 (3)	0.65779 (16)	0.7861 (5)	0.0462 (9)
N2	0.2189 (2)	0.53441 (15)	0.4048 (5)	0.0366 (8)
N3	0.0721 (2)	0.59219 (15)	0.3726 (5)	0.0437 (8)
N4	−0.2457 (2)	0.63479 (18)	0.3227 (6)	0.0571 (10)
O1	0.1870 (2)	0.69232 (16)	0.9378 (5)	0.0673 (9)
O2	0.0505 (2)	0.65481 (15)	0.7522 (5)	0.0588 (8)
O3	0.35157 (19)	0.45270 (13)	0.4224 (4)	0.0510 (8)
H3	0.3216	0.4252	0.4901	0.077*
C1	0.1637 (3)	0.58526 (18)	0.4877 (6)	0.0373 (9)
C2	0.1721 (3)	0.5161 (2)	0.1983 (6)	0.0533 (11)
H2A	0.1769	0.4653	0.1716	0.064*
H2B	0.2017	0.5427	0.0949	0.064*
C3	0.0639 (3)	0.5387 (2)	0.2069 (7)	0.0563 (12)
H3A	0.0341	0.5594	0.0774	0.068*
H3B	0.0233	0.4984	0.2386	0.068*
C4	0.2050 (3)	0.62191 (19)	0.6634 (6)	0.0388 (9)
C5	0.3162 (3)	0.61790 (18)	0.7288 (6)	0.0443 (10)
H5	0.3302	0.6297	0.8751	0.053*
C6	0.3494 (3)	0.54049 (19)	0.6983 (6)	0.0455 (10)
H6A	0.4208	0.5352	0.7467	0.055*
H6B	0.3123	0.5080	0.7752	0.055*
C7	0.3281 (3)	0.52359 (18)	0.4689 (6)	0.0388 (9)
C8	0.3893 (3)	0.57185 (19)	0.3484 (7)	0.0477 (10)
H8A	0.3741	0.5609	0.2032	0.057*
H8B	0.4605	0.5630	0.3904	0.057*
C9	0.3664 (3)	0.65028 (19)	0.3831 (7)	0.0515 (11)
H9A	0.4128	0.6797	0.3188	0.062*
H9B	0.2987	0.6609	0.3177	0.062*
C10	0.3751 (3)	0.6691 (2)	0.6090 (7)	0.0564 (12)
H10A	0.3502	0.7173	0.6229	0.068*
H10B	0.4455	0.6682	0.6680	0.068*
C11	0.0317 (3)	0.66343 (18)	0.3105 (6)	0.0400 (9)
H11A	0.0647	0.6811	0.1980	0.048*
H11B	0.0465	0.6963	0.4248	0.048*
C12	−0.0792 (3)	0.66095 (16)	0.2453 (6)	0.0347 (9)
C13	−0.1215 (3)	0.68244 (19)	0.0504 (6)	0.0450 (10)
H13	−0.0801	0.6977	−0.0435	0.054*
C14	−0.2246 (3)	0.6813 (2)	−0.0049 (7)	0.0539 (11)
H14	−0.2539	0.6961	−0.1346	0.065*
C15	−0.2822 (3)	0.6576 (2)	0.1372 (8)	0.0518 (11)
C16	−0.1457 (3)	0.6367 (2)	0.3742 (7)	0.0495 (11)
H16	−0.1190	0.6208	0.5044	0.059*

	U11	U22	U33	U12	U13	U23
Cl1	0.0386 (7)	0.1346 (13)	0.1228 (14)	0.0014 (7)	0.0000 (7)	0.0343 (10)
N1	0.055 (2)	0.042 (2)	0.042 (2)	0.0066 (15)	0.0090 (17)	−0.0048 (16)
N2	0.0401 (17)	0.0310 (17)	0.0390 (18)	0.0055 (12)	0.0071 (14)	−0.0050 (14)
N3	0.0452 (19)	0.0319 (17)	0.052 (2)	0.0061 (13)	−0.0022 (15)	−0.0140 (16)
N4	0.039 (2)	0.056 (2)	0.078 (3)	−0.0026 (15)	0.0113 (18)	0.014 (2)
O1	0.081 (2)	0.070 (2)	0.048 (2)	0.0147 (15)	0.0004 (16)	−0.0235 (16)
O2	0.0499 (19)	0.071 (2)	0.059 (2)	0.0059 (14)	0.0197 (14)	−0.0108 (15)
O3	0.0569 (18)	0.0363 (16)	0.064 (2)	0.0123 (12)	0.0222 (14)	0.0068 (13)
C1	0.034 (2)	0.032 (2)	0.047 (2)	−0.0027 (15)	0.0071 (16)	−0.0003 (18)
C2	0.067 (3)	0.042 (2)	0.049 (3)	0.0120 (19)	0.002 (2)	−0.012 (2)
C3	0.057 (3)	0.046 (2)	0.062 (3)	0.0052 (18)	−0.007 (2)	−0.017 (2)
C4	0.042 (2)	0.041 (2)	0.033 (2)	0.0023 (16)	0.0033 (16)	−0.0090 (17)
C5	0.050 (2)	0.041 (2)	0.040 (2)	0.0053 (17)	−0.0041 (18)	−0.0069 (18)
C6	0.044 (2)	0.045 (2)	0.046 (3)	0.0069 (17)	0.0016 (18)	0.0036 (19)
C7	0.045 (2)	0.026 (2)	0.047 (2)	0.0073 (15)	0.0114 (18)	0.0043 (17)
C8	0.044 (2)	0.046 (2)	0.055 (3)	0.0071 (17)	0.0116 (19)	0.005 (2)
C9	0.050 (2)	0.037 (2)	0.069 (3)	0.0002 (17)	0.012 (2)	0.014 (2)
C10	0.043 (2)	0.043 (2)	0.080 (3)	−0.0032 (17)	−0.003 (2)	−0.007 (2)
C11	0.043 (2)	0.033 (2)	0.046 (2)	−0.0023 (15)	0.0127 (17)	−0.0021 (17)
C12	0.041 (2)	0.0219 (18)	0.041 (2)	−0.0019 (14)	0.0067 (17)	0.0027 (16)
C13	0.045 (2)	0.040 (2)	0.050 (3)	0.0013 (16)	0.0093 (18)	0.0104 (19)
C14	0.050 (3)	0.057 (3)	0.053 (3)	0.002 (2)	0.001 (2)	0.018 (2)
C15	0.043 (2)	0.043 (2)	0.069 (3)	0.0056 (17)	0.007 (2)	0.013 (2)
C16	0.046 (2)	0.047 (2)	0.056 (3)	−0.0001 (17)	0.005 (2)	0.008 (2)

Cl1—C15	1.729 (4)	C5—H5	0.9800
N1—O1	1.254 (4)	C6—C7	1.529 (5)
N1—O2	1.258 (4)	C6—H6A	0.9700
N1—C4	1.386 (5)	C6—H6B	0.9700
N2—C1	1.363 (5)	C7—C8	1.515 (5)
N2—C2	1.456 (5)	C8—C9	1.523 (5)
N2—C7	1.480 (4)	C8—H8A	0.9700
N3—C1	1.357 (4)	C8—H8B	0.9700
N3—C3	1.472 (5)	C9—C10	1.515 (6)
N3—C11	1.475 (4)	C9—H9A	0.9700
N4—C15	1.320 (6)	C9—H9B	0.9700
N4—C16	1.337 (5)	C10—H10A	0.9700
O3—C7	1.407 (4)	C10—H10B	0.9700
O3—H3	0.8200	C11—C12	1.490 (5)
C1—C4	1.391 (5)	C11—H11A	0.9700
C2—C3	1.518 (5)	C11—H11B	0.9700
C2—H2A	0.9700	C12—C16	1.387 (5)
C2—H2B	0.9700	C12—C13	1.387 (5)
C3—H3A	0.9700	C13—C14	1.380 (5)
C3—H3B	0.9700	C13—H13	0.9300
C4—C5	1.495 (5)	C14—C15	1.364 (6)
C5—C10	1.527 (6)	C14—H14	0.9300
C5—C6	1.537 (5)	C16—H16	0.9300
O1—N1—O2	119.6 (3)	N2—C7—C8	110.8 (3)
O1—N1—C4	118.7 (3)	O3—C7—C6	113.1 (3)
O2—N1—C4	121.6 (3)	N2—C7—C6	107.2 (3)
C1—N2—C2	110.4 (3)	C8—C7—C6	110.5 (3)
C1—N2—C7	123.4 (3)	C7—C8—C9	111.2 (3)
C2—N2—C7	121.0 (3)	C7—C8—H8A	109.4
C1—N3—C3	108.5 (3)	C9—C8—H8A	109.4
C1—N3—C11	120.6 (3)	C7—C8—H8B	109.4
C3—N3—C11	115.0 (3)	C9—C8—H8B	109.4
C15—N4—C16	117.1 (4)	H8A—C8—H8B	108.0
C7—O3—H3	109.5	C10—C9—C8	112.4 (3)
N3—C1—N2	110.0 (3)	C10—C9—H9A	109.1
N3—C1—C4	129.9 (3)	C8—C9—H9A	109.1
N2—C1—C4	120.0 (3)	C10—C9—H9B	109.1
N2—C2—C3	101.0 (3)	C8—C9—H9B	109.1
N2—C2—H2A	111.6	H9A—C9—H9B	107.9
C3—C2—H2A	111.6	C9—C10—C5	112.6 (3)
N2—C2—H2B	111.6	C9—C10—H10A	109.1
C3—C2—H2B	111.6	C5—C10—H10A	109.1
H2A—C2—H2B	109.4	C9—C10—H10B	109.1
N3—C3—C2	104.0 (3)	C5—C10—H10B	109.1
N3—C3—H3A	110.9	H10A—C10—H10B	107.8
C2—C3—H3A	110.9	N3—C11—C12	111.4 (3)
N3—C3—H3B	110.9	N3—C11—H11A	109.4
C2—C3—H3B	110.9	C12—C11—H11A	109.4
H3A—C3—H3B	109.0	N3—C11—H11B	109.4
N1—C4—C1	121.8 (3)	C12—C11—H11B	109.4
N1—C4—C5	119.4 (3)	H11A—C11—H11B	108.0
C1—C4—C5	118.7 (3)	C16—C12—C13	116.4 (3)
C4—C5—C10	112.7 (3)	C16—C12—C11	122.2 (3)
C4—C5—C6	107.8 (3)	C13—C12—C11	121.4 (3)
C10—C5—C6	110.2 (4)	C14—C13—C12	120.4 (4)
C4—C5—H5	108.7	C14—C13—H13	119.8
C10—C5—H5	108.7	C12—C13—H13	119.8
C6—C5—H5	108.7	C15—C14—C13	117.7 (4)
C7—C6—C5	107.8 (3)	C15—C14—H14	121.2
C7—C6—H6A	110.2	C13—C14—H14	121.2
C5—C6—H6A	110.2	N4—C15—C14	124.4 (4)
C7—C6—H6B	110.2	N4—C15—Cl1	115.8 (3)
C5—C6—H6B	110.2	C14—C15—Cl1	119.8 (3)
H6A—C6—H6B	108.5	N4—C16—C12	124.0 (4)
O3—C7—N2	108.0 (3)	N4—C16—H16	118.0
O3—C7—C8	107.2 (3)	C12—C16—H16	118.0
C3—N3—C1—N2	3.5 (4)	C1—N2—C7—C8	−87.0 (4)
C11—N3—C1—N2	−132.3 (3)	C2—N2—C7—C8	65.2 (4)
C3—N3—C1—C4	−177.8 (4)	C1—N2—C7—C6	33.7 (4)
C11—N3—C1—C4	46.5 (6)	C2—N2—C7—C6	−174.1 (3)
C2—N2—C1—N3	13.0 (4)	C5—C6—C7—O3	−177.5 (3)
C7—N2—C1—N3	167.8 (3)	C5—C6—C7—N2	−58.5 (4)
C2—N2—C1—C4	−165.9 (3)	C5—C6—C7—C8	62.4 (4)
C7—N2—C1—C4	−11.1 (5)	O3—C7—C8—C9	178.1 (3)
C1—N2—C2—C3	−22.7 (4)	N2—C7—C8—C9	60.5 (4)
C7—N2—C2—C3	−178.2 (3)	C6—C7—C8—C9	−58.3 (4)
C1—N3—C3—C2	−17.4 (4)	C7—C8—C9—C10	51.5 (4)
C11—N3—C3—C2	121.1 (3)	C8—C9—C10—C5	−50.4 (5)
N2—C2—C3—N3	23.3 (4)	C4—C5—C10—C9	−65.2 (4)
O1—N1—C4—C1	−177.1 (3)	C6—C5—C10—C9	55.2 (4)
O2—N1—C4—C1	5.0 (5)	C1—N3—C11—C12	−162.0 (3)
O1—N1—C4—C5	7.4 (5)	C3—N3—C11—C12	64.9 (4)
O2—N1—C4—C5	−170.6 (3)	N3—C11—C12—C16	58.0 (4)
N3—C1—C4—N1	20.4 (6)	N3—C11—C12—C13	−121.5 (4)
N2—C1—C4—N1	−160.9 (3)	C16—C12—C13—C14	2.0 (5)
N3—C1—C4—C5	−164.0 (4)	C11—C12—C13—C14	−178.5 (3)
N2—C1—C4—C5	14.7 (5)	C12—C13—C14—C15	−0.8 (6)
N1—C4—C5—C10	−103.5 (4)	C16—N4—C15—C14	1.5 (6)
C1—C4—C5—C10	80.8 (4)	C16—N4—C15—Cl1	−178.9 (3)
N1—C4—C5—C6	134.7 (4)	C13—C14—C15—N4	−1.1 (7)
C1—C4—C5—C6	−41.0 (5)	C13—C14—C15—Cl1	179.3 (3)
C4—C5—C6—C7	63.1 (4)	C15—N4—C16—C12	0.0 (6)
C10—C5—C6—C7	−60.2 (4)	C13—C12—C16—N4	−1.7 (5)
C1—N2—C7—O3	155.9 (3)	C11—C12—C16—N4	178.8 (3)
C2—N2—C7—O3	−51.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···N4i	0.82	2.04	2.855 (4)	174
C11—H11A···O1ii	0.97	2.53	3.467 (5)	161
C13—H13···O2ii	0.93	2.48	3.265 (5)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯N4i	0.82	2.04	2.855 (4)	174
C11—H11A⋯O1ii	0.97	2.53	3.467 (5)	161
C13—H13⋯O2ii	0.93	2.48	3.265 (5)	142

Symmetry codes: (i) ; (ii) .