Crystal structure of 5,11-di-hydro-pyrido[2,3-b][1,4]benzodiazepin-6-one.

The title compound, C12H9N3O, is an inter-mediate in the synthesis of the muscarinic M2 receptor antagonist AFDX-384. The seven-membered ring adopts a boat conformation and the dihedral angle between the planes of the aromatic rings is 41.51 (9)°. In the crystal, mol-ecules are linked into [001] chains of alternating inversion dimers formed by pairs of N-H⋯O hydrogen bonds and pairs of N-H⋯N hydrogen bonds. In both cases, R 2 (2)(8) loops are generated.

Related literature

For the synthesis of the title compound, see: Holzgrabe & Heller (2003 ▸). For the biological activity of substituted 5,11-di­hydro­pyrido[2,3-b][1,4]benzodiazepin-6-ones, see: Mohr et al. (2004 ▸); Tahtaoui et al. (2004 ▸).

Experimental

Crystal data

C12H9N3O

M = 211.22

Triclinic,

a = 3.7598 (5) Å

b = 10.2467 (14) Å

c = 12.8768 (17) Å

α = 104.628 (6)°

β = 96.616 (5)°

γ = 98.009 (4)°

V = 469.43 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.35 × 0.26 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T min = 0.898, T max = 0.959

6425 measured reflections

2000 independent reflections

1467 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.110

S = 1.06

2000 reflections

153 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2013 ▸); cell refinement: SAINT (Bruker, 2013 ▸); data reduction: SAINT; program(s) used to solve structure: OLEX2.solve (Bourhis et al., 2015 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2, Mercury (Macrae et al., 2006 ▸) and enCIFer (Allen et al., 2004 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015006817/hb7396sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015006817/hb7396Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015006817/hb7396Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015006817/hb7396fig1.tif

ORTEP drawing of the title compound showing atom labeling and 50% probability displacement ellipsoids.

Click here for additional data file.

. DOI: 10.1107/S2056989015006817/hb7396fig2.tif

Unit-cell packing of the title compound showing two inverted molecules linked by hydrogen bonds indicated as dotted lines.

CCDC reference: 1024195

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H9N3O	Z = 2
Mr = 211.22	F(000) = 220
Triclinic, P1	Dx = 1.494 Mg m−3
a = 3.7598 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.2467 (14) Å	Cell parameters from 1512 reflections
c = 12.8768 (17) Å	θ = 2.3–26.2°
α = 104.628 (6)°	µ = 0.10 mm−1
β = 96.616 (5)°	T = 100 K
γ = 98.009 (4)°	Plate, colourless
V = 469.43 (11) Å3	0.35 × 0.26 × 0.06 mm

Bruker APEXII CCD diffractometer	1467 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.035
Absorption correction: multi-scan (SADABS; Bruker, 2013)	θmax = 26.8°, θmin = 1.7°
Tmin = 0.898, Tmax = 0.959	h = −4→4
6425 measured reflections	k = −12→12
2000 independent reflections	l = −16→16

Refinement on F2	Primary atom site location: iterative
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.110	w = 1/[σ2(Fo2) + (0.0437P)2 + 0.2092P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
2000 reflections	Δρmax = 0.23 e Å−3
153 parameters	Δρmin = −0.22 e Å−3
0 restraints

Experimental. Absorption correctiuon: SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0475 before and 0.0419 after correction. The Ratio of minimum to maximum transmission is 0.9367. The λ/2 correction factor is 0.0015.

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.

	x	y	z	Uiso*/Ueq
O1	0.3371 (4)	0.33046 (14)	0.49729 (10)	0.0196 (3)
N3	0.4460 (4)	0.42582 (15)	0.83790 (13)	0.0152 (4)
N1	0.3852 (4)	0.64248 (15)	0.93418 (12)	0.0157 (4)
N2	0.3945 (4)	0.51349 (17)	0.63963 (13)	0.0163 (4)
C4	0.3379 (5)	0.59565 (19)	0.74023 (14)	0.0143 (4)
C12	0.3836 (5)	0.55643 (19)	0.83732 (14)	0.0133 (4)
C1	0.3340 (5)	0.7706 (2)	0.93750 (16)	0.0174 (4)
H1	0.3431	0.8320	1.0051	0.021*
C10	0.0818 (5)	0.20571 (19)	0.81375 (15)	0.0148 (4)
H10	0.1291	0.2203	0.8887	0.018*
C3	0.2728 (5)	0.72576 (19)	0.74596 (15)	0.0168 (4)
H3A	0.2314	0.7535	0.6829	0.020*
C6	0.1477 (5)	0.28402 (18)	0.65494 (14)	0.0137 (4)
C7	−0.0602 (5)	0.15952 (19)	0.59213 (15)	0.0162 (4)
H7	−0.1071	0.1434	0.5171	0.019*
C11	0.2231 (5)	0.30746 (18)	0.76774 (14)	0.0130 (4)
C5	0.2998 (5)	0.37759 (19)	0.59331 (14)	0.0150 (4)
C2	0.2691 (5)	0.81567 (19)	0.84655 (15)	0.0170 (4)
H2A	0.2239	0.9039	0.8521	0.020*
C8	−0.1979 (5)	0.0597 (2)	0.63858 (16)	0.0177 (4)
H8	−0.3366	−0.0226	0.5956	0.021*
C9	−0.1254 (5)	0.08462 (19)	0.75055 (15)	0.0168 (4)
H9	−0.2180	0.0187	0.7831	0.020*
H3	0.497 (6)	0.419 (2)	0.9087 (19)	0.027 (6)*
H2	0.467 (6)	0.557 (2)	0.5943 (19)	0.031 (7)*

	U11	U22	U33	U12	U13	U23
O1	0.0270 (8)	0.0201 (7)	0.0118 (7)	0.0026 (6)	0.0058 (6)	0.0042 (6)
N3	0.0192 (9)	0.0143 (8)	0.0113 (8)	0.0023 (7)	−0.0008 (7)	0.0036 (7)
N1	0.0174 (8)	0.0157 (8)	0.0137 (8)	0.0016 (7)	0.0032 (6)	0.0039 (7)
N2	0.0212 (9)	0.0165 (9)	0.0122 (8)	0.0010 (7)	0.0043 (7)	0.0062 (7)
C4	0.0119 (9)	0.0174 (10)	0.0125 (9)	−0.0007 (8)	0.0012 (7)	0.0041 (8)
C12	0.0101 (9)	0.0155 (10)	0.0143 (9)	−0.0002 (7)	0.0015 (7)	0.0053 (8)
C1	0.0159 (10)	0.0178 (10)	0.0173 (10)	0.0024 (8)	0.0046 (8)	0.0018 (8)
C10	0.0158 (9)	0.0184 (10)	0.0128 (9)	0.0052 (8)	0.0031 (7)	0.0072 (8)
C3	0.0153 (10)	0.0203 (10)	0.0166 (10)	0.0021 (8)	0.0011 (8)	0.0097 (8)
C6	0.0117 (9)	0.0151 (10)	0.0154 (9)	0.0038 (8)	0.0046 (7)	0.0043 (8)
C7	0.0150 (10)	0.0192 (10)	0.0145 (9)	0.0047 (8)	0.0005 (7)	0.0044 (8)
C11	0.0105 (9)	0.0148 (9)	0.0139 (9)	0.0040 (7)	0.0027 (7)	0.0032 (8)
C5	0.0135 (9)	0.0193 (10)	0.0127 (9)	0.0029 (8)	0.0013 (7)	0.0056 (8)
C2	0.0160 (10)	0.0163 (10)	0.0209 (10)	0.0047 (8)	0.0045 (8)	0.0071 (9)
C8	0.0139 (10)	0.0151 (10)	0.0215 (10)	0.0012 (8)	0.0004 (8)	0.0024 (8)
C9	0.0135 (9)	0.0175 (10)	0.0229 (11)	0.0039 (8)	0.0054 (8)	0.0102 (9)

O1—C5	1.240 (2)	C10—C11	1.396 (3)
N3—C12	1.392 (2)	C10—C9	1.372 (3)
N3—C11	1.406 (2)	C3—H3A	0.9300
N3—H3	0.93 (2)	C3—C2	1.390 (3)
N1—C12	1.332 (2)	C6—C7	1.396 (3)
N1—C1	1.344 (2)	C6—C11	1.399 (2)
N2—C4	1.412 (2)	C6—C5	1.487 (3)
N2—C5	1.347 (2)	C7—H7	0.9300
N2—H2	0.87 (3)	C7—C8	1.380 (3)
C4—C12	1.406 (3)	C2—H2A	0.9300
C4—C3	1.374 (3)	C8—H8	0.9300
C1—H1	0.9300	C8—C9	1.387 (3)
C1—C2	1.372 (3)	C9—H9	0.9300
C10—H10	0.9300
C12—N3—C11	121.58 (15)	C7—C6—C11	119.17 (17)
C12—N3—H3	110.9 (13)	C7—C6—C5	115.70 (16)
C11—N3—H3	112.7 (13)	C11—C6—C5	124.91 (17)
C12—N1—C1	117.87 (16)	C6—C7—H7	119.2
C4—N2—H2	115.9 (15)	C8—C7—C6	121.68 (18)
C5—N2—C4	130.98 (17)	C8—C7—H7	119.2
C5—N2—H2	112.2 (15)	C10—C11—N3	117.55 (16)
C12—C4—N2	123.05 (17)	C10—C11—C6	118.58 (17)
C3—C4—N2	118.46 (17)	C6—C11—N3	123.83 (17)
C3—C4—C12	118.12 (17)	O1—C5—N2	119.17 (17)
N3—C12—C4	121.47 (16)	O1—C5—C6	119.73 (17)
N1—C12—N3	115.93 (16)	N2—C5—C6	121.09 (16)
N1—C12—C4	122.55 (17)	C1—C2—C3	118.16 (18)
N1—C1—H1	118.2	C1—C2—H2A	120.9
N1—C1—C2	123.52 (18)	C3—C2—H2A	120.9
C2—C1—H1	118.2	C7—C8—H8	120.7
C11—C10—H10	119.4	C7—C8—C9	118.69 (18)
C9—C10—H10	119.4	C9—C8—H8	120.7
C9—C10—C11	121.27 (17)	C10—C9—C8	120.60 (18)
C4—C3—H3A	120.2	C10—C9—H9	119.7
C4—C3—C2	119.64 (17)	C8—C9—H9	119.7
C2—C3—H3A	120.2
N1—C1—C2—C3	−3.0 (3)	C7—C6—C11—C10	−1.0 (3)
N2—C4—C12—N3	−7.9 (3)	C7—C6—C5—O1	−22.0 (3)
N2—C4—C12—N1	169.29 (18)	C7—C6—C5—N2	157.23 (17)
N2—C4—C3—C2	−170.60 (17)	C7—C8—C9—C10	−0.5 (3)
C4—N2—C5—O1	170.53 (18)	C11—N3—C12—N1	132.19 (18)
C4—N2—C5—C6	−8.7 (3)	C11—N3—C12—C4	−50.5 (2)
C4—C3—C2—C1	0.4 (3)	C11—C10—C9—C8	0.5 (3)
C12—N3—C11—C10	−129.09 (19)	C11—C6—C7—C8	1.0 (3)
C12—N3—C11—C6	53.5 (2)	C11—C6—C5—O1	152.47 (18)
C12—N1—C1—C2	2.1 (3)	C11—C6—C5—N2	−28.3 (3)
C12—C4—C3—C2	2.7 (3)	C5—N2—C4—C12	42.4 (3)
C1—N1—C12—N3	178.56 (16)	C5—N2—C4—C3	−144.7 (2)
C1—N1—C12—C4	1.3 (3)	C5—C6—C7—C8	175.82 (17)
C3—C4—C12—N3	179.21 (17)	C5—C6—C11—N3	2.0 (3)
C3—C4—C12—N1	−3.6 (3)	C5—C6—C11—C10	−175.34 (17)
C6—C7—C8—C9	−0.2 (3)	C9—C10—C11—N3	−177.23 (16)
C7—C6—C11—N3	176.35 (17)	C9—C10—C11—C6	0.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1i	0.87 (2)	1.98 (2)	2.840 (2)	175 (2)
N3—H3···N1ii	0.93 (2)	2.28 (2)	3.200 (2)	168.7 (19)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2O1i	0.87(2)	1.98(2)	2.840(2)	175(2)
N3H3N1ii	0.93(2)	2.28(2)	3.200(2)	168.7(19)

Symmetry codes: (i) ; (ii) .