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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3213.
Published online 2009 November 25. doi:  10.1107/S1600536809049836
PMCID: PMC2971997

2-Methyl-2,4-di-4-pyridyl-2,3-dihydro-1H-1,5-benzodiazepine acetic acid solvate

Abstract

In the title compound, C20H18N4·CH3COOH, the benzene ring forms dihedral angles of 81.34 (11) and 54.32 (11)° with the two pyridine rings. In the crystal, inter­molecular O—H(...)N hydrogen bonding links one 1,5-benzodiazepine mol­ecule and one acetic acid solvent mol­ecule into a dimer. These dimers, related by translation along the b axis, are further linked into chains via weak inter­molecular N—H(...)N hydrogen bonds.

Related literature

For details of the synthesis and a related compound, see Hou et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3213-scheme1.jpg

Experimental

Crystal data

  • C20H18N4·C2H4O2
  • M r = 374.44
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3213-efi1.jpg
  • a = 8.925 (6) Å
  • b = 10.172 (8) Å
  • c = 12.283 (9) Å
  • α = 68.56 (3)°
  • β = 75.41 (3)°
  • γ = 88.52 (3)°
  • V = 1001.8 (12) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 290 K
  • 0.11 × 0.10 × 0.09 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.991, T max = 0.993
  • 9946 measured reflections
  • 4547 independent reflections
  • 2400 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.211
  • S = 1.04
  • 4547 reflections
  • 256 parameters
  • H-atom parameters constrained
  • Δρmax = 0.24 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049836/cv2662sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049836/cv2662Isup2.hkl

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 20874038) and the National Basic Research Program of China (grant No. 2007CB936402).

supplementary crystallographic information

Comment

The title compound (I) was unexpectedly obtained during our study of the Schiff base bis-pyridine complex (Hou et al., 2007). In this paper, we report its crystal structure.

In (I) (Fig.1), the dihedral angles between benzene ring and two pyridine rings are 81.34 (11) ° and 54.32 (11) °, respectively. In the crystal structure, the intramolecular O—H···N and intermolecule N—H···N hydrogen bonds (Table 1) are observed.

Experimental

The title compound and its single crystals suitable for the X-ray diffraction were prepared by slow evaporation of the ethanol solution which contains o-phenylenediamine, 4-acetylpyridine and a small amount of acetic acid at room temperatue.

Refinement

All H atoms were placed in calculated positions (C—H 0.93 - 0.97 Å, N—H 0.86 Å, O—H 0.82 Å), and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2 or 1.5 Ueq of the parent atom.

Figures

Fig. 1.
The asymmetric unit of the title compound showing the atomic numbering. Displacement ellipsoids of non-H atoms are drawn at the 30% probability level.

Crystal data

C20H18N4·C2H4O2Z = 2
Mr = 374.44F(000) = 396
Triclinic, P1Dx = 1.241 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.925 (6) ÅCell parameters from 6051 reflections
b = 10.172 (8) Åθ = 3.1–27.5°
c = 12.283 (9) ŵ = 0.08 mm1
α = 68.56 (3)°T = 290 K
β = 75.41 (3)°Block, colourless
γ = 88.52 (3)°0.11 × 0.10 × 0.09 mm
V = 1001.8 (12) Å3

Data collection

Rigaku R-AXIS RAPID diffractometer4547 independent reflections
Radiation source: fine-focus sealed tube2400 reflections with I > 2σ(I)
graphiteRint = 0.039
ω scansθmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)h = −11→11
Tmin = 0.991, Tmax = 0.993k = −13→13
9946 measured reflectionsl = −15→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.064Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.211H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.1067P)2 + 0.0338P] where P = (Fo2 + 2Fc2)/3
4547 reflections(Δ/σ)max < 0.001
256 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = −0.36 e Å3

Special details

Experimental. (See detailed section in the paper)
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.2037 (3)0.2500 (2)1.0826 (2)0.0436 (6)
C20.1293 (3)0.2017 (3)1.2065 (3)0.0533 (7)
H20.09900.26791.24220.064*
C30.0993 (3)0.0601 (3)1.2775 (3)0.0603 (7)
H30.05190.03101.36000.072*
C40.1407 (3)−0.0376 (3)1.2242 (3)0.0598 (8)
H40.1206−0.13381.27070.072*
C50.2111 (3)0.0060 (2)1.1037 (3)0.0545 (7)
H50.2379−0.06231.06980.065*
C60.2455 (3)0.1504 (2)1.0273 (2)0.0448 (6)
C70.3831 (3)0.3117 (2)0.8120 (2)0.0456 (6)
C80.5137 (3)0.2748 (3)0.7236 (3)0.0616 (8)
H8A0.58780.22470.76520.092*
H8B0.56390.36030.65900.092*
H8C0.47170.21630.69070.092*
C90.2688 (3)0.3983 (2)0.7451 (2)0.0476 (6)
C100.1148 (4)0.3542 (3)0.7753 (3)0.0701 (9)
H100.07500.26810.83740.084*
C110.0187 (4)0.4432 (4)0.7092 (4)0.0911 (12)
H11−0.08580.41360.72940.109*
C120.2161 (5)0.6063 (4)0.5942 (3)0.0795 (10)
H120.25260.69340.53250.095*
C130.3180 (4)0.5278 (3)0.6521 (3)0.0652 (8)
H130.42160.56140.62900.078*
C140.4524 (3)0.4008 (2)0.8686 (2)0.0458 (6)
H14A0.50780.34040.92440.055*
H14B0.52630.47410.80500.055*
C150.3307 (3)0.4680 (2)0.9343 (2)0.0400 (5)
C160.3302 (3)0.6249 (2)0.8930 (2)0.0409 (5)
C170.4648 (3)0.7133 (2)0.8320 (2)0.0468 (6)
H170.55840.67660.80800.056*
C180.4577 (3)0.8567 (2)0.8072 (3)0.0533 (7)
H180.54990.91390.76900.064*
C190.1991 (3)0.8327 (3)0.8883 (3)0.0587 (7)
H190.10580.87330.90530.070*
C200.1949 (3)0.6889 (3)0.9202 (3)0.0534 (7)
H200.10130.63440.96010.064*
C210.6804 (5)0.8687 (5)0.4824 (4)0.1079 (15)
H21A0.57080.84320.50840.162*
H21B0.71330.90670.39550.162*
H21C0.70250.93870.51260.162*
C220.7639 (4)0.7424 (4)0.5294 (3)0.0768 (10)
N10.2212 (2)0.39891 (19)1.02797 (19)0.0445 (5)
N20.3101 (3)0.1793 (2)0.9066 (2)0.0551 (6)
H2A0.30690.10930.88360.066*
N30.0682 (4)0.5654 (3)0.6210 (3)0.0836 (9)
N40.3286 (3)0.9185 (2)0.8342 (2)0.0556 (6)
O10.7070 (3)0.6287 (3)0.6004 (3)0.1032 (9)
O20.9124 (3)0.7674 (3)0.5022 (3)0.1017 (9)
H2B0.94950.70150.54690.153*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0418 (12)0.0344 (12)0.0494 (14)−0.0018 (10)−0.0064 (11)−0.0128 (10)
C20.0505 (14)0.0459 (14)0.0580 (17)−0.0008 (11)−0.0022 (13)−0.0207 (12)
C30.0594 (16)0.0541 (16)0.0506 (16)−0.0054 (13)−0.0016 (13)−0.0082 (13)
C40.0639 (17)0.0381 (13)0.0614 (18)−0.0055 (12)−0.0059 (15)−0.0063 (12)
C50.0593 (16)0.0318 (12)0.0657 (18)0.0025 (11)−0.0113 (14)−0.0136 (12)
C60.0443 (13)0.0330 (11)0.0535 (15)0.0023 (10)−0.0088 (12)−0.0145 (10)
C70.0493 (13)0.0320 (11)0.0527 (14)0.0030 (10)−0.0068 (12)−0.0167 (10)
C80.0634 (17)0.0520 (15)0.0663 (18)0.0084 (13)−0.0006 (15)−0.0295 (14)
C90.0530 (15)0.0407 (12)0.0531 (15)0.0034 (11)−0.0099 (12)−0.0247 (11)
C100.0612 (18)0.0599 (17)0.089 (2)0.0034 (14)−0.0206 (17)−0.0266 (16)
C110.065 (2)0.099 (3)0.125 (3)0.009 (2)−0.034 (2)−0.053 (3)
C120.089 (3)0.074 (2)0.073 (2)0.0165 (19)−0.028 (2)−0.0203 (17)
C130.0704 (19)0.0555 (16)0.0571 (17)0.0060 (14)−0.0128 (15)−0.0090 (13)
C140.0445 (13)0.0332 (11)0.0576 (15)0.0035 (10)−0.0088 (12)−0.0175 (11)
C150.0426 (12)0.0310 (11)0.0477 (13)0.0001 (9)−0.0107 (11)−0.0166 (10)
C160.0439 (12)0.0337 (11)0.0467 (13)0.0007 (9)−0.0102 (11)−0.0178 (10)
C170.0439 (13)0.0386 (12)0.0554 (15)−0.0006 (10)−0.0055 (12)−0.0193 (11)
C180.0523 (15)0.0373 (13)0.0640 (17)−0.0072 (11)−0.0067 (13)−0.0167 (12)
C190.0472 (14)0.0398 (13)0.090 (2)0.0043 (11)−0.0119 (14)−0.0291 (14)
C200.0448 (13)0.0366 (12)0.0772 (19)−0.0015 (10)−0.0091 (13)−0.0235 (12)
C210.094 (3)0.110 (3)0.105 (3)0.022 (2)−0.039 (3)−0.015 (3)
C220.0560 (18)0.089 (2)0.081 (2)−0.0001 (17)−0.0146 (17)−0.028 (2)
N10.0446 (11)0.0336 (10)0.0524 (12)0.0004 (8)−0.0069 (10)−0.0163 (9)
N20.0783 (15)0.0291 (10)0.0525 (13)−0.0022 (10)−0.0052 (12)−0.0163 (9)
N30.104 (2)0.0753 (19)0.083 (2)0.0293 (17)−0.0411 (19)−0.0328 (16)
N40.0589 (13)0.0346 (10)0.0743 (16)0.0030 (10)−0.0151 (12)−0.0228 (10)
O10.0889 (18)0.0776 (17)0.108 (2)−0.0144 (14)0.0036 (16)−0.0122 (16)
O20.0828 (17)0.097 (2)0.094 (2)−0.0047 (14)−0.0226 (15)0.0014 (15)

Geometric parameters (Å, °)

C1—C21.400 (4)C12—C131.358 (4)
C1—C61.408 (4)C12—H120.9300
C1—N11.409 (3)C13—H130.9300
C2—C31.375 (4)C14—C151.491 (3)
C2—H20.9300C14—H14A0.9700
C3—C41.373 (4)C14—H14B0.9700
C3—H30.9300C15—N11.284 (3)
C4—C51.360 (4)C15—C161.488 (3)
C4—H40.9300C16—C201.381 (4)
C5—C61.415 (3)C16—C171.387 (3)
C5—H50.9300C17—C181.380 (3)
C6—N21.370 (4)C17—H170.9300
C7—N21.452 (3)C18—N41.325 (3)
C7—C81.522 (4)C18—H180.9300
C7—C91.529 (3)C19—N41.334 (3)
C7—C141.546 (4)C19—C201.368 (4)
C8—H8A0.9600C19—H190.9300
C8—H8B0.9600C20—H200.9300
C8—H8C0.9600C21—C221.471 (5)
C9—C101.371 (4)C21—H21A0.9600
C9—C131.382 (4)C21—H21B0.9600
C10—C111.410 (5)C21—H21C0.9600
C10—H100.9300C22—O11.194 (4)
C11—N31.309 (5)C22—O21.290 (4)
C11—H110.9300N2—H2A0.8600
C12—N31.317 (5)O2—H2B0.8200
C2—C1—C6119.0 (2)C12—C13—H13119.8
C2—C1—N1112.7 (2)C9—C13—H13119.8
C6—C1—N1128.2 (2)C15—C14—C7112.2 (2)
C3—C2—C1122.5 (3)C15—C14—H14A109.2
C3—C2—H2118.7C7—C14—H14A109.2
C1—C2—H2118.7C15—C14—H14B109.2
C4—C3—C2118.7 (3)C7—C14—H14B109.2
C4—C3—H3120.6H14A—C14—H14B107.9
C2—C3—H3120.6N1—C15—C16115.3 (2)
C5—C4—C3120.2 (2)N1—C15—C14124.3 (2)
C5—C4—H4119.9C16—C15—C14120.4 (2)
C3—C4—H4119.9C20—C16—C17116.8 (2)
C4—C5—C6123.1 (3)C20—C16—C15120.8 (2)
C4—C5—H5118.4C17—C16—C15122.3 (2)
C6—C5—H5118.5C18—C17—C16119.0 (2)
N2—C6—C1126.6 (2)C18—C17—H17120.5
N2—C6—C5116.9 (2)C16—C17—H17120.5
C1—C6—C5116.5 (2)N4—C18—C17124.4 (2)
N2—C7—C8107.2 (2)N4—C18—H18117.8
N2—C7—C9112.2 (2)C17—C18—H18117.8
C8—C7—C9109.8 (2)N4—C19—C20124.1 (2)
N2—C7—C14109.4 (2)N4—C19—H19117.9
C8—C7—C14109.2 (2)C20—C19—H19117.9
C9—C7—C14108.97 (19)C19—C20—C16119.8 (2)
C7—C8—H8A109.5C19—C20—H20120.1
C7—C8—H8B109.5C16—C20—H20120.1
H8A—C8—H8B109.5C22—C21—H21A109.5
C7—C8—H8C109.5C22—C21—H21B109.5
H8A—C8—H8C109.5H21A—C21—H21B109.5
H8B—C8—H8C109.5C22—C21—H21C109.5
C10—C9—C13117.3 (3)H21A—C21—H21C109.5
C10—C9—C7122.5 (2)H21B—C21—H21C109.5
C13—C9—C7120.2 (2)O1—C22—O2118.9 (3)
C9—C10—C11117.9 (3)O1—C22—C21126.4 (4)
C9—C10—H10121.0O2—C22—C21113.9 (3)
C11—C10—H10121.0C15—N1—C1123.9 (2)
N3—C11—C10123.7 (3)C6—N2—C7129.0 (2)
N3—C11—H11118.1C6—N2—H2A115.5
C10—C11—H11118.1C7—N2—H2A115.5
N3—C12—C13123.3 (3)C11—N3—C12117.4 (3)
N3—C12—H12118.3C18—N4—C19115.8 (2)
C13—C12—H12118.3C22—O2—H2B109.5
C12—C13—C9120.4 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···N4i0.862.233.079 (4)172
O2—H2B···N3ii0.821.832.640 (4)168

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2662).

References

  • Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
  • Hou, Q.-F., Ye, L. & Jiang, S.-M. (2007). Acta Cryst. E63, o939–o940.
  • Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC & Rigaku Corporation (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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