organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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10,10′-Methyl­enebis[2,3-di­hydro-1H-benzo[e]pyrrolo[1,2-a][1,4]diazepine-5,11(10H,11aH)-dione] dihydrate

aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, bService Commun Rayons X, Université Paul Sabatier, Bâtiment 2R1, 118 route de Narbonne, 31062 Toulouse, France, cHétérochimie Fondamentale et Appliquée, Université Paul Sabatier, UMR 5069, 118 Route de Narbonne, 31062 Toulouse, France, and dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
*Correspondence e-mail: seikweng@um.edu.my

(Received 29 September 2009; accepted 5 October 2009; online 10 October 2009)

The organic mol­ecule and uncoordinated water mol­ecule in the crystal of the title compound, C25H24N4O4·2H2O, both lie on special positions of twofold symmetry. A twofold rotation axis passes through the methyl­ene C atom connecting the two dihydro­benzopyrrolodiazepindionyl parts. The seven-membered C5N2 ring adopts a boat conformation.

Related literature

Pyrrolo[2,1-c][1,4]benzodiazepines are a group of potent chemicals produced by Streptomyces species. For their anti-cancer activity, see: Bose et al. (1992[Bose, D. S., Thompson, A. S., Chin, J., Hartley, J. A., Berardini, M. D., Jenkins, T. C., Neidle, S., Hurley, L. H. & Thurston, D. E. (1992). J. Am. Chem. Soc. 114, 4939-4941.]); Cargill et al. (1974[Cargill, C., Bachmann, E. & Zbinden, G. (1974). J. Natl. Cancer Inst. 53, 481-486.]); Gregson et al. (2004[Gregson, S. T., Howard, P. W., Gullick, D. R., Hamaguchi, A., Corcoran, K. E., Brooks, N. A., Hartley, J. A., Jenkins, T. C., Patel, S., Guille, M. J. & Thurston, D. E. (2004). J. Med. Chem. 47, 1161-1174.]).

[Scheme 1]

Experimental

Crystal data
  • C25H24N4O4·2H2O

  • Mr = 480.51

  • Trigonal, P 31 21

  • a = 11.9901 (2) Å

  • c = 13.6054 (2) Å

  • V = 1693.90 (4) Å3

  • Z = 3

  • Mo Kα radiation

  • μ = 0.10 mm−1

  • T = 193 K

  • 0.20 × 0.20 × 0.10 mm

Data collection
  • Bruker APEXII diffractometer

  • Absorption correction: none

  • 23041 measured reflections

  • 1572 independent reflections

  • 1472 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.126

  • S = 1.18

  • 1572 reflections

  • 159 parameters

  • H-atom parameters constrained

  • Δρmax = 0.46 e Å−3

  • Δρmin = −0.48 e Å−3

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: X-SEED (Barbour, 2001[Barbour, L. J. (2001). J. Supramol. Chem. 1, 189-191.]); software used to prepare material for publication: publCIF (Westrip, 2009[Westrip, S. P. (2009). publCIF. In preparation.]).

Supporting information


Related literature top

Pyrrolo[2,1-c][1,4]benzodiazepines are a group of potent chemicals produced by Streptomyces species. For their anti-cancer activity, see: Bose et al. (1992); Cargill et al. (1974); Gregson et al. (2004).

Experimental top

2,3-Dihydro-1H-benzo[e]pyrrolo[1,2-a][1,4]diazepine-5,11(10H,11aH)-dione (1.1 g, 6 mmol), dibromomethane (1.8 ml, 2.54 mmol), potassium carbonate (0.71 g, 6 mmol) and a catalytic quantity of tetra-n-butylammonium bromide were stirred in N,N-dimethylformamide (20 ml) for 24 h. The insoluble salts were filtered off and the solvent was removed under vacuum. The residue was separated by chromatography on silica gel with an n-hexane:ethyl acetate (8:2) solvent system. The compound was obtained as colorless crystals in 70% yield upon evaporation of the solvent.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C). The location of the water-bound H-atoms were ambiguous owing to disorder. The H1w1 atom was placed in a chemically sensible position on the basis of its hydrogen bonding to the O2 atom but was not refined. The water molecules are arranged along the c-axis with O1w···O1w separations of 2.741 (5) and 2.757 (5) Å, indicative of hydrogen bonding interactions. The assigned position for the second hydrogen atom (O-H = 0.84 Å), with full occupancy represents an intermediate position.

Structure description top

Pyrrolo[2,1-c][1,4]benzodiazepines are a group of potent chemicals produced by Streptomyces species. For their anti-cancer activity, see: Bose et al. (1992); Cargill et al. (1974); Gregson et al. (2004).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C25H24N4O4.H2O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Unlabelled atoms are related by a twofold axis.
10,10'-Methylenebis[2,3-dihydro-1H- benzo[e]pyrrolo[1,2-a][1,4]diazepine- 5,11(10H,11aH)-dione] dihydrate top
Crystal data top
C25H24N4O4·2H2ODx = 1.413 Mg m3
Mr = 480.51Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3121Cell parameters from 9284 reflections
Hall symbol: P 31 2"θ = 5.0–28.3°
a = 11.9901 (2) ŵ = 0.10 mm1
c = 13.6054 (2) ÅT = 193 K
V = 1693.90 (4) Å3Block, colorless
Z = 30.20 × 0.20 × 0.10 mm
F(000) = 762
Data collection top
Bruker APEXII
diffractometer
1472 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.043
Graphite monochromatorθmax = 28.3°, θmin = 5.2°
φ and ω scansh = 130
23041 measured reflectionsk = 015
1572 independent reflectionsl = 018
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.126 w = 1/[σ2(Fo2) + (0.0716P)2 + 0.3837P]
where P = (Fo2 + 2Fc2)/3
S = 1.18(Δ/σ)max = 0.001
1572 reflectionsΔρmax = 0.46 e Å3
159 parametersΔρmin = 0.48 e Å3
0 restraintsAbsolute structure: nd
Primary atom site location: structure-invariant direct methods
Crystal data top
C25H24N4O4·2H2OZ = 3
Mr = 480.51Mo Kα radiation
Trigonal, P3121µ = 0.10 mm1
a = 11.9901 (2) ÅT = 193 K
c = 13.6054 (2) Å0.20 × 0.20 × 0.10 mm
V = 1693.90 (4) Å3
Data collection top
Bruker APEXII
diffractometer
1472 reflections with I > 2σ(I)
23041 measured reflectionsRint = 0.043
1572 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.126H-atom parameters constrained
S = 1.18Δρmax = 0.46 e Å3
1572 reflectionsΔρmin = 0.48 e Å3
159 parametersAbsolute structure: nd
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
O10.57170 (18)0.14709 (17)0.22350 (11)0.0274 (4)
O20.7198 (2)0.0623 (2)0.57106 (13)0.0362 (5)
O1W0.9339 (4)0.0162 (4)0.5795 (2)0.0819 (10)
H1W10.87580.03490.56920.123*
H1W21.00690.07980.56450.123*
N10.47771 (19)0.1028 (2)0.37359 (13)0.0219 (4)
N20.7341 (2)0.16144 (19)0.42630 (14)0.0235 (4)
C10.4814 (2)0.1364 (2)0.47532 (15)0.0233 (5)
C20.3891 (3)0.1666 (3)0.50682 (18)0.0303 (5)
H20.33100.16890.46060.036*
C30.3812 (3)0.1934 (3)0.60537 (19)0.0361 (6)
H30.31950.21600.62610.043*
C40.4645 (3)0.1867 (3)0.67300 (18)0.0382 (7)
H40.45810.20190.74070.046*
C50.5571 (3)0.1577 (2)0.64133 (16)0.0303 (6)
H50.61330.15290.68820.036*
C60.5699 (2)0.1355 (2)0.54191 (16)0.0243 (5)
C70.3561 (3)0.00000.33330.0239 (6)
H7A0.29000.03530.38580.029*0.50
H7B0.32530.03530.28090.029*0.50
C80.5813 (2)0.1646 (2)0.31219 (16)0.0224 (5)
C90.7077 (2)0.2487 (2)0.36580 (15)0.0225 (5)
H90.70200.31410.40780.027*
C100.8238 (2)0.3128 (3)0.29721 (17)0.0296 (5)
H10A0.89380.39300.32650.036*
H10B0.79970.33320.23290.036*
C110.8645 (3)0.2109 (3)0.28641 (18)0.0320 (6)
H11A0.95490.24990.26410.038*
H11B0.80800.14250.23970.038*
C120.8482 (3)0.1579 (3)0.39173 (18)0.0317 (6)
H12A0.83340.06900.39180.038*
H12B0.92450.21330.43270.038*
C130.6801 (2)0.1157 (2)0.51428 (16)0.0251 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0330 (9)0.0290 (9)0.0170 (7)0.0132 (8)0.0008 (6)0.0000 (6)
O20.0427 (11)0.0404 (11)0.0284 (9)0.0229 (9)0.0039 (8)0.0068 (8)
O1W0.082 (2)0.126 (3)0.0681 (18)0.075 (2)0.0051 (16)0.0110 (19)
N10.0235 (9)0.0246 (9)0.0173 (8)0.0117 (8)0.0014 (7)0.0033 (7)
N20.0260 (10)0.0253 (10)0.0196 (8)0.0131 (8)0.0018 (7)0.0005 (7)
C10.0273 (11)0.0201 (10)0.0184 (9)0.0088 (9)0.0018 (9)0.0020 (8)
C20.0304 (13)0.0304 (12)0.0296 (12)0.0148 (11)0.0025 (9)0.0054 (10)
C30.0323 (13)0.0361 (14)0.0334 (13)0.0122 (12)0.0061 (11)0.0124 (11)
C40.0365 (15)0.0363 (14)0.0242 (11)0.0050 (12)0.0091 (11)0.0074 (10)
C50.0330 (13)0.0259 (12)0.0178 (10)0.0042 (10)0.0009 (9)0.0005 (9)
C60.0267 (11)0.0209 (10)0.0181 (10)0.0064 (9)0.0014 (8)0.0009 (8)
C70.0248 (11)0.0276 (16)0.0203 (13)0.0138 (8)0.0021 (6)0.0041 (12)
C80.0271 (11)0.0212 (10)0.0206 (10)0.0134 (9)0.0005 (8)0.0010 (8)
C90.0271 (11)0.0212 (10)0.0173 (9)0.0106 (9)0.0013 (8)0.0014 (8)
C100.0287 (12)0.0278 (12)0.0247 (10)0.0084 (10)0.0034 (9)0.0017 (9)
C110.0294 (12)0.0387 (14)0.0277 (12)0.0168 (11)0.0022 (10)0.0014 (11)
C120.0299 (13)0.0382 (14)0.0287 (12)0.0183 (11)0.0029 (10)0.0031 (10)
C130.0293 (12)0.0227 (11)0.0193 (9)0.0099 (9)0.0037 (9)0.0002 (8)
Geometric parameters (Å, º) top
O1—C81.220 (3)C5—C61.402 (3)
O2—C131.240 (3)C5—H50.9500
O1W—H1W10.8429C6—C131.502 (4)
O1W—H1W20.8500C7—N1i1.466 (3)
N1—C81.367 (3)C7—H7A0.9900
N1—C11.436 (3)C7—H7B0.9900
N1—C71.466 (3)C8—C91.522 (3)
N2—C131.341 (3)C9—C101.526 (3)
N2—C121.466 (3)C9—H91.0000
N2—C91.485 (3)C10—C111.533 (4)
C1—C21.393 (3)C10—H10A0.9900
C1—C61.399 (3)C10—H10B0.9900
C2—C31.393 (3)C11—C121.540 (3)
C2—H20.9500C11—H11A0.9900
C3—C41.389 (4)C11—H11B0.9900
C3—H30.9500C12—H12A0.9900
C4—C51.387 (4)C12—H12B0.9900
C4—H40.9500
H1W1—O1W—H1W2109.8O1—C8—N1121.9 (2)
C8—N1—C1122.97 (19)O1—C8—C9124.4 (2)
C8—N1—C7118.68 (17)N1—C8—C9113.59 (18)
C1—N1—C7118.32 (17)N2—C9—C8106.93 (18)
C13—N2—C12122.8 (2)N2—C9—C10103.41 (19)
C13—N2—C9123.6 (2)C8—C9—C10113.32 (18)
C12—N2—C9111.90 (18)N2—C9—H9111.0
C2—C1—C6120.4 (2)C8—C9—H9111.0
C2—C1—N1116.9 (2)C10—C9—H9111.0
C6—C1—N1122.6 (2)C9—C10—C11103.3 (2)
C1—C2—C3120.7 (2)C9—C10—H10A111.1
C1—C2—H2119.6C11—C10—H10A111.1
C3—C2—H2119.6C9—C10—H10B111.1
C4—C3—C2119.4 (3)C11—C10—H10B111.1
C4—C3—H3120.3H10A—C10—H10B109.1
C2—C3—H3120.3C10—C11—C12102.4 (2)
C5—C4—C3119.8 (2)C10—C11—H11A111.3
C5—C4—H4120.1C12—C11—H11A111.3
C3—C4—H4120.1C10—C11—H11B111.3
C4—C5—C6121.6 (2)C12—C11—H11B111.3
C4—C5—H5119.2H11A—C11—H11B109.2
C6—C5—H5119.2N2—C12—C11102.4 (2)
C1—C6—C5117.9 (2)N2—C12—H12A111.3
C1—C6—C13124.7 (2)C11—C12—H12A111.3
C5—C6—C13117.4 (2)N2—C12—H12B111.3
N1i—C7—N1109.8 (3)C11—C12—H12B111.3
N1i—C7—H7A109.7H12A—C12—H12B109.2
N1—C7—H7A109.7O2—C13—N2122.4 (2)
N1i—C7—H7B109.7O2—C13—C6121.4 (2)
N1—C7—H7B109.7N2—C13—C6116.2 (2)
H7A—C7—H7B108.2
C8—N1—C1—C2124.6 (2)C12—N2—C9—C8113.4 (2)
C7—N1—C1—C253.5 (3)C13—N2—C9—C10158.9 (2)
C8—N1—C1—C657.4 (3)C12—N2—C9—C106.5 (2)
C7—N1—C1—C6124.5 (2)O1—C8—C9—N2112.1 (2)
C6—C1—C2—C31.6 (4)N1—C8—C9—N264.2 (2)
N1—C1—C2—C3176.4 (2)O1—C8—C9—C101.1 (3)
C1—C2—C3—C41.6 (4)N1—C8—C9—C10177.5 (2)
C2—C3—C4—C52.1 (4)N2—C9—C10—C1129.1 (2)
C3—C4—C5—C60.4 (4)C8—C9—C10—C1186.3 (2)
C2—C1—C6—C54.0 (3)C9—C10—C11—C1240.6 (2)
N1—C1—C6—C5173.9 (2)C13—N2—C12—C11175.9 (2)
C2—C1—C6—C13174.4 (2)C9—N2—C12—C1118.6 (3)
N1—C1—C6—C137.7 (4)C10—C11—C12—N235.9 (2)
C4—C5—C6—C13.4 (4)C12—N2—C13—O23.0 (4)
C4—C5—C6—C13175.1 (2)C9—N2—C13—O2166.9 (2)
C8—N1—C7—N1i59.77 (17)C12—N2—C13—C6175.5 (2)
C1—N1—C7—N1i122.0 (2)C9—N2—C13—C611.7 (3)
C1—N1—C8—O1169.7 (2)C1—C6—C13—O2148.6 (2)
C7—N1—C8—O18.4 (3)C5—C6—C13—O233.0 (3)
C1—N1—C8—C913.9 (3)C1—C6—C13—N232.9 (3)
C7—N1—C8—C9168.02 (19)C5—C6—C13—N2145.5 (2)
C13—N2—C9—C881.2 (3)
Symmetry code: (i) xy, y, z+2/3.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O20.842.062.886 (4)168

Experimental details

Crystal data
Chemical formulaC25H24N4O4·2H2O
Mr480.51
Crystal system, space groupTrigonal, P3121
Temperature (K)193
a, c (Å)11.9901 (2), 13.6054 (2)
V3)1693.90 (4)
Z3
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.20 × 0.20 × 0.10
Data collection
DiffractometerBruker APEXII
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
23041, 1572, 1472
Rint0.043
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.126, 1.18
No. of reflections1572
No. of parameters159
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.48
Absolute structureNd

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

 

Acknowledgements

We thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

References

First citationBarbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.  CrossRef CAS Google Scholar
First citationBose, D. S., Thompson, A. S., Chin, J., Hartley, J. A., Berardini, M. D., Jenkins, T. C., Neidle, S., Hurley, L. H. & Thurston, D. E. (1992). J. Am. Chem. Soc. 114, 4939–4941.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCargill, C., Bachmann, E. & Zbinden, G. (1974). J. Natl. Cancer Inst. 53, 481–486.  CAS PubMed Web of Science Google Scholar
First citationGregson, S. T., Howard, P. W., Gullick, D. R., Hamaguchi, A., Corcoran, K. E., Brooks, N. A., Hartley, J. A., Jenkins, T. C., Patel, S., Guille, M. J. & Thurston, D. E. (2004). J. Med. Chem. 47, 1161–1174.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2009). publCIF. In preparation.  Google Scholar

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