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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

N,N′-Bis(2-chloro­nicotinoyl)-N-(3-nitro­phen­yl)hydrazine monohydrate: complex sheets built from O—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds

aFundação Oswaldo Cruz, Far Manguinhos, Rua Sizenando Nabuco, 100 Manguinhos, 21041-250 Rio de Janeiro, RJ, Brazil, bInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, cDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 2 February 2006; accepted 7 February 2006; online 11 March 2006)

In the title compound, C18H11Cl2N5O4·H2O, the two components are linked into complex sheets by a combination of five independent hydrogen bonds, viz. one of N—H⋯O type and two each of O—H⋯N and C—H⋯O types.

Comment

The title compound, (I)[link] (Fig. 1[link]), was obtained as an adventitious by-product, in low yield, during the attempted preparation of N-(2-chloro­nicotinoyl)-3-nitro­phenyl­hydrazine, (II).

[Scheme 1]

Within the hydrazine component in (I)[link], both N atoms (N17 and N21) have effectively planar coordination, and the N—N bond distance (Table 1[link]) is typical of the value in hydrazines with both N atoms having planar coordination (the mean value is 1.401 Å; Allen et al., 1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]). The fragment C13—C17(=O1)—N17—N21 is effectively planar, as shown by the key torsion angles, but the corresponding fragment encompassing atoms N21 and C37 shows a markedly non-planar conformation. The mol­ecule overall has no inter­nal symmetry and hence it is chiral.

The independent mol­ecular components in (I)[link] are linked into sheets of considerable complexity by a combination of five independent hydrogen bonds, of O—H⋯N, N—H⋯O and C—H⋯O types (Table 2[link]). Within the selected asymmetric unit (Fig. 1[link]) the components are linked by an O—H⋯N hydrogen bond, and four further hydrogen bonds generate the sheet. The formation of the sheet is readily analysed in terms of three substructures, viz. one finite (zero-dimensional) substructure and two distinct one-dimensional substructures.

The finite substructure is built from the two O—H⋯N hydrogen bonds. Water atom O4 at (x, y, z) acts as a hydrogen-bond donor, via H4A and H4B, respectively, to atoms N11 at (x, y, z) and N31 at (−x + 1, −y + 1, −z + 1), thereby generating a cyclic centrosymmetric four-mol­ecule aggregate of R44(26) type (Bernstein et al., 1995[Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555-1573.]) and centred at ([1\over2], [1\over2], [1\over2]) (Fig. 2[link]). The two independent one-dimensional substructures result from two different modes of linking of these R44(26) aggregates; one mode utilizes the single N—H⋯O hydrogen bond, while the other utilizes the concerted action of the two C—H⋯O hydrogen bonds.

In the simpler of the two one-dimensional substructures, atoms N17 in the hydrazine mol­ecules at (x, y, z) and (−x + 1, −y + 1, −z + 1), which form part of the R44(26) aggregate centred at ([1\over 2], [1\over2], [1\over2]), act as hydrogen-bond donors, respectively, to water atoms O4 at (x + 1, y, z) and (x − 1, y, z), which themselves lie in the R44(26) aggregates centred at ([3\over2], [1\over2], [1\over2]) and (−[1\over2], [1\over2], [1\over2]), respectively. Propagation of this hydrogen bond by translation and inversion then generates a chain of edge-fused rings running parallel to the [100] direction, with R44(26) rings centred at (n + [1\over2], [1\over2], [1\over2]) (n = zero or integer) and R44(18) rings centred at (n, [1\over2], [1\over2]) (n = zero or integer) (Fig. 3[link]).

In the second of the one-dimensional substructures, atoms C15 and C26 at (x, y, z) act as hydrogen-bond donors, respectively, to atoms O1 and O2, both at (x, y + 1, z), thereby generating by translation a C(6)C(7)[R22(19)] chain of rings running parallel to the [010] direction (Fig. 4[link]). In combination with the R44(26) aggregates (Fig. 2[link]), these C—H⋯O hydrogen bonds then generate a complex ribbon containing three distinct types of ring. The central strip of the ribbon consists of edge-fused centrosymmetric R44(26) and R66(30) rings generated by inversion, with the R44(26) rings centred at ([1\over2], n + [1\over2], [1\over2]) (n = zero or integer) and the R66(30) rings centred at ([1\over2], n, [1\over2]) (n = zero or integer), while there are two antiparallel chains of edge-fused R22(19) rings, generated by translation, along the two edges of the ribbon (Fig. 4[link]).

The combination of the [100] and [010] chains of rings, containing two and three distinct types of ring, respectively, then generates a complex (001) sheet. A single sheet of this type passes through each unit cell, but there are no direction-specific inter­actions between adjacent sheets.

[Figure 1]
Figure 1
The mol­ecular components of (I)[link], showing the atom-labelling scheme and the O—H⋯N hydrogen bond (dashed line) within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2]
Figure 2
Part of the crystal structure of (I)[link], showing the formation of a centrosymmetric R44(26) aggregate of four mol­ecules. For the sake of clarity, H atoms bonded to C and N atoms have been omitted. Atoms marked with an asterisk (*) are at the symmetry position (−x + 1, −y + 1, −z + 1).
[Figure 3]
Figure 3
A stereoview of part of the crystal structure of (I)[link], showing the formation of a [100] chain of edge-fused R44(18) and R44(26) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 4]
Figure 4
A stereoview of part of the crystal structure of (I)[link], showing the formation of a [010] ribbon containing edge-fused R22(19), R44(26) and R66(30) rings. For the sake of clarity, H atoms not involved in the hydrogen bonds shown have been omitted.

Experimental

A solution of 2-chloro­nicotinoyl chloride (2 mmol), 3-nitro­phenyl­hydrazine hydro­chloride (2 mmol) and triethyl­amine (1 ml) in 1,2-dichloro­ethane (30 ml) was boiled under reflux for 60 min; the solution was cooled to ambient temperature and filtered to remove the precipitate of triethyl­ammonium chloride. The filtrate was left to stand overnight at ambient temperature and crystals of (I)[link], which had formed in very low yield, were collected by filtration. These were found to be suitable for single-crystal X-ray diffraction analysis. IR (cm−1, KBr pellet): 3230 (NH), 1684 (CO).

Crystal data
  • C18H11Cl2N5O4·H2O

  • Mr = 450.23

  • Triclinic, [P \overline 1]

  • a = 7.4435 (3) Å

  • b = 7.8829 (5) Å

  • c = 16.2657 (10) Å

  • α = 99.564 (2)°

  • β = 96.806 (3)°

  • γ = 90.842 (3)°

  • V = 933.94 (9) Å3

  • Z = 2

  • Dx = 1.601 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 4263 reflections

  • θ = 3.1–27.5°

  • μ = 0.39 mm−1

  • T = 120 (2) K

  • Plate, yellow

  • 0.16 × 0.14 × 0.03 mm

Data collection
  • Bruker KappaCCD diffractometer

  • φ and ω scans

  • Absorption correction: multi-scan(SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.])Tmin = 0.960, Tmax = 0.988

  • 19029 measured reflections

  • 4263 independent reflections

  • 2991 reflections with I > 2σ(I)

  • Rint = 0.076

  • θmax = 27.5°

  • h = −9 → 9

  • k = −10 → 10

  • l = −21 → 21

Refinement
  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.050

  • wR(F2) = 0.120

  • S = 1.04

  • 4263 reflections

  • 271 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(Fo2) + (0.0464P)2 + 0.5704P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max < 0.001

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.37 e Å−3

Table 1
Selected geometric parameters (Å, °)

N17—N21 1.399 (3) 
C13—C17—N17—N21 −173.63 (19)
C17—N17—N21—C21 78.5 (3)
C17—N17—N21—C37 −116.7 (2)
N17—N21—C37—C33 30.2 (3)
N17—N21—C37—O37 −156.2 (2)
C12—C13—C17—N17 −110.2 (3)
N17—N21—C21—C22 −142.1 (2)
N21—C37—C33—C32 −133.4 (2)
C21—N21—C37—O37 8.0 (3)
C21—N21—C37—C33 −165.7 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O4—H4A⋯N11 0.84 2.06 2.891 (3) 170
O4—H4B⋯N31i 0.84 1.97 2.805 (3) 171
N17—H17⋯O4ii 0.87 1.88 2.747 (3) 175
C15—H15⋯O1iii 0.95 2.56 3.228 (3) 127
C26—H26⋯O2iii 0.95 2.42 3.158 (3) 134
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y, z; (iii) x, y+1, z.

Crystals of (I)[link] are triclinic; the space group P[\overline{1}] was selected and confirmed by the successful structure analysis. All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.95 Å, N—H distances of 0.87 Å and O—H distances of 0.84 Å, and with Uiso(H) values set at 1.2Ueq(C,N,O).

Data collection: COLLECT (Hooft, 1999[Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003[McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.]) and SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999[Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.]).

Supporting information


Comment top

The title compound, (I) (Fig. 1), was obtained as an adventitious by-product, in low yield, during the attempted preparation of N-(2-chloronicotinoyl)-3-nitrophenylhydrazine, (II).

Within the hydrazine component in (I), both N atoms, N17 and N21, have effectively planar coordination, and the N—N bond distance (Table 1) is typical of the value in hydrazines with both N atoms having planar coordination [mean value 1.401 Å (Allen et al., 1987)]. The fragment C13—C17(O1)—N17—N21 is effectively planar, as shown by the key torsion angles, but the corresponding fragment encompassing N21 and C37 shows a markedly non-planar conformation. The molecule overall has no internal symmetry and hence it is chiral.

The independent molecular components in (I) are linked into sheets of considerable complexity by a combination of five independent hydrogen bonds, of O—H···N, N—H···O and C—H···O types (Table 2). Within the selected asymmetric unit (Fig. 1) the components are linked by an O—H···N hydrogen bond, and four further hydrogen bonds generate the sheet. The formation of the sheet is readily analysed in terms of three substructures, viz. one finite (zero-dimensional) sub-structure and two distinct one-dimensional substructures.

The finite substructure is built from the two O—H···N hydrogen bonds. Water atom O4 at (x, y, z) acts as a hydrogen-bond donor, via H4A and H4B, respectively, to atom N11 at (x, y, z) and N31 at (1 − x, 1 − y, 1 − z), thereby generating a cyclic centrosymmetric four-molecule aggregate of R44(26) type (Bernstein et al., 1995) and centred at (1/2, 1/2, 1/2) (Fig. 2). The two independent one-dimensional substructures result from two different modes of linking of these R44(26) aggregates; one mode utilizes the single N—H···O hydrogen bond, while the other utilizes the concerted action of the two C—H···O hydrogen bonds.

In the simpler of the two one-dimensional substructures, atoms N17 in the hydrazine molecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which form part of the R44(26) aggregate centred at (1/2, 1/2, 1/2), act as hydrogen-bond donors, respectively, to the water atoms O4 at (1 + x, y, z) and (−1 + x, y, z), which themselves lie in the R44(26) aggregates centred at (3/2, 1/2, 1/2) and (−1/2, 1/2, 1/2), respectively. Propagation of this hydrogen bond by translation and inversion then generates a chain of edge fused rings running parallel to the [100] direction, with R44(26) rings centred at (n + 1/2, 1/2, 1/2) (n = zero or integer) and R44(18) rings centred at (n, 1/2, 1/2) (n = zero or integer) (Fig. 3).

In the second of the one-dimensional substructures, the atoms C15 and C26 at (x, y, z) act as hydrogen-bond donors, respectively, to atoms O1 and O2, both at (x, 1 + y, z), thereby generating by translation a C(6)C(7)[R22(19)] chain of rings running parallel to the [010] direction (Fig. 4). In combination with the R44(26) aggregates (Fig. 2), these C—H···O hydrogen bonds then generate a complex ribbon containing three distinct types of ring. The central strip of the ribbon consists of edge-fused centrosymmetric R44(26) and R66(30) rings generated by inversion, with the R44(26) rings centred at (1/2, n + 1/2, 1/2) (n = zero or integer) and the R66(30) rings centred at (1/2, n, 1/2) (n = zero or integer), while there are two anti-parallel chains of edge-fused R22(19) rings, generated by translation, along the two edges of the ribbon (Fig. 4).

The combination of the [100] and [010] chains of rings, containing two and three distinct types of ring, respectively, then generates a complex (001) sheet. A single sheet of this type passes through each unit cell, but there are no direction-specific interactions between adjacent sheets.

Experimental top

A solution of 2-chloronicotinoyl chloride (2 mmol), 3-nitrophenylhydrazine hydrochloride (2 mmol) and triethylamine (1 ml) in 1,2-dichloroethane (30 ml) was boiled under reflux for 60 min; the solution was cooled to ambient temperature and filtered to remove the precipitate of triethylammonium chloride. The filtrate was left to stand overnight at ambient temperature and the crystals of (I), which had formed in very low yield, were collected by filtration. These were found to be suitable for single-crystal X-ray diffraction. IR (cm−1, KBr pellet) 3230 (NH), 1684 (CO).

Refinement top

Crystals of (I) are triclinic: the space group P1 was selected, and confirmed by the successful structure analysis. All H atoms were located in difference maps and then treated as riding atoms, with C—H distances of 0.95 Å, N—H distances of 0.87 Å and O—H distances of 0.84 Å, and with Uiso(H) set to 1.2Ueq(C,N,O).

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top
[Figure 1] Fig. 1. The molecular components of (I), showing the atom-labelling scheme and the O—H···N hydrogen bond (dashed line) within the asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of a centrosymmetric R44(26) aggregate of four molecules. For the sake of clarity, H atoms bonded to C and N atoms have been omitted. The atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).
[Figure 3] Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a [100] chain of edge-fused R44(18) and R44(26) rings. For the sake of clarity, H atoms bonded to C atoms have been omitted.
[Figure 4] Fig. 4. A stereoview of part of the crystal structure of (I), showing the formation of a [010] ribbon containing edge-fused R22(19), R44(26) and R66(30) rings. For the sake of clarity, H atoms not involved in the hydrogen bonds shown have been omitted.
N,N'-Bis(2-chloronicotinoyl)-N-(3-nitrophenyl)hydrazine monohydrate top
Crystal data top
C18H11Cl2N5O4·H2OZ = 2
Mr = 450.23F(000) = 460
Triclinic, P1Dx = 1.601 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.4435 (3) ÅCell parameters from 4263 reflections
b = 7.8829 (5) Åθ = 3.1–27.5°
c = 16.2657 (10) ŵ = 0.39 mm1
α = 99.564 (2)°T = 120 K
β = 96.806 (3)°Plate, yellow
γ = 90.842 (3)°0.16 × 0.14 × 0.03 mm
V = 933.94 (9) Å3
Data collection top
Bruker KappaCCD
diffractometer
4263 independent reflections
Radiation source: Bruker–Nonius FR91 rotating anode2991 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.076
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.1°
ϕ and ω scansh = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1010
Tmin = 0.960, Tmax = 0.988l = 2121
19029 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.120H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0464P)2 + 0.5704P]
where P = (Fo2 + 2Fc2)/3
4263 reflections(Δ/σ)max < 0.001
271 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.37 e Å3
Crystal data top
C18H11Cl2N5O4·H2Oγ = 90.842 (3)°
Mr = 450.23V = 933.94 (9) Å3
Triclinic, P1Z = 2
a = 7.4435 (3) ÅMo Kα radiation
b = 7.8829 (5) ŵ = 0.39 mm1
c = 16.2657 (10) ÅT = 120 K
α = 99.564 (2)°0.16 × 0.14 × 0.03 mm
β = 96.806 (3)°
Data collection top
Bruker KappaCCD
diffractometer
4263 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2991 reflections with I > 2σ(I)
Tmin = 0.960, Tmax = 0.988Rint = 0.076
19029 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0500 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.04Δρmax = 0.31 e Å3
4263 reflectionsΔρmin = 0.37 e Å3
271 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N110.4366 (3)0.6858 (3)0.26707 (13)0.0269 (5)
C120.5144 (3)0.5347 (3)0.26165 (15)0.0242 (5)
Cl10.43696 (9)0.39613 (9)0.32321 (4)0.03520 (19)
C130.6526 (3)0.4850 (3)0.21336 (15)0.0223 (5)
C140.7134 (3)0.6058 (3)0.16870 (15)0.0253 (5)
C150.6351 (3)0.7646 (3)0.17356 (16)0.0269 (5)
C160.4981 (3)0.7992 (3)0.22355 (16)0.0267 (6)
C170.7378 (3)0.3126 (3)0.21136 (15)0.0231 (5)
O10.6603 (2)0.1760 (2)0.18064 (11)0.0300 (4)
N170.9097 (3)0.3293 (3)0.25017 (13)0.0231 (4)
N211.0178 (3)0.1851 (2)0.24758 (12)0.0227 (4)
C211.0972 (3)0.1296 (3)0.17180 (15)0.0219 (5)
C221.1079 (3)0.0451 (3)0.14428 (15)0.0219 (5)
C231.1877 (3)0.0963 (3)0.07221 (15)0.0246 (5)
N231.2042 (3)0.2814 (3)0.04422 (14)0.0322 (5)
O21.1227 (3)0.3818 (2)0.07800 (13)0.0441 (5)
O31.3006 (3)0.3275 (3)0.01064 (13)0.0502 (6)
C241.2544 (3)0.0178 (3)0.02643 (16)0.0281 (6)
C251.2375 (3)0.1923 (3)0.05439 (16)0.0293 (6)
C261.1601 (3)0.2479 (3)0.12691 (16)0.0273 (6)
C371.0781 (3)0.1285 (3)0.32211 (15)0.0229 (5)
O371.2127 (2)0.0444 (2)0.32949 (11)0.0279 (4)
N310.9130 (3)0.2394 (3)0.53495 (13)0.0300 (5)
C321.0152 (3)0.2294 (3)0.47291 (16)0.0256 (5)
Cl31.23392 (9)0.31684 (9)0.50258 (4)0.03484 (18)
C330.9556 (3)0.1614 (3)0.38995 (15)0.0241 (5)
C340.7766 (3)0.1030 (3)0.37153 (17)0.0283 (6)
C350.6665 (3)0.1133 (4)0.43502 (17)0.0310 (6)
C360.7399 (3)0.1801 (4)0.51493 (17)0.0316 (6)
O40.0590 (2)0.6577 (2)0.29033 (11)0.0299 (4)
H140.80830.57930.13500.030*
H150.67470.84820.14310.032*
H160.44520.90870.22720.032*
H170.96300.43080.26340.028*
H221.06200.12710.17390.026*
H241.30990.02180.02260.034*
H251.27940.27400.02350.035*
H261.15000.36760.14600.033*
H340.72930.05600.31540.034*
H350.54310.07480.42320.037*
H360.66520.18520.55870.038*
H4A0.16990.67520.28860.036*
H4B0.05740.68030.34260.036*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N110.0232 (10)0.0232 (11)0.0338 (12)0.0027 (9)0.0048 (9)0.0022 (9)
C120.0215 (12)0.0245 (13)0.0270 (14)0.0017 (10)0.0027 (10)0.0064 (11)
Cl10.0327 (4)0.0339 (4)0.0447 (4)0.0031 (3)0.0142 (3)0.0163 (3)
C130.0223 (12)0.0161 (12)0.0270 (13)0.0008 (9)0.0012 (9)0.0010 (10)
C140.0257 (12)0.0224 (13)0.0271 (14)0.0024 (10)0.0045 (10)0.0011 (11)
C150.0309 (13)0.0206 (13)0.0292 (14)0.0006 (10)0.0023 (10)0.0055 (11)
C160.0230 (12)0.0191 (13)0.0362 (15)0.0018 (10)0.0006 (10)0.0012 (11)
C170.0287 (13)0.0172 (13)0.0242 (13)0.0009 (10)0.0073 (10)0.0034 (10)
O10.0364 (10)0.0198 (9)0.0324 (10)0.0012 (8)0.0015 (8)0.0024 (8)
N170.0253 (11)0.0132 (10)0.0310 (12)0.0032 (8)0.0054 (8)0.0023 (8)
N210.0259 (11)0.0172 (11)0.0267 (11)0.0059 (8)0.0073 (8)0.0052 (9)
C210.0222 (12)0.0208 (13)0.0242 (13)0.0047 (9)0.0061 (9)0.0051 (10)
C220.0221 (12)0.0192 (12)0.0252 (13)0.0007 (9)0.0028 (9)0.0061 (10)
C230.0286 (13)0.0198 (13)0.0244 (13)0.0035 (10)0.0026 (10)0.0010 (10)
N230.0442 (13)0.0257 (12)0.0264 (12)0.0075 (10)0.0057 (10)0.0017 (10)
O20.0689 (14)0.0202 (10)0.0473 (13)0.0016 (9)0.0227 (11)0.0067 (9)
O30.0756 (16)0.0350 (12)0.0432 (13)0.0106 (11)0.0305 (11)0.0014 (10)
C240.0291 (13)0.0326 (15)0.0236 (13)0.0042 (11)0.0068 (10)0.0051 (11)
C250.0327 (14)0.0296 (15)0.0284 (14)0.0007 (11)0.0071 (11)0.0105 (12)
C260.0331 (14)0.0215 (13)0.0282 (14)0.0022 (10)0.0062 (10)0.0051 (11)
C370.0259 (13)0.0187 (12)0.0235 (13)0.0039 (10)0.0032 (10)0.0023 (10)
O370.0287 (9)0.0256 (10)0.0299 (10)0.0053 (8)0.0046 (7)0.0051 (8)
N310.0317 (12)0.0311 (13)0.0283 (12)0.0007 (9)0.0079 (9)0.0052 (10)
C320.0284 (13)0.0201 (13)0.0286 (14)0.0011 (10)0.0053 (10)0.0036 (10)
Cl30.0300 (3)0.0395 (4)0.0331 (4)0.0070 (3)0.0042 (3)0.0011 (3)
C330.0284 (13)0.0191 (13)0.0261 (13)0.0035 (10)0.0074 (10)0.0046 (10)
C340.0330 (14)0.0244 (14)0.0269 (14)0.0021 (11)0.0024 (10)0.0038 (11)
C350.0281 (13)0.0353 (16)0.0316 (15)0.0040 (11)0.0062 (11)0.0098 (12)
C360.0323 (14)0.0326 (15)0.0332 (15)0.0029 (11)0.0123 (11)0.0094 (12)
O40.0283 (9)0.0289 (10)0.0312 (10)0.0024 (7)0.0062 (7)0.0002 (8)
Geometric parameters (Å, º) top
N11—C121.326 (3)C23—N231.466 (3)
N11—C161.336 (3)N23—O31.223 (3)
C12—C131.389 (3)N23—O21.227 (3)
C12—Cl11.735 (2)C24—C251.387 (4)
C13—C141.390 (3)C24—H240.95
C13—C171.505 (3)C25—C261.383 (4)
C14—C151.383 (3)C25—H250.95
C14—H140.95C26—H260.95
C15—C161.381 (3)C37—O371.214 (3)
C15—H150.95C37—C331.506 (3)
C16—H160.95N31—C321.327 (3)
C17—O11.215 (3)N31—C361.348 (3)
C17—N171.353 (3)C32—C331.384 (4)
N17—N211.399 (3)C32—Cl31.740 (2)
N17—H170.87C33—C341.385 (4)
N21—C371.388 (3)C34—C351.385 (4)
N21—C211.436 (3)C34—H340.95
C21—C221.383 (3)C35—C361.364 (4)
C21—C261.384 (3)C35—H350.95
C22—C231.380 (3)C36—H360.95
C22—H220.95O4—H4A0.84
C23—C241.381 (4)O4—H4B0.84
C12—N11—C16117.2 (2)C24—C23—N23118.9 (2)
N11—C12—C13125.0 (2)O3—N23—O2123.5 (2)
N11—C12—Cl1115.36 (18)O3—N23—C23118.3 (2)
C13—C12—Cl1119.63 (18)O2—N23—C23118.2 (2)
C12—C13—C14116.4 (2)C23—C24—C25117.8 (2)
C12—C13—C17122.3 (2)C23—C24—H24121.1
C14—C13—C17121.3 (2)C25—C24—H24121.1
C15—C14—C13119.8 (2)C26—C25—C24120.4 (2)
C15—C14—H14120.1C26—C25—H25119.8
C13—C14—H14120.1C24—C25—H25119.8
C16—C15—C14118.6 (2)C25—C26—C21120.2 (2)
C16—C15—H15120.7C25—C26—H26119.9
C14—C15—H15120.7C21—C26—H26119.9
N11—C16—C15123.0 (2)O37—C37—N21122.1 (2)
N11—C16—H16118.5O37—C37—C33121.9 (2)
C15—C16—H16118.5N21—C37—C33115.7 (2)
O1—C17—N17124.5 (2)C32—N31—C36117.2 (2)
O1—C17—C13124.3 (2)N31—C32—C33124.2 (2)
N17—C17—C13111.2 (2)N31—C32—Cl3114.70 (19)
C17—N17—N21119.7 (2)C33—C32—Cl3121.06 (19)
C17—N17—H17119.6C32—C33—C34117.0 (2)
N21—N17—H17118.2C32—C33—C37123.8 (2)
C37—N21—N17119.03 (19)C34—C33—C37118.8 (2)
C37—N21—C21121.76 (19)C33—C34—C35120.0 (2)
N17—N21—C21117.37 (18)C33—C34—H34120.0
C22—C21—C26120.7 (2)C35—C34—H34120.0
C22—C21—N21118.3 (2)C36—C35—C34118.2 (2)
C26—C21—N21120.9 (2)C36—C35—H35120.9
C23—C22—C21117.6 (2)C34—C35—H35120.9
C23—C22—H22121.2N31—C36—C35123.4 (2)
C21—C22—H22121.2N31—C36—H36118.3
C22—C23—C24123.3 (2)C35—C36—H36118.3
C22—C23—N23117.8 (2)H4A—O4—H4B99.2
C13—C17—N17—N21173.63 (19)C26—C21—C22—C231.8 (3)
C17—N17—N21—C2178.5 (3)N21—C21—C22—C23178.8 (2)
C17—N17—N21—C37116.7 (2)C21—C22—C23—C240.8 (4)
N17—N21—C37—C3330.2 (3)C21—C22—C23—N23178.2 (2)
N17—N21—C37—O37156.2 (2)C22—C23—N23—O3167.9 (2)
C12—C13—C17—N17110.2 (3)C24—C23—N23—O311.1 (4)
N17—N21—C21—C22142.1 (2)C22—C23—N23—O211.0 (3)
N21—C37—C33—C32133.4 (2)C24—C23—N23—O2169.9 (2)
C21—N21—C37—O378.0 (3)C22—C23—C24—C250.8 (4)
C21—N21—C37—C33165.7 (2)N23—C23—C24—C25179.8 (2)
C16—N11—C12—C131.0 (4)C23—C24—C25—C261.5 (4)
C16—N11—C12—Cl1177.08 (18)C24—C25—C26—C210.6 (4)
N11—C12—C13—C140.9 (4)C22—C21—C26—C251.1 (4)
Cl1—C12—C13—C14177.12 (18)N21—C21—C26—C25179.5 (2)
N11—C12—C13—C17178.7 (2)C36—N31—C32—C330.5 (4)
Cl1—C12—C13—C170.8 (3)C36—N31—C32—Cl3177.30 (19)
C12—C13—C14—C150.5 (4)N31—C32—C33—C341.0 (4)
C17—C13—C14—C15178.4 (2)Cl3—C32—C33—C34176.65 (19)
C13—C14—C15—C160.4 (4)N31—C32—C33—C37171.4 (2)
C12—N11—C16—C150.8 (4)Cl3—C32—C33—C3710.9 (3)
C14—C15—C16—N110.5 (4)O37—C37—C33—C3252.9 (3)
C12—C13—C17—O168.1 (3)O37—C37—C33—C34119.3 (3)
C14—C13—C17—O1114.1 (3)N21—C37—C33—C3454.3 (3)
C14—C13—C17—N1767.5 (3)C32—C33—C34—C350.4 (4)
O1—C17—N17—N218.0 (4)C37—C33—C34—C35172.4 (2)
C37—N21—C21—C2253.5 (3)C33—C34—C35—C360.6 (4)
C37—N21—C21—C26127.1 (2)C32—N31—C36—C350.6 (4)
N17—N21—C21—C2637.3 (3)C34—C35—C36—N311.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···N110.842.062.891 (3)170
O4—H4B···N31i0.841.972.805 (3)171
N17—H17···O4ii0.871.882.747 (3)175
C15—H15···O1iii0.952.563.228 (3)127
C26—H26···O2iii0.952.423.158 (3)134
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC18H11Cl2N5O4·H2O
Mr450.23
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)7.4435 (3), 7.8829 (5), 16.2657 (10)
α, β, γ (°)99.564 (2), 96.806 (3), 90.842 (3)
V3)933.94 (9)
Z2
Radiation typeMo Kα
µ (mm1)0.39
Crystal size (mm)0.16 × 0.14 × 0.03
Data collection
DiffractometerBruker KappaCCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.960, 0.988
No. of measured, independent and
observed [I > 2σ(I)] reflections
19029, 4263, 2991
Rint0.076
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.050, 0.120, 1.04
No. of reflections4263
No. of parameters271
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.37

Computer programs: COLLECT (Hooft, 1999), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top
N17—N211.399 (3)
C13—C17—N17—N21173.63 (19)C12—C13—C17—N17110.2 (3)
C17—N17—N21—C2178.5 (3)N17—N21—C21—C22142.1 (2)
C17—N17—N21—C37116.7 (2)N21—C37—C33—C32133.4 (2)
N17—N21—C37—C3330.2 (3)C21—N21—C37—O378.0 (3)
N17—N21—C37—O37156.2 (2)C21—N21—C37—C33165.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4A···N110.842.062.891 (3)170
O4—H4B···N31i0.841.972.805 (3)171
N17—H17···O4ii0.871.882.747 (3)175
C15—H15···O1iii0.952.563.228 (3)127
C26—H26···O2iii0.952.423.158 (3)134
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z; (iii) x, y+1, z.
 

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff of the Service for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Web of Science Google Scholar
First citationBernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573.  CrossRef CAS Web of Science Google Scholar
First citationFerguson, G. (1999). PRPKAPPA. University of Guelph, Canada.  Google Scholar
First citationHooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
First citationMcArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland.  Google Scholar
First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany.  Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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