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

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ISSN: 2056-9890

1,2-Bis(1H-pyrrol-2-ylmethyl­ene)di­azane monohydrate

aInstitute of Pharmacy, Henan University, Kaifeng 475004, People's Republic of China, bKey Laboratory of Natural Medicine and Immunal Engineering, Henan University, Kaifeng 475004, People's Republic of China, cHenan Chemical Industry Senior Technician School, Kaifeng 475001, People's Republic of China, and dInstitute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, People's Republic of China
*Correspondence e-mail: yanlin_online@163.com

(Received 26 June 2009; accepted 1 July 2009; online 8 July 2009)

The mol­ecular structure of title compound, C10H10N4·H2O, has an inversion centre located on the mid-point of the N—N bond of the mol­ecule. A twofold rotation axis passes through the water O atom. In the crystal structure, a two-dimensional network is constructed through N—H⋯O and O—H⋯N hydrogen bonds.

Related literature

For the biological properties of azines, see: Khodair & Bertrand (1998[Khodair, A. I. & Bertrand, P. (1998). Tetrahedron, 54, 4859-4862.]). For their potential applications, see: Espinet et al. (1998[Espinet, P., Etxebarria, J., Marcos, M., Péres, J., Remón, A. & Serrano, J. L. (1998). Angew. Chem. Int. Ed. Engl. 28, 1065-1066.]); Nalwa et al. (1993[Nalwa, H. S., Kakatu, A. & Mukoh, A. (1993). J. Appl. Phys. 73, 4743-4745.]); Schweizer et al. (1993[Schweizer, E. E., Rheingold, A. L. & Bruch, M. (1993). J. Org. Chem. 58, 4339-4345.]).

[Scheme 1]

Experimental

Crystal data
  • C10H10N4·H2O

  • Mr = 204.24

  • Monoclinic, P 2/c

  • a = 12.006 (4) Å

  • b = 6.5806 (19) Å

  • c = 6.914 (2) Å

  • β = 105.253 (6)°

  • V = 527.0 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 296 K

  • 0.23 × 0.17 × 0.10 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2001[Sheldrick, G. M. (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.980, Tmax = 0.991

  • 2143 measured reflections

  • 910 independent reflections

  • 583 reflections with I > 2σ(I)

  • Rint = 0.052

Refinement
  • R[F2 > 2σ(F2)] = 0.065

  • wR(F2) = 0.191

  • S = 1.05

  • 910 reflections

  • 74 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.16 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1A⋯O1W 0.86 2.07 2.910 (3) 167
O1W—H1W⋯N2i 0.826 (10) 2.132 (16) 2.917 (3) 159 (4)
Symmetry code: (i) [x, -y+1, z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 2001[Bruker (2001). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2001[Bruker (2001). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; 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: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: PLATON.

Supporting information


Comment top

Recently, dinucleating diazine ligands containing a single N—N bond have received considerable attention due to their biological properties (Khodair, et al. 1998), their potential applicability in bond formations (Schweizer, et al., 1993), the design of liquid crystals (Espinet, et al., 1998) as well as non-linear optical materials (Nalwa, et al., 1993). we now report the structure of the title compound, (I).

Compound (I) consists of a 1,2-bis((1H-pyrrol-2-yl)methylene)hydrazine organic molecule and a crystal water molecule (Fig.1). The molecular structure of title compound has an inversion centre located on the midpoint of the N—N bond of the molecule. A two-fold rotation axis pass through the water O atom. The N1/C1–C4 ring in (I) is coplanar, in which the C–N bond distances range from 1.344 (4) to 1.377 (4) Å. However, C5—N2 [1.308 (4) Å] is typical for a CN double bond. The N2—N2b bond distance is 1.395 (5), indicating a N—N single bond.

Two intra and intermolecular hydrogen bonds N—H···O and O—H···N (Table 1) help to establish the molecular conformation, and constructing infinite two-dimensional network along [100] plane (Fig. 2).

Related literature top

For the biological properties of dinucleating diazine ligands, see: Khodair & Bertrand (1998). For their potential applications, see: Espinet et al. (1998); Nalwa et al. (1993); Schweizer et al. (1993).

Experimental top

An ethanol solution containing hydrazine hydrate (0.20 g, 4 mmol) was added dropwise with constant stirring and slow heating to a solution of pyrrole-2-carboxaldehyde (0.38 g, 4 mmol) in the same solvent with five drops of acetic acid. The solution was refluxed for 2 h. Then the resultant solution was filtered. Red crystals suitable for X-ray studies were obtained by slow evaporation of the ethanol solution [yield: 65%].

Refinement top

The water H atom was found from a difference Fourier map and refined freely. Other H atoms were treated as riding, with C—H distances of 0.93 Å and N—H distances of 0.86 Å, and were refined as riding with Uiso(H)=1.2Ueq(C and N).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Two-dimensional structure of (I) along [100] direction. Hydrogen bonds are shown in the dashing line.
1,2-Bis(1H-pyrrol-2-ylmethylene)diazane monohydrate top
Crystal data top
C10H10N4·H2OF(000) = 216
Mr = 204.24Dx = 1.287 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 519 reflections
a = 12.006 (4) Åθ = 3.1–23.4°
b = 6.5806 (19) ŵ = 0.09 mm1
c = 6.914 (2) ÅT = 296 K
β = 105.253 (6)°Block, red
V = 527.0 (3) Å30.23 × 0.17 × 0.10 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer
910 independent reflections
Radiation source: fine-focus sealed tube583 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ϕ and ω scansθmax = 25.1°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
h = 1412
Tmin = 0.980, Tmax = 0.991k = 77
2143 measured reflectionsl = 86
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)] = 0.065H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.191 w = 1/[σ2(Fo2) + (0.1036P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
910 reflectionsΔρmax = 0.24 e Å3
74 parametersΔρmin = 0.16 e Å3
1 restraintExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.06 (2)
Crystal data top
C10H10N4·H2OV = 527.0 (3) Å3
Mr = 204.24Z = 2
Monoclinic, P2/cMo Kα radiation
a = 12.006 (4) ŵ = 0.09 mm1
b = 6.5806 (19) ÅT = 296 K
c = 6.914 (2) Å0.23 × 0.17 × 0.10 mm
β = 105.253 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
910 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
583 reflections with I > 2σ(I)
Tmin = 0.980, Tmax = 0.991Rint = 0.052
2143 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0651 restraint
wR(F2) = 0.191H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.24 e Å3
910 reflectionsΔρmin = 0.16 e Å3
74 parameters
Special details top

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) top
xyzUiso*/Ueq
C10.1938 (3)0.5705 (6)0.1197 (5)0.0584 (11)
H1B0.18620.44180.17020.070*
C20.1062 (3)0.7050 (6)0.0509 (6)0.0622 (11)
H2C0.02870.68460.04480.075*
C30.1546 (3)0.8794 (5)0.0091 (6)0.0614 (11)
H3A0.11520.99730.06070.074*
C40.2711 (3)0.8453 (5)0.0221 (5)0.0456 (9)
C50.3587 (3)0.9809 (5)0.0076 (5)0.0489 (9)
H5A0.33981.11580.04080.059*
N10.2931 (2)0.6536 (4)0.1029 (4)0.0499 (9)
H1A0.35970.59620.13720.060*
N20.4646 (2)0.9192 (4)0.0110 (4)0.0481 (8)
O1W0.50000.4090 (5)0.25000.0531 (10)
H1W0.487 (3)0.342 (5)0.343 (4)0.055 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.056 (2)0.056 (2)0.065 (2)0.0124 (18)0.0201 (17)0.0022 (18)
C20.041 (2)0.064 (2)0.084 (3)0.0099 (17)0.0200 (19)0.000 (2)
C30.050 (2)0.056 (2)0.079 (3)0.0044 (17)0.0179 (18)0.0031 (19)
C40.0428 (18)0.0454 (18)0.0471 (19)0.0032 (15)0.0095 (14)0.0033 (15)
C50.048 (2)0.0484 (19)0.050 (2)0.0017 (15)0.0106 (15)0.0009 (16)
N10.0400 (16)0.0477 (17)0.0600 (19)0.0018 (12)0.0099 (13)0.0041 (14)
N20.0531 (18)0.0462 (16)0.0456 (17)0.0090 (12)0.0142 (13)0.0017 (13)
O1W0.051 (2)0.0377 (19)0.074 (3)0.0000.0219 (19)0.000
Geometric parameters (Å, º) top
C1—N11.344 (4)C4—N11.377 (4)
C1—C21.361 (5)C4—C51.435 (5)
C1—H1B0.9300C5—N21.308 (4)
C2—C31.397 (5)C5—H5A0.9300
C2—H2C0.9300N1—H1A0.8600
C3—C41.376 (5)N2—N2i1.395 (5)
C3—H3A0.9300O1W—H1W0.826 (10)
N1—C1—C2109.1 (3)C3—C4—C5129.0 (3)
N1—C1—H1B125.5N1—C4—C5123.9 (3)
C2—C1—H1B125.5N2—C5—C4121.5 (3)
C1—C2—C3107.1 (3)N2—C5—H5A119.2
C1—C2—H2C126.4C4—C5—H5A119.2
C3—C2—H2C126.4C1—N1—C4109.1 (3)
C4—C3—C2107.7 (3)C1—N1—H1A125.4
C4—C3—H3A126.1C4—N1—H1A125.4
C2—C3—H3A126.1C5—N2—N2i110.9 (3)
C3—C4—N1106.9 (3)
Symmetry code: (i) x+1, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1W0.862.072.910 (3)167
O1W—H1W···N2ii0.83 (1)2.13 (2)2.917 (3)159 (4)
Symmetry code: (ii) x, y+1, z+1/2.

Experimental details

Crystal data
Chemical formulaC10H10N4·H2O
Mr204.24
Crystal system, space groupMonoclinic, P2/c
Temperature (K)296
a, b, c (Å)12.006 (4), 6.5806 (19), 6.914 (2)
β (°) 105.253 (6)
V3)527.0 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.23 × 0.17 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2001)
Tmin, Tmax0.980, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
2143, 910, 583
Rint0.052
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.065, 0.191, 1.05
No. of reflections910
No. of parameters74
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.16

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1W0.862.072.910 (3)166.6
O1W—H1W···N2i0.826 (10)2.132 (16)2.917 (3)159 (4)
Symmetry code: (i) x, y+1, z+1/2.
 

References

First citationBruker (2001). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationEspinet, P., Etxebarria, J., Marcos, M., Péres, J., Remón, A. & Serrano, J. L. (1998). Angew. Chem. Int. Ed. Engl. 28, 1065–1066.  CrossRef Web of Science Google Scholar
First citationKhodair, A. I. & Bertrand, P. (1998). Tetrahedron, 54, 4859–4862.  Web of Science CrossRef CAS Google Scholar
First citationNalwa, H. S., Kakatu, A. & Mukoh, A. (1993). J. Appl. Phys. 73, 4743–4745.  CrossRef CAS Web of Science Google Scholar
First citationSchweizer, E. E., Rheingold, A. L. & Bruch, M. (1993). J. Org. Chem. 58, 4339–4345.  CSD CrossRef CAS Web of Science Google Scholar
First citationSheldrick, G. M. (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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