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

Yan, L.; Zhao, H.; Chen, C.-L.

doi:10.1107/S1600536809025422

organic compounds

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doi:10.1107/S1600536809025422

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

Lin Yan,^a,^b ^* Hong Zhao ^c and Chun-Ling Chen ^d

^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 ). For their potential applications, see: Espinet et al. (1998 ); Nalwa et al. (1993 ); Schweizer et al. (1993 ).

Experimental

Crystal data

C₁₀H₁₀N₄·H₂O
M_r = 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 ) T_min = 0.980, T_max = 0.991
2143 measured reflections
910 independent reflections
583 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025422/at2834sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025422/at2834Isup2.hkl

checkCIF report

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 C═N 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%].

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

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	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·H₂O	F(000) = 216
M_r = 204.24	D_x = 1.287 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 519 reflections
a = 12.006 (4) Å	θ = 3.1–23.4°
b = 6.5806 (19) Å	µ = 0.09 mm⁻¹
c = 6.914 (2) Å	T = 296 K
β = 105.253 (6)°	Block, red
V = 527.0 (3) Å³	0.23 × 0.17 × 0.10 mm
Z = 2

Data collection top

Bruker SMART CCD area-detector diffractometer	910 independent reflections
Radiation source: fine-focus sealed tube	583 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ϕ and ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −14→12
T_min = 0.980, T_max = 0.991	k = −7→7
2143 measured reflections	l = −8→6

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.065	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.191	w = 1/[σ²(F_o²) + (0.1036P)²] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
910 reflections	Δρ_max = 0.24 e Å⁻³
74 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.06 (2)

Crystal data top

C₁₀H₁₀N₄·H₂O	V = 527.0 (3) Å³
M_r = 204.24	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 12.006 (4) Å	µ = 0.09 mm⁻¹
b = 6.5806 (19) Å	T = 296 K
c = 6.914 (2) Å	0.23 × 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)
T_min = 0.980, T_max = 0.991	R_int = 0.052
2143 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	1 restraint
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.24 e Å⁻³
910 reflections	Δρ_min = −0.16 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	0.1938 (3)	0.5705 (6)	0.1197 (5)	0.0584 (11)
H1B	0.1862	0.4418	0.1702	0.070*
C2	0.1062 (3)	0.7050 (6)	0.0509 (6)	0.0622 (11)
H2C	0.0287	0.6846	0.0448	0.075*
C3	0.1546 (3)	0.8794 (5)	−0.0091 (6)	0.0614 (11)
H3A	0.1152	0.9973	−0.0607	0.074*
C4	0.2711 (3)	0.8453 (5)	0.0221 (5)	0.0456 (9)
C5	0.3587 (3)	0.9809 (5)	−0.0076 (5)	0.0489 (9)
H5A	0.3398	1.1158	−0.0408	0.059*
N1	0.2931 (2)	0.6536 (4)	0.1029 (4)	0.0499 (9)
H1A	0.3597	0.5962	0.1372	0.060*
N2	0.4646 (2)	0.9192 (4)	0.0110 (4)	0.0481 (8)
O1W	0.5000	0.4090 (5)	0.2500	0.0531 (10)
H1W	0.487 (3)	0.342 (5)	0.343 (4)	0.055 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.056 (2)	0.056 (2)	0.065 (2)	−0.0124 (18)	0.0201 (17)	0.0022 (18)
C2	0.041 (2)	0.064 (2)	0.084 (3)	−0.0099 (17)	0.0200 (19)	0.000 (2)
C3	0.050 (2)	0.056 (2)	0.079 (3)	0.0044 (17)	0.0179 (18)	−0.0031 (19)
C4	0.0428 (18)	0.0454 (18)	0.0471 (19)	−0.0032 (15)	0.0095 (14)	−0.0033 (15)
C5	0.048 (2)	0.0484 (19)	0.050 (2)	0.0017 (15)	0.0106 (15)	0.0009 (16)
N1	0.0400 (16)	0.0477 (17)	0.0600 (19)	−0.0018 (12)	0.0099 (13)	0.0041 (14)
N2	0.0531 (18)	0.0462 (16)	0.0456 (17)	−0.0090 (12)	0.0142 (13)	−0.0017 (13)
O1W	0.051 (2)	0.0377 (19)	0.074 (3)	0.000	0.0219 (19)	0.000

Geometric parameters (Å, º) top

C1—N1	1.344 (4)	C4—N1	1.377 (4)
C1—C2	1.361 (5)	C4—C5	1.435 (5)
C1—H1B	0.9300	C5—N2	1.308 (4)
C2—C3	1.397 (5)	C5—H5A	0.9300
C2—H2C	0.9300	N1—H1A	0.8600
C3—C4	1.376 (5)	N2—N2ⁱ	1.395 (5)
C3—H3A	0.9300	O1W—H1W	0.826 (10)

N1—C1—C2	109.1 (3)	C3—C4—C5	129.0 (3)
N1—C1—H1B	125.5	N1—C4—C5	123.9 (3)
C2—C1—H1B	125.5	N2—C5—C4	121.5 (3)
C1—C2—C3	107.1 (3)	N2—C5—H5A	119.2
C1—C2—H2C	126.4	C4—C5—H5A	119.2
C3—C2—H2C	126.4	C1—N1—C4	109.1 (3)
C4—C3—C2	107.7 (3)	C1—N1—H1A	125.4
C4—C3—H3A	126.1	C4—N1—H1A	125.4
C2—C3—H3A	126.1	C5—N2—N2ⁱ	110.9 (3)
C3—C4—N1	106.9 (3)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1W	0.86	2.07	2.910 (3)	167
O1W—H1W···N2ⁱⁱ	0.83 (1)	2.13 (2)	2.917 (3)	159 (4)

Symmetry code: (ii) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₁₀N₄·H₂O
M_r	204.24
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	296
a, b, c (Å)	12.006 (4), 6.5806 (19), 6.914 (2)
β (°)	105.253 (6)
V (Å³)	527.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.17 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.980, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	2143, 910, 583
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.191, 1.05
No. of reflections	910
No. of parameters	74
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1W	0.86	2.07	2.910 (3)	166.6
O1W—H1W···N2ⁱ	0.826 (10)	2.132 (16)	2.917 (3)	159 (4)

Symmetry code: (i) x, −y+1, z+1/2.

References

Bruker (2001). SAINT-Plus and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Espinet, 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
Khodair, A. I. & Bertrand, P. (1998). Tetrahedron, 54, 4859–4862. Web of Science CrossRef CAS Google Scholar
Nalwa, H. S., Kakatu, A. & Mukoh, A. (1993). J. Appl. Phys. 73, 4743–4745. CrossRef CAS Web of Science Google Scholar
Schweizer, E. E., Rheingold, A. L. & Bruch, M. (1993). J. Org. Chem. 58, 4339–4345. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1787

doi:10.1107/S1600536809025422

Open

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