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

Abstract

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,

• a = 12.006 (4) Å

• b = 6.5806 (19) Å

• c = 6.914 (2) Å

• β = 105.253 (6)°

• V = 527.0 (3) ų

• 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[F ² > 2σ(F ²)] = 0.065

• wR(F ²) = 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

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.

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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

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 U_iso(H)=1.2U_eq(C and N).

Figures

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.

Crystal data

C10H10N4·H2O	F(000) = 216
Mr = 204.24	Dx = 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

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

Refinement

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(Fo2) + (0.1036P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
910 reflections	Δρmax = 0.24 e Å−3
74 parameters	Δρmin = −0.15 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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1, −y+2, −z.

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···N2ii	0.83 (1)	2.13 (2)	2.917 (3)	159 (4)

Symmetry codes: (ii) x, −y+1, z+1/2.