N'-[(E)-(3-Fluoro-pyridin-2-yl)methyl-idene]pyridine-3-carbohydrazide dihydrate.

The organic molecule in the title dihydrate, C12H9FN4O·2H2O, exists in the E conformation with respect to the azo-methane C=N double bond. The mol-ecule is approximately planar, with a maximum deviation of 0.117 (1) Å for the carbonyl O atom from the mean plane of the mol-ecule. Both pyridine rings are essentially coplanar with the central C(=O)N2C unit [dihedral angles = 1.99 (7) and 5.71 (8)°], exhibiting a significant difference in dihedral angles from its benzohydrazide analogue. The crystal packing features N-H⋯O, O-H⋯N and O-H⋯O hydrogen-bond inter-actions, which lead to the formation of a chain along the c-axis direction through one of the water mol-ecules present, and these chains are stacked one over the other by means of π-π inter-actions [with centroid-centroid distances of 3.7099 (10) and 3.6322 (10) Å] between the aromatic rings in neighbouring anti-parallel mol-ecules, building a three-dimensional supra-molecular network.

Related literature

For the biological activity of carbohydrazide derivatives, see: Sreeja et al. (2004 ▶); Havanur et al. (2010 ▶); Despaigne et al. (2010 ▶). For the synthesis of related compounds, see: Kuriakose et al. (2007 ▶). For a related structure, see Nair et al. (2012 ▶).

Experimental

Crystal data

C12H9FN4O·2H2O

M = 280.26

Monoclinic,

a = 7.3023 (7) Å

b = 14.4031 (17) Å

c = 12.6422 (13) Å

β = 94.842 (3)°

V = 1324.9 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 296 K

0.41 × 0.21 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.963, T max = 0.969

9779 measured reflections

3237 independent reflections

2339 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.149

S = 1.04

3237 reflections

202 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) Global, I. DOI: 10.1107/S1600536814006072/bv2232sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814006072/bv2232Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814006072/bv2232Isup3.cml

CCDC reference: 992525

Additional supporting information: crystallographic information; 3D view; checkCIF report

C12H9FN4O·2H2O	F(000) = 584
Mr = 280.26	Dx = 1.405 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4225 reflections
a = 7.3023 (7) Å	θ = 2.8–28.0°
b = 14.4031 (17) Å	µ = 0.11 mm−1
c = 12.6422 (13) Å	T = 296 K
β = 94.842 (3)°	Needle, colorless
V = 1324.9 (2) Å3	0.41 × 0.21 × 0.20 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	3237 independent reflections
Radiation source: fine-focus sealed tube	2339 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 8.33 pixels mm-1	θmax = 28.2°, θmin = 2.8°
ω and φ scan	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −17→19
Tmin = 0.963, Tmax = 0.969	l = −16→16
9779 measured reflections

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)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.149	w = 1/[σ2(Fo2) + (0.0712P)2 + 0.3471P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3237 reflections	Δρmax = 0.29 e Å−3
202 parameters	Δρmin = −0.20 e Å−3
7 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.079 (6)

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.

	x	y	z	Uiso*/Ueq
O2S	0.5863 (3)	0.45901 (12)	0.25212 (11)	0.0835 (5)
F1	0.77433 (17)	1.26247 (8)	0.16447 (8)	0.0683 (4)
O1	0.7242 (2)	0.88186 (10)	−0.13894 (9)	0.0770 (5)
O1S	0.7875 (3)	0.96417 (11)	0.24957 (11)	0.0792 (5)
N1	0.60794 (18)	1.20176 (10)	−0.10083 (10)	0.0470 (3)
C6	0.7337 (2)	1.10213 (11)	0.04205 (11)	0.0427 (4)
H6	0.7710	1.0945	0.1137	0.051*
N2	0.73006 (18)	1.03335 (9)	−0.02053 (10)	0.0440 (3)
N4	0.8628 (2)	0.62144 (10)	−0.03962 (11)	0.0543 (4)
C1	0.5563 (2)	1.28602 (13)	−0.13628 (13)	0.0530 (4)
H1	0.5071	1.2915	−0.2063	0.064*
C2	0.5718 (2)	1.36560 (12)	−0.07482 (15)	0.0548 (4)
H2	0.5331	1.4226	−0.1031	0.066*
C3	0.6450 (3)	1.35901 (12)	0.02835 (14)	0.0540 (4)
H3	0.6583	1.4109	0.0721	0.065*
C4	0.6980 (2)	1.27194 (11)	0.06413 (12)	0.0455 (4)
C5	0.6785 (2)	1.19411 (10)	0.00027 (11)	0.0396 (3)
N3	0.78095 (19)	0.94872 (9)	0.02199 (10)	0.0435 (3)
C7	0.7743 (2)	0.87503 (11)	−0.04464 (11)	0.0452 (4)
C8	0.8311 (2)	0.78321 (10)	0.00146 (11)	0.0396 (3)
C9	0.8966 (2)	0.76657 (11)	0.10573 (12)	0.0475 (4)
H9	0.9101	0.8151	0.1543	0.057*
C10	0.9414 (2)	0.67696 (12)	0.13635 (13)	0.0514 (4)
H10	0.9836	0.6638	0.2062	0.062*
C11	0.9223 (2)	0.60731 (12)	0.06144 (14)	0.0530 (4)
H11	0.9528	0.5471	0.0828	0.064*
C12	0.8172 (2)	0.70823 (12)	−0.06745 (12)	0.0479 (4)
H12	0.7734	0.7191	−0.1376	0.057*
H3'	0.809 (3)	0.9462 (13)	0.0910 (8)	0.057 (5)*
H2A	0.597 (3)	0.4119 (11)	0.2949 (16)	0.088 (8)*
H1A	0.807 (4)	0.9453 (19)	0.3148 (10)	0.110 (9)*
H2B	0.623 (4)	0.5053 (11)	0.2904 (17)	0.097 (9)*
H1B	0.902 (2)	0.962 (3)	0.233 (3)	0.19 (2)*

	U11	U22	U33	U12	U13	U23
O2S	0.1384 (15)	0.0589 (9)	0.0478 (7)	−0.0012 (9)	−0.0228 (8)	−0.0033 (7)
F1	0.1063 (9)	0.0553 (6)	0.0417 (5)	0.0069 (6)	−0.0038 (5)	−0.0027 (4)
O1	0.1404 (14)	0.0510 (8)	0.0373 (6)	0.0225 (8)	−0.0057 (7)	−0.0003 (5)
O1S	0.1276 (15)	0.0674 (9)	0.0409 (7)	0.0091 (9)	−0.0028 (8)	0.0039 (6)
N1	0.0501 (7)	0.0474 (8)	0.0426 (7)	0.0026 (6)	−0.0009 (5)	0.0049 (6)
C6	0.0482 (8)	0.0418 (8)	0.0377 (7)	0.0021 (6)	0.0007 (6)	0.0040 (6)
N2	0.0547 (8)	0.0379 (7)	0.0393 (6)	0.0069 (5)	0.0033 (5)	0.0047 (5)
N4	0.0634 (9)	0.0430 (8)	0.0545 (8)	0.0091 (6)	−0.0071 (6)	−0.0092 (6)
C1	0.0532 (10)	0.0578 (10)	0.0474 (8)	0.0067 (8)	0.0002 (7)	0.0133 (7)
C2	0.0565 (10)	0.0453 (9)	0.0638 (10)	0.0106 (7)	0.0123 (8)	0.0164 (8)
C3	0.0659 (11)	0.0395 (9)	0.0584 (10)	0.0046 (7)	0.0159 (8)	0.0007 (7)
C4	0.0525 (9)	0.0449 (8)	0.0397 (7)	0.0033 (7)	0.0069 (6)	0.0023 (6)
C5	0.0403 (8)	0.0389 (8)	0.0400 (7)	0.0023 (6)	0.0061 (6)	0.0042 (6)
N3	0.0568 (8)	0.0372 (7)	0.0360 (6)	0.0067 (5)	0.0011 (5)	0.0033 (5)
C7	0.0582 (9)	0.0418 (8)	0.0359 (7)	0.0072 (7)	0.0060 (6)	0.0005 (6)
C8	0.0404 (8)	0.0397 (8)	0.0390 (7)	0.0041 (6)	0.0048 (6)	−0.0008 (6)
C9	0.0596 (10)	0.0420 (8)	0.0406 (8)	0.0068 (7)	0.0021 (7)	−0.0035 (6)
C10	0.0610 (10)	0.0500 (9)	0.0419 (8)	0.0113 (7)	−0.0033 (7)	0.0036 (7)
C11	0.0577 (10)	0.0408 (9)	0.0589 (10)	0.0112 (7)	−0.0036 (8)	0.0016 (7)
C12	0.0540 (9)	0.0465 (9)	0.0417 (8)	0.0070 (7)	−0.0041 (6)	−0.0045 (6)

O2S—H2A	0.866 (9)	C2—C3	1.371 (2)
O2S—H2B	0.855 (9)	C2—H2	0.9300
F1—C4	1.3486 (18)	C3—C4	1.377 (2)
O1—C7	1.2211 (18)	C3—H3	0.9300
O1S—H1A	0.869 (10)	C4—C5	1.382 (2)
O1S—H1B	0.881 (10)	N3—C7	1.3534 (19)
N1—C1	1.337 (2)	N3—H3'	0.880 (9)
N1—C5	1.3417 (18)	C7—C8	1.490 (2)
C6—N2	1.267 (2)	C8—C9	1.385 (2)
C6—C5	1.470 (2)	C8—C12	1.386 (2)
C6—H6	0.9300	C9—C10	1.379 (2)
N2—N3	1.3707 (17)	C9—H9	0.9300
N4—C11	1.330 (2)	C10—C11	1.379 (2)
N4—C12	1.333 (2)	C10—H10	0.9300
C1—C2	1.384 (3)	C11—H11	0.9300
C1—H1	0.9300	C12—H12	0.9300
H2A—O2S—H2B	104.5 (17)	C4—C5—C6	120.63 (13)
H1A—O1S—H1B	97.5 (19)	C7—N3—N2	117.32 (12)
C1—N1—C5	117.95 (14)	C7—N3—H3'	125.3 (13)
N2—C6—C5	119.32 (13)	N2—N3—H3'	117.3 (13)
N2—C6—H6	120.3	O1—C7—N3	122.44 (14)
C5—C6—H6	120.3	O1—C7—C8	120.26 (14)
C6—N2—N3	117.37 (13)	N3—C7—C8	117.29 (13)
C11—N4—C12	116.80 (14)	C9—C8—C12	117.69 (14)
N1—C1—C2	123.80 (15)	C9—C8—C7	126.03 (13)
N1—C1—H1	118.1	C12—C8—C7	116.28 (13)
C2—C1—H1	118.1	C10—C9—C8	118.94 (14)
C3—C2—C1	118.92 (15)	C10—C9—H9	120.5
C3—C2—H2	120.5	C8—C9—H9	120.5
C1—C2—H2	120.5	C11—C10—C9	118.72 (15)
C2—C3—C4	116.87 (16)	C11—C10—H10	120.6
C2—C3—H3	121.6	C9—C10—H10	120.6
C4—C3—H3	121.6	N4—C11—C10	123.68 (15)
F1—C4—C3	118.90 (15)	N4—C11—H11	118.2
F1—C4—C5	118.79 (14)	C10—C11—H11	118.2
C3—C4—C5	122.30 (15)	N4—C12—C8	124.16 (14)
N1—C5—C4	120.16 (14)	N4—C12—H12	117.9
N1—C5—C6	119.21 (13)	C8—C12—H12	117.9
C5—C6—N2—N3	−179.37 (13)	N2—N3—C7—O1	−0.6 (3)
C5—N1—C1—C2	0.1 (3)	N2—N3—C7—C8	179.54 (13)
N1—C1—C2—C3	0.4 (3)	O1—C7—C8—C9	177.57 (17)
C1—C2—C3—C4	−0.3 (3)	N3—C7—C8—C9	−2.5 (2)
C2—C3—C4—F1	178.65 (15)	O1—C7—C8—C12	−2.0 (2)
C2—C3—C4—C5	−0.3 (3)	N3—C7—C8—C12	177.88 (14)
C1—N1—C5—C4	−0.8 (2)	C12—C8—C9—C10	−1.2 (2)
C1—N1—C5—C6	179.01 (14)	C7—C8—C9—C10	179.25 (15)
F1—C4—C5—N1	−178.09 (13)	C8—C9—C10—C11	1.1 (3)
C3—C4—C5—N1	0.9 (2)	C12—N4—C11—C10	−1.1 (3)
F1—C4—C5—C6	2.1 (2)	C9—C10—C11—N4	0.0 (3)
C3—C4—C5—C6	−178.89 (15)	C11—N4—C12—C8	1.1 (3)
N2—C6—C5—N1	6.6 (2)	C9—C8—C12—N4	0.0 (3)
N2—C6—C5—C4	−173.62 (15)	C7—C8—C12—N4	179.68 (16)
C6—N2—N3—C7	179.03 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3′···O1S	0.88 (1)	2.04 (1)	2.8821 (19)	160 (2)
O2S—H2A···N1i	0.87 (1)	2.10 (1)	2.965 (2)	177 (2)
O1S—H1A···N4i	0.87 (1)	2.09 (1)	2.946 (2)	170 (3)
O2S—H2B···O1i	0.86 (1)	1.97 (1)	2.816 (2)	172 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3′⋯O1S	0.88 (1)	2.04 (1)	2.8821 (19)	160 (2)
O1S—H1A⋯N4i	0.87 (1)	2.09 (1)	2.946 (2)	170 (3)
O2S—H2A⋯N1i	0.87 (1)	2.10 (1)	2.965 (2)	177 (2)
O2S—H2B⋯O1i	0.86 (1)	1.97 (1)	2.816 (2)	172 (2)

Symmetry code: (i) .