Crystal structure of 4-formyl-pyridine semicarbazone hemihydrate.

The mol-ecule of the title compound C7H8N4O·0.5H2O, alternatively called (E)-1-(pyridin-4-yl-methyl-ene)semi-carb-azide hemihydrate, is in the E conformation and is almost planar; the r.m.s. deviation of the positions of the atoms of the pyridine ring from the best-fit plane is 0.0039 Å. The C, N and O atoms of the rest of the mol-ecule sits close on this plane with a largest deviation of 0.115 (4) Å for the O atom of the semicarbazone moiety. There is an intra-molecular N-H⋯N hydrogen bond. In the crystal, mol-ecules are linked into an infinite three-dimensional network by classical N-H⋯Os (s = semicarbazone) and Ow-H⋯N (w = water) hydrogen bonds.

Related literature

For the preparation of coordination compounds of 4-formyl­pyridine semicarbazone with cobalt and zinc, see: Zhou et al. (2006a ▸,b ▸). For the spectroscopic (FT–IR, NMR and UV–vis) properties of 4- and 3-formyl­pyridine semicarbazones, see: Beraldo et al. (2001 ▸). For the crystal structure of 4-formyl­pyridine thio­semicarbazone, see: Restivo & Palenik (1970 ▸). For the crystal structures of 2-formyl­pyridine semicarbazone and several coordination compounds published by our group, see: Garbelini et al. (2008 ▸, 2009 ▸, 2011 ▸, 2012 ▸). Geometrical analysis was performed with Mogul (Bruno et al., 2004 ▸).

Experimental

Crystal data

2C7H8N4O·H2O

M = 346.36

Monoclinic,

a = 25.0636 (13) Å

b = 5.3725 (3) Å

c = 13.0124 (7) Å

β = 111.717 (3)°

V = 1627.81 (16) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 296 K

0.82 × 0.27 × 0.20 mm

Data collection

Bruker X8 Kappa APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T min = 0.860, T max = 0.937

20739 measured reflections

1795 independent reflections

1502 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.094

S = 1.04

1795 reflections

127 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015 ▸ ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸ ▸); molecular graphics: DIAMOND (Crystal Impact, 2014 ▸); software used to prepare material for publication: SHELXL2014.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015007276/lr2134sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015007276/lr2134Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015007276/lr2134Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015007276/lr2134fig1.tif

View of the title mol­ecule·Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b a . DOI: 10.1107/S2056989015007276/lr2134fig2.tif

The mol­ecular packing viewed down the crystallograpic b axis, with the a axis pointed down, showing the three dimensional hydrogen bonding network.

CCDC reference: 1059160

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

2C7H8N4O·H2O	F(000) = 728
Mr = 346.36	Dx = 1.413 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.0636 (13) Å	Cell parameters from 5941 reflections
b = 5.3725 (3) Å	θ = 2.8–26.2°
c = 13.0124 (7) Å	µ = 0.11 mm−1
β = 111.717 (3)°	T = 296 K
V = 1627.81 (16) Å3	Block, clear light colourless
Z = 4	0.82 × 0.27 × 0.20 mm

Bruker X8 Kappa APEXII diffractometer	1795 independent reflections
Radiation source: sealed ceramic X ray tube, Siemens KFF	1502 reflections with I > 2σ(I)
Graphite crystal monochromator	Rint = 0.029
Detector resolution: 8.3333 pixels mm-1	θmax = 27.1°, θmin = 1.8°
0.5 ° ω & φ scans	h = −32→32
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −6→6
Tmin = 0.860, Tmax = 0.937	l = −16→16
20739 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.094	w = 1/[σ2(Fo2) + (0.0436P)2 + 0.8364P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
1795 reflections	Δρmax = 0.23 e Å−3
127 parameters	Δρmin = −0.20 e Å−3
1 restraint	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0067 (8)

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.

	x	y	z	Uiso*/Ueq
O1	0.74966 (4)	−0.16017 (16)	0.36432 (7)	0.0411 (2)
N1	0.70517 (5)	0.2096 (2)	0.30449 (9)	0.0410 (3)
H1NA	0.6859 (8)	0.326 (3)	0.3188 (14)	0.061*
H1NB	0.7226 (7)	0.234 (3)	0.2545 (15)	0.061*
N2	0.69806 (5)	0.00971 (19)	0.45499 (9)	0.0373 (3)
H2N	0.7110 (7)	−0.107 (3)	0.5079 (14)	0.056*
N3	0.66491 (4)	0.20246 (18)	0.46659 (8)	0.0336 (3)
N4	0.54246 (5)	0.7238 (2)	0.61921 (10)	0.0430 (3)
C1	0.71939 (5)	0.0154 (2)	0.37260 (9)	0.0315 (3)
C2	0.65096 (5)	0.1908 (2)	0.55129 (10)	0.0329 (3)
H2	0.6646	0.0596	0.6007	0.039*
C3	0.61410 (5)	0.3783 (2)	0.57272 (9)	0.0309 (3)
C4	0.59797 (5)	0.3495 (2)	0.66315 (10)	0.0374 (3)
H4	0.6108	0.2134	0.71	0.045*
C5	0.56274 (6)	0.5251 (3)	0.68271 (11)	0.0431 (3)
H5	0.5526	0.5034	0.744	0.052*
C6	0.59294 (5)	0.5840 (2)	0.50545 (10)	0.0369 (3)
H6	0.6025	0.6106	0.4437	0.044*
C7	0.55757 (6)	0.7483 (2)	0.53140 (11)	0.0411 (3)
H7	0.5434	0.8843	0.4851	0.049*
O1W	0.5	1.0598 (3)	0.75	0.1046 (9)
H1WA	0.5078 (14)	0.965 (5)	0.703 (2)	0.157*

	U11	U22	U33	U12	U13	U23
O1	0.0538 (6)	0.0380 (5)	0.0420 (5)	0.0108 (4)	0.0303 (4)	0.0010 (4)
N1	0.0519 (7)	0.0410 (6)	0.0391 (6)	0.0099 (5)	0.0274 (5)	0.0071 (5)
N2	0.0484 (6)	0.0338 (5)	0.0396 (6)	0.0118 (5)	0.0278 (5)	0.0057 (4)
N3	0.0372 (5)	0.0318 (5)	0.0370 (5)	0.0045 (4)	0.0198 (4)	−0.0008 (4)
N4	0.0427 (6)	0.0411 (6)	0.0521 (7)	0.0027 (5)	0.0257 (5)	−0.0070 (5)
C1	0.0351 (6)	0.0328 (6)	0.0304 (6)	−0.0009 (5)	0.0164 (5)	−0.0032 (4)
C2	0.0353 (6)	0.0327 (6)	0.0349 (6)	0.0026 (5)	0.0178 (5)	0.0007 (4)
C3	0.0304 (6)	0.0318 (6)	0.0334 (6)	−0.0030 (4)	0.0150 (5)	−0.0058 (4)
C4	0.0397 (7)	0.0393 (6)	0.0385 (6)	0.0015 (5)	0.0208 (5)	0.0015 (5)
C5	0.0462 (7)	0.0492 (7)	0.0443 (7)	−0.0004 (6)	0.0289 (6)	−0.0046 (6)
C6	0.0427 (7)	0.0369 (6)	0.0363 (6)	0.0018 (5)	0.0206 (5)	−0.0003 (5)
C7	0.0435 (7)	0.0339 (6)	0.0472 (7)	0.0041 (5)	0.0185 (6)	0.0000 (5)
O1W	0.200 (3)	0.0427 (9)	0.1390 (19)	0	0.142 (2)	0

O1—C1	1.2399 (14)	C2—H2	0.93
N1—C1	1.3294 (16)	C3—C4	1.3870 (16)
N1—H1NA	0.854 (18)	C3—C6	1.3875 (17)
N1—H1NB	0.917 (19)	C4—C5	1.3789 (17)
N2—C1	1.3639 (15)	C4—H4	0.93
N2—N3	1.3706 (13)	C5—H5	0.93
N2—H2N	0.899 (17)	C6—C7	1.3789 (17)
N3—C2	1.2752 (15)	C6—H6	0.93
N4—C5	1.3301 (18)	C7—H7	0.93
N4—C7	1.3366 (18)	O1W—H1WA	0.874 (17)
C2—C3	1.4616 (15)
C1—N1—H1NA	117.8 (12)	C4—C3—C2	119.22 (11)
C1—N1—H1NB	120.2 (10)	C6—C3—C2	123.34 (10)
H1NA—N1—H1NB	120.5 (16)	C5—C4—C3	119.20 (12)
C1—N2—N3	119.97 (10)	C5—C4—H4	120.4
C1—N2—H2N	118.8 (11)	C3—C4—H4	120.4
N3—N2—H2N	120.3 (11)	N4—C5—C4	123.92 (12)
C2—N3—N2	115.43 (10)	N4—C5—H5	118.0
C5—N4—C7	116.50 (11)	C4—C5—H5	118.0
O1—C1—N1	124.12 (11)	C7—C6—C3	119.07 (11)
O1—C1—N2	118.79 (10)	C7—C6—H6	120.5
N1—C1—N2	117.08 (10)	C3—C6—H6	120.5
N3—C2—C3	121.72 (11)	N4—C7—C6	123.87 (12)
N3—C2—H2	119.1	N4—C7—H7	118.1
C3—C2—H2	119.1	C6—C7—H7	118.1
C4—C3—C6	117.43 (11)
C1—N2—N3—C2	−174.35 (11)	C2—C3—C4—C5	−179.38 (11)
N3—N2—C1—O1	179.42 (10)	C7—N4—C5—C4	0.5 (2)
N3—N2—C1—N1	−1.82 (17)	C3—C4—C5—N4	0.4 (2)
N2—N3—C2—C3	−177.87 (10)	C4—C3—C6—C7	0.24 (17)
N3—C2—C3—C4	176.79 (11)	C2—C3—C6—C7	178.81 (11)
N3—C2—C3—C6	−1.76 (18)	C5—N4—C7—C6	−1.1 (2)
C6—C3—C4—C5	−0.74 (18)	C3—C6—C7—N4	0.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···N3	0.852 (18)	2.273 (18)	2.6541 (16)	107.3 (13)
N1—H1NB···O1i	0.917 (19)	1.998 (18)	2.9046 (15)	169.3 (16)
N2—H2N···O1ii	0.898 (17)	2.022 (17)	2.9141 (14)	171.9 (16)
O1W—H1WA···N4	0.87 (3)	2.08 (3)	2.9373 (16)	168 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1NAN3	0.852(18)	2.273(18)	2.6541(16)	107.3(13)
N1H1NBO1i	0.917(19)	1.998(18)	2.9046(15)	169.3(16)
N2H2NO1ii	0.898(17)	2.022(17)	2.9141(14)	171.9(16)
O1WH1WAN4	0.87(3)	2.08(3)	2.9373(16)	168(3)

Symmetry codes: (i) ; (ii) .