Ethyl 5-{[(E)-2-(isonicotinoyl)hydrazinyl-idene]methyl}-3,4-dimethyl-1H-pyrrole-2-carboxyl-ate dihydrate.

In the title compound, C(16)H(18)N(4)O(3)·2H(2)O, the dihedral angle between the pyrrole and pyridine rings in the hydrazone mol-ecule is 7.12 (3)°. In the crystal structure, inter-molecular N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds link the hydrazone and water mol-ecules into double layers parallel to (101). The crystal packing exhibits weak π-π inter-actions between the pyrrole and pyridine rings of neighbouring hydrazone mol-ecules [centroid-centroid distance = 3.777 (3) Å]. The crystal studied was a non-merohedral twin, the refined ratio of twin domains being 0.73 (3):0.27 (3).

Related literature

For the anti­oxidant and DNA-binding properties of hydrazone complexes, see: Liu & Yang (2009 ▶). For the synthesis and structure of 5-formyl-3,4-dimethyl-1H-pyrrole-2-carboxyl­ate, see: Wu et al. (2009 ▶). For the similar structure of ethyl 5-[(3,4-dimethyl-1H-pyrrole-2-carboxyl­imino)-meth­yl]-3,4-dimethyl-1H-pyrrole-2-carboxyl­ate monohydrate, see: Wang et al. (2009 ▶).

Experimental

Crystal data

C16H18N4O3·2H2O

M = 350.38

Monoclinic,

a = 8.297 (4) Å

b = 18.120 (6) Å

c = 11.834 (4) Å

β = 91.814 (4)°

V = 1778.3 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 296 K

0.23 × 0.21 × 0.16 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.977, T max = 0.984

10998 measured reflections

3839 independent reflections

2671 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.074

wR(F 2) = 0.176

S = 1.02

3839 reflections

241 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017132/cv5084sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017132/cv5084Isup2.hkl

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

C16H18N4O3·2H2O	F(000) = 744
Mr = 350.38	Dx = 1.309 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.297 (4) Å	θ = 2.7–25.3°
b = 18.120 (6) Å	µ = 0.10 mm−1
c = 11.834 (4) Å	T = 296 K
β = 91.814 (4)°	Prism, yellow
V = 1778.3 (11) Å3	0.23 × 0.21 × 0.16 mm
Z = 4

Bruker SMART APEX CCD diffractometer	3839 independent reflections
Radiation source: fine-focus sealed tube	2671 reflections with I > 2σ(I)
graphite	Rint = 0.037
φ and ω scans	θmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
Tmin = 0.977, Tmax = 0.984	k = −9→24
10998 measured reflections	l = −15→15

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.176	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.02P)2 + 3.5P] where P = (Fo2 + 2Fc2)/3
3839 reflections	(Δ/σ)max = 0.069
241 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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
O1	0.6319 (3)	0.46189 (12)	0.4160 (2)	0.0530 (6)
O2	1.1091 (4)	0.29040 (14)	0.9756 (2)	0.0660 (8)
O3	0.9696 (3)	0.27423 (12)	0.8122 (2)	0.0564 (7)
N1	0.4775 (4)	0.68078 (16)	0.1780 (2)	0.0532 (8)
N2	0.7766 (3)	0.55247 (14)	0.5019 (2)	0.0406 (6)
H2A	0.8043	0.5982	0.5024	0.049*
N3	0.8374 (3)	0.50452 (14)	0.5828 (2)	0.0420 (6)
N4	0.9761 (3)	0.41573 (14)	0.7584 (2)	0.0415 (6)
H4A	0.9158	0.3892	0.7141	0.050*
C1	0.4299 (4)	0.6106 (2)	0.1836 (3)	0.0545 (9)
H1	0.3507	0.5946	0.1319	0.065*
C2	0.4901 (4)	0.56074 (19)	0.2606 (3)	0.0498 (8)
H2	0.4522	0.5124	0.2604	0.060*
C3	0.6076 (4)	0.58255 (17)	0.3388 (3)	0.0385 (7)
C4	0.6579 (5)	0.65506 (18)	0.3348 (3)	0.0531 (9)
H4	0.7355	0.6730	0.3861	0.064*
C5	0.5898 (5)	0.70012 (19)	0.2527 (3)	0.0605 (10)
H5	0.6267	0.7485	0.2500	0.073*
C6	0.6727 (4)	0.52615 (16)	0.4219 (3)	0.0380 (7)
C7	0.9388 (4)	0.53192 (17)	0.6540 (3)	0.0418 (7)
H7A	0.9686	0.5811	0.6471	0.050*
C8	1.0084 (4)	0.48875 (17)	0.7448 (3)	0.0412 (7)
C9	1.1112 (4)	0.51125 (18)	0.8322 (3)	0.0428 (8)
C10	1.1406 (4)	0.44984 (18)	0.9021 (3)	0.0423 (7)
C11	1.0555 (4)	0.39167 (17)	0.8543 (3)	0.0411 (7)
C12	1.1778 (5)	0.5870 (2)	0.8501 (3)	0.0654 (11)
H12A	1.1754	0.6131	0.7795	0.098*
H12B	1.2870	0.5837	0.8789	0.098*
H12C	1.1137	0.6129	0.9033	0.098*
C13	1.2480 (5)	0.4481 (2)	1.0061 (3)	0.0589 (10)
H13A	1.1894	0.4654	1.0695	0.088*
H13B	1.3398	0.4792	0.9954	0.088*
H13C	1.2835	0.3984	1.0201	0.088*
C14	1.0502 (4)	0.31492 (18)	0.8893 (3)	0.0452 (8)
C15	0.9548 (5)	0.19650 (18)	0.8342 (3)	0.0609 (10)
H15A	0.8978	0.1883	0.9034	0.073*
H15B	1.0605	0.1738	0.8420	0.073*
C16	0.8642 (7)	0.1652 (2)	0.7371 (4)	0.0830 (15)
H16A	0.7623	0.1900	0.7281	0.125*
H16B	0.8461	0.1135	0.7498	0.125*
H16C	0.9247	0.1715	0.6700	0.125*
O1W	0.4291 (4)	0.80318 (15)	0.0290 (3)	0.0654 (8)
H1C	0.428 (7)	0.770 (3)	0.059 (5)	0.098*
H1D	0.528 (6)	0.813 (3)	0.001 (4)	0.098*
O2W	0.7783 (3)	0.34071 (15)	0.5656 (2)	0.0588 (7)
H2C	0.704 (6)	0.305 (3)	0.544 (4)	0.088*
H2D	0.744 (6)	0.380 (3)	0.541 (4)	0.088*

	U11	U22	U33	U12	U13	U23
O1	0.0688 (16)	0.0297 (12)	0.0598 (15)	−0.0029 (11)	−0.0066 (12)	0.0035 (10)
O2	0.102 (2)	0.0431 (14)	0.0513 (15)	0.0040 (14)	−0.0203 (15)	0.0099 (12)
O3	0.0790 (18)	0.0327 (12)	0.0562 (15)	−0.0080 (12)	−0.0160 (13)	0.0066 (11)
N1	0.0622 (19)	0.0453 (17)	0.0512 (18)	0.0079 (14)	−0.0106 (15)	0.0081 (14)
N2	0.0489 (15)	0.0314 (13)	0.0412 (15)	0.0009 (11)	−0.0045 (12)	0.0071 (11)
N3	0.0514 (16)	0.0334 (14)	0.0412 (15)	0.0061 (12)	0.0007 (12)	0.0060 (11)
N4	0.0479 (15)	0.0373 (14)	0.0388 (14)	−0.0002 (12)	−0.0063 (12)	0.0009 (11)
C1	0.055 (2)	0.056 (2)	0.051 (2)	−0.0028 (17)	−0.0150 (17)	0.0018 (17)
C2	0.053 (2)	0.0374 (18)	0.058 (2)	−0.0064 (15)	−0.0077 (17)	0.0021 (16)
C3	0.0430 (17)	0.0327 (16)	0.0396 (17)	0.0022 (13)	0.0000 (13)	−0.0006 (13)
C4	0.069 (2)	0.0373 (18)	0.052 (2)	−0.0048 (16)	−0.0192 (18)	0.0029 (15)
C5	0.079 (3)	0.0298 (18)	0.072 (3)	−0.0034 (17)	−0.017 (2)	0.0099 (17)
C6	0.0437 (17)	0.0295 (16)	0.0410 (17)	0.0023 (13)	0.0040 (14)	0.0027 (13)
C7	0.0525 (19)	0.0333 (16)	0.0396 (17)	0.0013 (14)	0.0019 (15)	0.0003 (13)
C8	0.0459 (18)	0.0379 (17)	0.0399 (17)	0.0056 (14)	0.0024 (14)	0.0016 (14)
C9	0.0515 (19)	0.0367 (17)	0.0404 (17)	0.0011 (14)	0.0029 (15)	−0.0014 (13)
C10	0.0501 (19)	0.0384 (17)	0.0383 (17)	0.0027 (14)	−0.0022 (14)	−0.0018 (14)
C11	0.0502 (18)	0.0368 (17)	0.0359 (16)	0.0040 (14)	−0.0030 (14)	0.0018 (13)
C12	0.092 (3)	0.042 (2)	0.061 (2)	−0.008 (2)	−0.011 (2)	0.0002 (18)
C13	0.072 (3)	0.056 (2)	0.047 (2)	0.0001 (19)	−0.0138 (18)	−0.0002 (17)
C14	0.057 (2)	0.0384 (18)	0.0404 (18)	0.0043 (15)	−0.0020 (15)	0.0007 (14)
C15	0.086 (3)	0.0304 (18)	0.065 (2)	−0.0057 (18)	−0.004 (2)	0.0070 (16)
C16	0.118 (4)	0.043 (2)	0.086 (3)	−0.005 (2)	−0.025 (3)	−0.005 (2)
O1W	0.0706 (18)	0.0443 (16)	0.081 (2)	0.0111 (14)	−0.0049 (16)	0.0186 (14)
O2W	0.0681 (18)	0.0384 (14)	0.0692 (18)	0.0038 (12)	−0.0093 (14)	−0.0031 (13)

O1—C6	1.214 (4)	C7—H7A	0.9300
O2—C14	1.204 (4)	C8—C9	1.382 (5)
O3—C14	1.336 (4)	C9—C10	1.403 (4)
O3—C15	1.438 (4)	C9—C12	1.492 (5)
N1—C5	1.312 (5)	C10—C11	1.380 (4)
N1—C1	1.334 (5)	C10—C13	1.497 (5)
N2—C6	1.347 (4)	C11—C14	1.452 (4)
N2—N3	1.377 (3)	C12—H12A	0.9600
N2—H2A	0.8600	C12—H12B	0.9600
N3—C7	1.273 (4)	C12—H12C	0.9600
N4—C8	1.361 (4)	C13—H13A	0.9600
N4—C11	1.366 (4)	C13—H13B	0.9600
N4—H4A	0.8600	C13—H13C	0.9600
C1—C2	1.366 (5)	C15—C16	1.468 (5)
C1—H1	0.9300	C15—H15A	0.9700
C2—C3	1.380 (4)	C15—H15B	0.9700
C2—H2	0.9300	C16—H16A	0.9600
C3—C4	1.380 (4)	C16—H16B	0.9600
C3—C6	1.506 (4)	C16—H16C	0.9600
C4—C5	1.376 (5)	O1W—H1C	0.69 (5)
C4—H4	0.9300	O1W—H1D	0.91 (5)
C5—H5	0.9300	O2W—H2C	0.92 (5)
C7—C8	1.435 (4)	O2W—H2D	0.82 (5)
C14—O3—C15	117.4 (3)	C11—C10—C9	106.7 (3)
C5—N1—C1	115.2 (3)	C11—C10—C13	127.2 (3)
C6—N2—N3	118.5 (3)	C9—C10—C13	126.1 (3)
C6—N2—H2A	120.7	N4—C11—C10	108.9 (3)
N3—N2—H2A	120.7	N4—C11—C14	121.6 (3)
C7—N3—N2	115.7 (3)	C10—C11—C14	129.4 (3)
C8—N4—C11	108.5 (3)	C9—C12—H12A	109.5
C8—N4—H4A	125.8	C9—C12—H12B	109.5
C11—N4—H4A	125.8	H12A—C12—H12B	109.5
N1—C1—C2	124.1 (3)	C9—C12—H12C	109.5
N1—C1—H1	117.9	H12A—C12—H12C	109.5
C2—C1—H1	117.9	H12B—C12—H12C	109.5
C1—C2—C3	119.6 (3)	C10—C13—H13A	109.5
C1—C2—H2	120.2	C10—C13—H13B	109.5
C3—C2—H2	120.2	H13A—C13—H13B	109.5
C4—C3—C2	117.2 (3)	C10—C13—H13C	109.5
C4—C3—C6	124.5 (3)	H13A—C13—H13C	109.5
C2—C3—C6	118.3 (3)	H13B—C13—H13C	109.5
C3—C4—C5	118.1 (3)	O2—C14—O3	123.9 (3)
C3—C4—H4	120.9	O2—C14—C11	125.5 (3)
C5—C4—H4	120.9	O3—C14—C11	110.7 (3)
N1—C5—C4	125.7 (3)	O3—C15—C16	106.3 (3)
N1—C5—H5	117.1	O3—C15—H15A	110.5
C4—C5—H5	117.1	C16—C15—H15A	110.5
O1—C6—N2	123.4 (3)	O3—C15—H15B	110.5
O1—C6—C3	121.3 (3)	C16—C15—H15B	110.5
N2—C6—C3	115.3 (3)	H15A—C15—H15B	108.7
N3—C7—C8	121.7 (3)	C15—C16—H16A	109.5
N3—C7—H7A	119.2	C15—C16—H16B	109.5
C8—C7—H7A	119.2	H16A—C16—H16B	109.5
N4—C8—C9	108.5 (3)	C15—C16—H16C	109.5
N4—C8—C7	122.9 (3)	H16A—C16—H16C	109.5
C9—C8—C7	128.6 (3)	H16B—C16—H16C	109.5
C8—C9—C10	107.4 (3)	H1C—O1W—H1D	112 (5)
C8—C9—C12	126.5 (3)	H2C—O2W—H2D	107 (4)
C10—C9—C12	126.1 (3)
C6—N2—N3—C7	177.9 (3)	C7—C8—C9—C10	177.6 (3)
C5—N1—C1—C2	0.3 (6)	N4—C8—C9—C12	179.8 (3)
N1—C1—C2—C3	0.1 (6)	C7—C8—C9—C12	−1.8 (6)
C1—C2—C3—C4	0.3 (5)	C8—C9—C10—C11	0.4 (4)
C1—C2—C3—C6	−179.4 (3)	C12—C9—C10—C11	179.9 (3)
C2—C3—C4—C5	−1.0 (5)	C8—C9—C10—C13	178.8 (3)
C6—C3—C4—C5	178.7 (3)	C12—C9—C10—C13	−1.8 (6)
C1—N1—C5—C4	−1.1 (6)	C8—N4—C11—C10	−0.5 (4)
C3—C4—C5—N1	1.5 (7)	C8—N4—C11—C14	−177.4 (3)
N3—N2—C6—O1	−1.4 (5)	C9—C10—C11—N4	0.0 (4)
N3—N2—C6—C3	178.1 (3)	C13—C10—C11—N4	−178.3 (3)
C4—C3—C6—O1	−174.7 (3)	C9—C10—C11—C14	176.6 (3)
C2—C3—C6—O1	5.0 (5)	C13—C10—C11—C14	−1.7 (6)
C4—C3—C6—N2	5.8 (5)	C15—O3—C14—O2	−0.7 (5)
C2—C3—C6—N2	−174.5 (3)	C15—O3—C14—C11	179.5 (3)
N2—N3—C7—C8	178.2 (3)	N4—C11—C14—O2	−175.6 (3)
C11—N4—C8—C9	0.8 (4)	C10—C11—C14—O2	8.2 (6)
C11—N4—C8—C7	−177.7 (3)	N4—C11—C14—O3	4.3 (5)
N3—C7—C8—N4	2.6 (5)	C10—C11—C14—O3	−172.0 (3)
N3—C7—C8—C9	−175.5 (3)	C14—O3—C15—C16	−179.3 (4)
N4—C8—C9—C10	−0.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1Wi	0.86	2.08	2.919 (4)	164
N4—H4A···O2W	0.86	2.24	3.084 (4)	165
O1W—H1C···N1	0.69 (5)	2.18 (5)	2.854 (4)	164 (6)
O1W—H1D···O2Wii	0.91 (5)	1.88 (5)	2.790 (5)	174 (5)
O2W—H2C···O2iii	0.92 (5)	2.06 (5)	2.941 (4)	160 (4)
O2W—H2D···O1	0.82 (5)	2.27 (5)	3.048 (4)	159 (5)
O2W—H2D···N3	0.82 (5)	2.43 (5)	3.014 (4)	129 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1Wi	0.86	2.08	2.919 (4)	164
N4—H4A⋯O2W	0.86	2.24	3.084 (4)	165
O1W—H1C⋯N1	0.69 (5)	2.18 (5)	2.854 (4)	164 (6)
O1W—H1D⋯O2Wii	0.91 (5)	1.88 (5)	2.790 (5)	174 (5)
O2W—H2C⋯O2iii	0.92 (5)	2.06 (5)	2.941 (4)	160 (4)
O2W—H2D⋯O1	0.82 (5)	2.27 (5)	3.048 (4)	159 (5)
O2W—H2D⋯N3	0.82 (5)	2.43 (5)	3.014 (4)	129 (4)

Symmetry codes: (i) ; (ii) ; (iii) .