4-Methoxy­benzaldehyde 2-methyl­propanoylhydrazone

The title compound, C₁₂H₁₈N₂O₃, was prepared by the reaction between p-methoxy­benzaldehyde and propionyl­hydrazine. With the exception of the two methyl groups of the ⁱPr and the H atoms of the OMe group, the molecule is essentially planar. The crystal structure is stabilized by N—H...O, O—H...O and O—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.154
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTY03_ALERT_1_C  The _exptl_absorpt_correction_type has been given as none.
            However values have been given for Tmin and Tmax. Remove
            these if an absorption correction has not been applied.
  From the CIF: _exptl_absorpt_correction_T_min   0.979
  From the CIF: _exptl_absorpt_correction_T_max   0.984
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         43 Perc.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        300 Ang.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C12 H18 N2 O3
            Atom count from _chemical_formula_moiety:C12 H20 N2 O4
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         15

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

As an extension of our work on the structural characterization of Schiff base compound, herein we report the crystal and moulecular structures of the title compound (I). The title compound (I) is roughly planar. In (I), the bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). The C8—N1 distance of 1.274 (3) Å is similar to the reported value of 1.287 Å by Tucker et al. (1975). The C9—O2 distance of 1.227 (3) Å is shorter than the distance value of 1.298 Å reported by Sutherland & Hoy (1968).

The crystal structure of (I) is stabilized by N—H···O, O—H···O and O—H···N hydrogen bonds. (Table 1).

Related literature

For related literature, see: Allen et al. (1987); Sutherland & Hoy (1968); Tucker et al. (1975).

S2. Experimental

A mixture of the p-methoxybenzaldehyde (0.1 mol), and propionylhydrazine (0.1 mol) was stirred in refluxing ethanol (30 ml) for 5 h to afford the title compound (I) (0.087 mol, yield 87%). Single crystals of (I) suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93–0.97 Å, N—H distances = 0.8600 Å and with U_iso = 1.2–1.5U_eq.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The structure of the title molecule (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme.

4-Methoxybenzaldehyde 2-methylpropanoylhydrazone

Crystal data

C12H18N2O3·H2O	Z = 4
Mr = 238.28	F(000) = 512
Monoclinic, P21/c	Dx = 1.133 Mg m^−3
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 11.184 (3) Å	θ = 2.0–26.5°
b = 12.732 (3) Å	µ = 0.08 mm^−1
c = 10.634 (3) Å	T = 294 K
β = 112.636 (4)°	Block, colourless
V = 1397.5 (6) Å^3	0.26 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1213 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.049
Graphite monochromator	θmax = 26.5°, θmin = 2.0°
φ and ω scans	h = −13→10
7894 measured reflections	k = −15→14
2852 independent reflections	l = −12→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0667P)^2 + 0.0773P] where P = (Fo^2 + 2Fc^2)/3
2852 reflections	(Δ/σ)max < 0.001
165 parameters	Δρmax = 0.13 e Å^−3
15 restraints	Δρmin = −0.16 e Å^−3

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
O1	0.36412 (18)	0.09825 (15)	0.47380 (19)	0.0995 (6)
O2	1.00629 (16)	0.38689 (14)	1.11832 (17)	0.0863 (6)
N1	0.82345 (19)	0.23666 (15)	1.0247 (2)	0.0638 (5)
N2	0.91436 (18)	0.23964 (15)	1.1570 (2)	0.0670 (6)
H2	0.9144	0.1918	1.2141	0.080*
C1	0.2678 (3)	0.0190 (2)	0.4440 (3)	0.1101 (10)
H1A	0.3086	−0.0487	0.4649	0.165*
H1B	0.2125	0.0218	0.3491	0.165*
H1C	0.2170	0.0301	0.4980	0.165*
C2	0.4509 (2)	0.1095 (2)	0.6048 (3)	0.0722 (7)
C3	0.5326 (2)	0.1952 (2)	0.6278 (3)	0.0833 (8)
H3	0.5244	0.2406	0.5564	0.100*
C4	0.6260 (2)	0.21393 (19)	0.7550 (3)	0.0747 (7)
H4	0.6795	0.2723	0.7689	0.090*
C5	0.6414 (2)	0.14673 (18)	0.8632 (2)	0.0617 (6)
C6	0.5582 (3)	0.0617 (2)	0.8380 (3)	0.0781 (7)
H6	0.5665	0.0157	0.9088	0.094*
C7	0.4627 (3)	0.0433 (2)	0.7104 (3)	0.0795 (8)
H7	0.4071	−0.0137	0.6965	0.095*
C8	0.7410 (2)	0.16238 (18)	0.9976 (2)	0.0644 (7)
H8	0.7448	0.1164	1.0670	0.077*
C9	1.0029 (2)	0.3173 (2)	1.1967 (3)	0.0678 (7)
C10	1.0954 (3)	0.3134 (2)	1.3437 (3)	0.0921 (9)
H10	1.0901	0.2444	1.3820	0.111*
C11	1.2333 (3)	0.3322 (3)	1.3537 (3)	0.1332 (13)
H11A	1.2557	0.2799	1.3015	0.200*
H11B	1.2920	0.3279	1.4473	0.200*
H11C	1.2391	0.4007	1.3186	0.200*
C12	1.0567 (3)	0.3982 (3)	1.4220 (3)	0.1276 (13)
H12A	1.0604	0.4657	1.3835	0.191*
H12B	1.1153	0.3970	1.5159	0.191*
H12C	0.9701	0.3852	1.4161	0.191*
O3	0.88004 (18)	0.41283 (14)	0.83391 (17)	0.0768 (5)
H3A	0.917 (3)	0.4731 (13)	0.837 (3)	0.121 (11)*
H3B	0.905 (3)	0.386 (2)	0.9159 (16)	0.147 (14)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0838 (13)	0.1059 (15)	0.0950 (15)	−0.0318 (11)	0.0190 (12)	−0.0025 (11)
O2	0.0979 (13)	0.0678 (11)	0.0771 (12)	−0.0194 (9)	0.0160 (10)	0.0196 (9)
N1	0.0636 (12)	0.0576 (12)	0.0679 (14)	0.0022 (10)	0.0228 (11)	0.0047 (10)
N2	0.0715 (13)	0.0582 (13)	0.0657 (14)	−0.0021 (10)	0.0203 (12)	0.0131 (10)
C1	0.088 (2)	0.116 (2)	0.112 (2)	−0.0408 (19)	0.0237 (18)	−0.023 (2)
C2	0.0594 (16)	0.0748 (17)	0.0794 (19)	−0.0090 (13)	0.0234 (15)	−0.0017 (15)
C3	0.0695 (17)	0.0817 (19)	0.089 (2)	−0.0175 (14)	0.0195 (16)	0.0179 (15)
C4	0.0640 (16)	0.0633 (16)	0.0880 (19)	−0.0132 (12)	0.0196 (15)	0.0106 (14)
C5	0.0605 (15)	0.0534 (14)	0.0760 (17)	0.0002 (11)	0.0315 (14)	0.0012 (12)
C6	0.0850 (18)	0.0704 (17)	0.0829 (19)	−0.0131 (14)	0.0365 (17)	0.0089 (14)
C7	0.0737 (18)	0.0677 (17)	0.097 (2)	−0.0193 (13)	0.0331 (17)	−0.0017 (16)
C8	0.0677 (16)	0.0557 (15)	0.0751 (18)	0.0040 (12)	0.0331 (15)	0.0060 (12)
C9	0.0714 (17)	0.0540 (15)	0.0742 (17)	−0.0011 (13)	0.0239 (14)	0.0095 (14)
C10	0.093 (2)	0.081 (2)	0.081 (2)	−0.0171 (16)	0.0100 (17)	0.0248 (16)
C11	0.081 (2)	0.137 (3)	0.146 (3)	0.007 (2)	0.004 (2)	0.033 (2)
C12	0.149 (3)	0.148 (3)	0.088 (2)	−0.042 (2)	0.049 (2)	−0.013 (2)
O3	0.1092 (15)	0.0565 (11)	0.0653 (12)	−0.0040 (10)	0.0342 (10)	−0.0018 (9)

Geometric parameters (Å, º)

O1—C2	1.365 (3)	C5—C8	1.448 (3)
O1—C1	1.421 (3)	C6—C7	1.386 (3)
O2—C9	1.227 (3)	C6—H6	0.9300
N1—C8	1.274 (3)	C7—H7	0.9300
N1—N2	1.383 (2)	C8—H8	0.9300
N2—C9	1.347 (3)	C9—C10	1.507 (3)
N2—H2	0.8600	C10—C11	1.524 (4)
C1—H1A	0.9600	C10—C12	1.524 (4)
C1—H1B	0.9600	C10—H10	0.9800
C1—H1C	0.9600	C11—H11A	0.9600
C2—C7	1.369 (3)	C11—H11B	0.9600
C2—C3	1.383 (3)	C11—H11C	0.9600
C3—C4	1.375 (3)	C12—H12A	0.9600
C3—H3	0.9300	C12—H12B	0.9600
C4—C5	1.390 (3)	C12—H12C	0.9600
C4—H4	0.9300	O3—H3A	0.865 (10)
C5—C6	1.385 (3)	O3—H3B	0.874 (10)
C2—O1—C1	118.9 (2)	C2—C7—H7	120.2
C8—N1—N2	115.8 (2)	C6—C7—H7	120.2
C9—N2—N1	120.18 (19)	N1—C8—C5	122.7 (2)
C9—N2—H2	119.9	N1—C8—H8	118.7
N1—N2—H2	119.9	C5—C8—H8	118.7
O1—C1—H1A	109.5	O2—C9—N2	121.9 (2)
O1—C1—H1B	109.5	O2—C9—C10	122.6 (2)
H1A—C1—H1B	109.5	N2—C9—C10	115.4 (2)
O1—C1—H1C	109.5	C9—C10—C11	109.9 (2)
H1A—C1—H1C	109.5	C9—C10—C12	108.5 (2)
H1B—C1—H1C	109.5	C11—C10—C12	110.1 (3)
O1—C2—C7	125.3 (2)	C9—C10—H10	109.4
O1—C2—C3	115.2 (2)	C11—C10—H10	109.4
C7—C2—C3	119.5 (3)	C12—C10—H10	109.4
C4—C3—C2	120.7 (2)	C10—C11—H11A	109.5
C4—C3—H3	119.6	C10—C11—H11B	109.5
C2—C3—H3	119.6	H11A—C11—H11B	109.5
C3—C4—C5	120.9 (2)	C10—C11—H11C	109.5
C3—C4—H4	119.6	H11A—C11—H11C	109.5
C5—C4—H4	119.6	H11B—C11—H11C	109.5
C6—C5—C4	117.4 (2)	C10—C12—H12A	109.5
C6—C5—C8	120.2 (2)	C10—C12—H12B	109.5
C4—C5—C8	122.4 (2)	H12A—C12—H12B	109.5
C5—C6—C7	121.9 (2)	C10—C12—H12C	109.5
C5—C6—H6	119.0	H12A—C12—H12C	109.5
C7—C6—H6	119.0	H12B—C12—H12C	109.5
C2—C7—C6	119.6 (2)	H3A—O3—H3B	110.1 (15)
C8—N1—N2—C9	−177.8 (2)	C3—C2—C7—C6	−1.3 (4)
C1—O1—C2—C7	7.3 (4)	C5—C6—C7—C2	1.1 (4)
C1—O1—C2—C3	−173.5 (2)	N2—N1—C8—C5	−178.47 (19)
O1—C2—C3—C4	−178.7 (2)	C6—C5—C8—N1	177.0 (2)
C7—C2—C3—C4	0.5 (4)	C4—C5—C8—N1	−2.3 (3)
C2—C3—C4—C5	0.7 (4)	N1—N2—C9—O2	−0.1 (3)
C3—C4—C5—C6	−1.0 (4)	N1—N2—C9—C10	179.0 (2)
C3—C4—C5—C8	178.3 (2)	O2—C9—C10—C11	−46.6 (4)
C4—C5—C6—C7	0.1 (4)	N2—C9—C10—C11	134.3 (3)
C8—C5—C6—C7	−179.2 (2)	O2—C9—C10—C12	73.9 (3)
O1—C2—C7—C6	177.8 (2)	N2—C9—C10—C12	−105.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3^i	0.86	1.98	2.830 (2)	170
O3—H3A···O2^ii	0.87 (1)	1.96 (1)	2.807 (2)	167 (3)
O3—H3B···O2	0.87 (1)	2.01 (2)	2.822 (2)	154 (2)
O3—H3B···N1	0.87 (1)	2.57 (2)	3.246 (3)	135 (2)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, −y+1, −z+2.