3,4,5-Trimethoxy­benzohydrazidium chloride

The title compound, C₁₀H₁₅N₂O₄⁺·Cl⁻, was obtained as an unexpected by-product during the synthesis of 1-[2-(substituted ar­yl)]-3-methyl­pyrazol-5-ones. The hydrazide group is essentially planar, with an r.s.m. deviation of 0.020 (2) Å, and is oriented at a dihedral angle of 30.52 (3)° with respect to the benzene ring. In the crystal structure, the cations and anions are linked through N—H...O and N—H...Cl hydrogen bonds, forming a mol­ecular tape running along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.040
• wR factor = 0.111
• Data-to-parameter ratio = 22.0

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   223.000
            Value of melting point given =     0.000
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.72

Alert level G
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          3

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

   0 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
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

3,4,5-Trimethoxybenzohydrazide is an intermediate toward variety of hetero- cyclic systems. Thioether derivatives bearing 1,3,4-thiadiazole and 3,4,5-tri- methoxyphenyl moieties and N-substituted benzylidene-3,4,5-trimethoxybenzo- hydrazide and 3-acetyl-2-substituted phenyl-5-(3,4,5-trimethoxyphenyl)-2,3 -dihydro-1,3,4-oxadiazole derivatives were proved to have good anti-cancer and anti-tumor bioactivities (Song et al., 2005; Jin et al., 2006). 4-Alkyl(aryl)- thioquinazoline derivatives synthesized from gallic acid were highly effective against cancer cell lines (Yang et al., 2007). The title compound was obtained as an unexpected by-product during synthesis of 1-[2-(substituted aryl)]-3 -methylpyrazol-5-ones, and we report herein its crystal structure.

In the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges, and may be compared with the corresponding ones in 3,4,5-trimethoxybenzohydrazide hemihydrate (Zareef et al., 2006). The (N1/N2/O4/C7) plane is oriented with respect to ring A (C1-C6) at a dihedral angle of 30.52 (3)°, which is larger than the corresponding one [9.27 (10)°] in 3,4,5-trimethoxybenzohydrazide hemihydrate.

In the crystal structure, the molecules are linked through N-H···O and N-H···Cl hydrogen bonds, forming a molecular tape running along the b axis (Fig. 2). No significant interaction is observed between the tapes (Fig. 3).

Related literature

For general background, see: Jin et al. (2006); Song et al. (2005); Yang et al. (2007). For a related structure, see: Zareef et al. (2006). For bond-length data, see: Allen et al. (1987).

S2. Experimental

A mixture of 3,4,5-trimethoxybenzohydrazide (0.01 mol) and ethyl acetoacetate (0.01 mol) was refluxed in methanol (25 ml), containing concentrated hydrochloric acid (1 ml) for 8 h in a water-bath. The resulting solution was then concentrated and cooled at room temperature. The solid thus separated was washed with methanol, dried and recrystallized with acetone. Anal. calcd. for C₁₀H₁₅Cl_N2_O4: C 45.72, H 5.76, N 10.66%; found: C 45.57, H 5.64, N 10.69%.

S3. Refinement

H1 atom (for NH) was located in difference synthesis and refined isotropically [N-H = 0.876 (19) Å and U_iso(H) = 0.039 (5) Ų]. The remaining H atoms were positioned geometrically, with N-H = 0.90 Å (for NH₃) and C-H = 0.94 and 0.97 Å for aromatic and metyl H, respectively, and constrained to ride on their parent atoms with U_iso(H) = xU_eq(C,N), where x = 1.2 for aromatic H and x = 1.5 for all other H atoms.

Computing details

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2003).

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial packing diagram, showing the molecular tape running along the b axis. Hydrogen bonds are shown as dashed lines.
	Fig. 3. A crystal packing diagram, viewed along the b axis.

3,4,5-Trimethoxybenzohydrazidium chloride

Crystal data

C10H15N2O4^+·Cl^−	F(000) = 1104.00
Mr = 262.69	Dx = 1.455 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -C 2yc	Cell parameters from 12804 reflections
a = 38.587 (3) Å	θ = 3.0–30.0°
b = 4.8202 (3) Å	µ = 0.32 mm^−1
c = 13.5915 (10) Å	T = 223 K
β = 108.459 (2)°	Platelet, colorless
V = 2397.9 (3) Å^3	0.29 × 0.28 × 0.05 mm
Z = 8

Data collection

Rigaku R-AXIS RAPIDII diffractometer	2987 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.035
ω scans	θmax = 30.0°
Absorption correction: numerical (ABSCOR; Higashi, 1999)	h = −54→50
Tmin = 0.930, Tmax = 0.984	k = −6→6
15536 measured reflections	l = −19→19
3483 independent reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0672P)^2 + 0.9082P] where P = (Fo^2 + 2Fc^2)/3
3483 reflections	(Δ/σ)max = 0.003
158 parameters	Δρmax = 0.51 e Å^−3
0 restraints	Δρmin = −0.19 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
Cl1	0.531194 (8)	0.74543 (6)	0.14789 (2)	0.02591 (11)
O1	0.29508 (2)	−0.1702 (2)	0.04400 (7)	0.0261 (2)
O2	0.29359 (2)	0.12014 (18)	0.20875 (7)	0.02407 (19)
O3	0.35072 (3)	0.4308 (2)	0.31676 (7)	0.0301 (2)
O4	0.43237 (2)	−0.16714 (18)	0.07270 (7)	0.02515 (19)
N1	0.44683 (3)	0.2704 (2)	0.12743 (9)	0.0220 (2)
N2	0.47777 (3)	0.24854 (19)	0.09232 (9)	0.0222 (2)
H2NA	0.4900	0.0916	0.1173	0.033*
H2NB	0.4925	0.3956	0.1150	0.033*
H2NC	0.4703	0.2446	0.0225	0.033*
C1	0.38998 (3)	0.0818 (2)	0.13600 (9)	0.0198 (2)
C2	0.35979 (3)	−0.0716 (2)	0.07763 (9)	0.0207 (2)
H2	0.3616	−0.1909	0.0248	0.025*
C3	0.32687 (3)	−0.0453 (2)	0.09891 (8)	0.0204 (2)
C4	0.32509 (3)	0.1212 (2)	0.18165 (9)	0.0209 (2)
C5	0.35556 (3)	0.2748 (2)	0.23870 (9)	0.0217 (2)
C6	0.38830 (3)	0.2592 (2)	0.21544 (9)	0.0212 (2)
H6	0.4087	0.3656	0.2524	0.025*
C7	0.42422 (3)	0.0465 (2)	0.10930 (8)	0.0189 (2)
C8	0.29543 (4)	−0.3376 (3)	−0.04212 (10)	0.0302 (3)
H8A	0.3035	−0.2270	−0.0904	0.045*
H8B	0.2710	−0.4073	−0.0767	0.045*
H8C	0.3120	−0.4923	−0.0179	0.045*
C9	0.27160 (4)	0.3649 (3)	0.17816 (11)	0.0297 (3)
H9A	0.2862	0.5274	0.2066	0.045*
H9B	0.2509	0.3552	0.2041	0.045*
H9C	0.2628	0.3775	0.1031	0.045*
C10	0.38005 (4)	0.6091 (3)	0.37142 (10)	0.0311 (3)
H10A	0.4011	0.4981	0.4084	0.047*
H10B	0.3726	0.7210	0.4205	0.047*
H10C	0.3864	0.7294	0.3225	0.047*
H1	0.4380 (5)	0.439 (4)	0.1231 (14)	0.039 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.02223 (16)	0.02581 (17)	0.02881 (17)	−0.00046 (9)	0.00682 (12)	−0.00128 (10)
O1	0.0225 (4)	0.0335 (5)	0.0239 (4)	−0.0077 (3)	0.0095 (3)	−0.0079 (4)
O2	0.0240 (4)	0.0253 (4)	0.0279 (4)	−0.0016 (3)	0.0153 (3)	0.0007 (3)
O3	0.0292 (4)	0.0377 (5)	0.0280 (4)	−0.0087 (4)	0.0158 (4)	−0.0148 (4)
O4	0.0266 (4)	0.0200 (4)	0.0313 (5)	−0.0006 (3)	0.0127 (4)	−0.0037 (3)
N1	0.0220 (5)	0.0169 (5)	0.0317 (5)	−0.0004 (3)	0.0149 (4)	−0.0014 (4)
N2	0.0214 (5)	0.0202 (5)	0.0280 (5)	−0.0019 (3)	0.0122 (4)	−0.0009 (4)
C1	0.0209 (5)	0.0190 (5)	0.0213 (5)	0.0004 (4)	0.0092 (4)	0.0015 (4)
C2	0.0234 (5)	0.0199 (5)	0.0208 (5)	−0.0012 (4)	0.0099 (4)	−0.0010 (4)
C3	0.0218 (5)	0.0207 (5)	0.0195 (5)	−0.0028 (4)	0.0074 (4)	0.0005 (4)
C4	0.0216 (5)	0.0228 (5)	0.0213 (5)	−0.0010 (4)	0.0109 (4)	0.0008 (4)
C5	0.0246 (6)	0.0229 (5)	0.0199 (5)	−0.0010 (4)	0.0103 (4)	−0.0022 (4)
C6	0.0216 (5)	0.0215 (5)	0.0217 (5)	−0.0025 (4)	0.0086 (4)	−0.0020 (4)
C7	0.0202 (5)	0.0180 (5)	0.0186 (5)	0.0010 (4)	0.0062 (4)	0.0019 (4)
C8	0.0284 (6)	0.0371 (7)	0.0255 (6)	−0.0072 (5)	0.0092 (5)	−0.0091 (5)
C9	0.0275 (6)	0.0294 (6)	0.0358 (7)	0.0029 (5)	0.0152 (5)	0.0030 (5)
C10	0.0328 (6)	0.0344 (7)	0.0274 (6)	−0.0074 (5)	0.0112 (5)	−0.0118 (5)

Geometric parameters (Å, º)

O1—C3	1.3581 (14)	C2—C3	1.3950 (15)
O1—C8	1.4251 (15)	C2—H2	0.9400
O2—C4	1.3771 (13)	C3—C4	1.4009 (15)
O2—C9	1.4356 (16)	C4—C5	1.3982 (16)
O3—C5	1.3605 (14)	C5—C6	1.3981 (16)
O3—C10	1.4280 (15)	C6—H6	0.9400
O4—C7	1.2271 (14)	C8—H8A	0.9700
N1—C7	1.3602 (14)	C8—H8B	0.9700
N1—N2	1.4230 (13)	C8—H8C	0.9700
N1—H1	0.876 (19)	C9—H9A	0.9700
N2—H2NA	0.9000	C9—H9B	0.9700
N2—H2NB	0.9000	C9—H9C	0.9700
N2—H2NC	0.9000	C10—H10A	0.9700
C1—C6	1.3947 (15)	C10—H10B	0.9700
C1—C2	1.3958 (15)	C10—H10C	0.9700
C1—C7	1.4867 (15)
C3—O1—C8	117.43 (9)	C4—C5—C6	120.52 (10)
C4—O2—C9	114.20 (9)	C1—C6—C5	118.34 (10)
C5—O3—C10	117.16 (9)	C1—C6—H6	120.8
C7—N1—N2	116.00 (9)	C5—C6—H6	120.8
C7—N1—H1	120.7 (11)	O4—C7—N1	120.50 (10)
N2—N1—H1	113.3 (11)	O4—C7—C1	123.82 (10)
N1—N2—H2NA	109.5	N1—C7—C1	115.68 (10)
N1—N2—H2NB	109.5	O1—C8—H8A	109.5
H2NA—N2—H2NB	109.5	O1—C8—H8B	109.5
N1—N2—H2NC	109.5	H8A—C8—H8B	109.5
H2NA—N2—H2NC	109.5	O1—C8—H8C	109.5
H2NB—N2—H2NC	109.5	H8A—C8—H8C	109.5
C6—C1—C2	121.99 (10)	H8B—C8—H8C	109.5
C6—C1—C7	121.46 (10)	O2—C9—H9A	109.5
C2—C1—C7	116.55 (10)	O2—C9—H9B	109.5
C3—C2—C1	119.01 (10)	H9A—C9—H9B	109.5
C3—C2—H2	120.5	O2—C9—H9C	109.5
C1—C2—H2	120.5	H9A—C9—H9C	109.5
O1—C3—C2	124.68 (10)	H9B—C9—H9C	109.5
O1—C3—C4	115.46 (10)	O3—C10—H10A	109.5
C2—C3—C4	119.86 (10)	O3—C10—H10B	109.5
O2—C4—C5	120.82 (10)	H10A—C10—H10B	109.5
O2—C4—C3	118.97 (10)	O3—C10—H10C	109.5
C5—C4—C3	120.13 (10)	H10A—C10—H10C	109.5
O3—C5—C4	115.21 (10)	H10B—C10—H10C	109.5
O3—C5—C6	124.26 (11)
C6—C1—C2—C3	0.46 (17)	O2—C4—C5—O3	−3.67 (16)
C7—C1—C2—C3	−179.61 (10)	C3—C4—C5—O3	179.53 (10)
C8—O1—C3—C2	−0.71 (17)	O2—C4—C5—C6	175.34 (10)
C8—O1—C3—C4	178.87 (11)	C3—C4—C5—C6	−1.46 (17)
C1—C2—C3—O1	175.98 (10)	C2—C1—C6—C5	2.13 (17)
C1—C2—C3—C4	−3.58 (16)	C7—C1—C6—C5	−177.79 (10)
C9—O2—C4—C5	77.58 (14)	O3—C5—C6—C1	177.30 (11)
C9—O2—C4—C3	−105.59 (12)	C4—C5—C6—C1	−1.62 (17)
O1—C3—C4—O2	7.64 (15)	N2—N1—C7—O4	5.88 (16)
C2—C3—C4—O2	−172.76 (10)	N2—N1—C7—C1	−173.78 (10)
O1—C3—C4—C5	−175.50 (10)	C6—C1—C7—O4	150.77 (11)
C2—C3—C4—C5	4.09 (17)	C2—C1—C7—O4	−29.15 (16)
C10—O3—C5—C4	−174.81 (11)	C6—C1—C7—N1	−29.58 (15)
C10—O3—C5—C6	6.22 (18)	C2—C1—C7—N1	150.50 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^i	0.876 (19)	2.007 (19)	2.8200 (13)	154.0 (18)
N2—H2NA···Cl1^ii	0.90	2.25	3.1169 (11)	162
N2—H2NB···Cl1	0.90	2.20	3.0937 (11)	171
N2—H2NC···Cl1^iii	0.90	2.30	3.1724 (12)	164

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