N²-[1-(2-Hydroxy­phen­yl)ethyl­idene]-N^2′-(1H-indol-3-ylmethyl­ene)carbonic dihydrazide

In the crystal structure of the title compound {alternative name: 1-[1-(2-hydroxy­phen­yl)ethyl­ideneamino]-3-(1H-indol-3-ylmethyl­eneamino)urea}, C₁₈H₁₇N₅O₂, the planar indole component is twisted at an angle of 63.7 (10)° with respect to the rest of the mol­ecule. This compound is one of a series being studied for biological activity. The hydr­oxy groups are involved in both intra­molecular (O—H...N) and inter­molecular (N—H...O) hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.044
• wR factor = 0.122
• Data-to-parameter ratio = 20.8

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.821     0.986
            Tmin(prime) and Tmax expected:      0.961     0.986
            RR(prime) =      0.854
            Please check that your absorption correction is appropriate.
            Value of measurement temperature given =   100.000
            Value of melting point given =     0.000
PLAT414_ALERT_2_C Short Intra D-H..H-X       H4B    ..  H12C    ..       1.94 Ang.
PLAT061_ALERT_4_C Tmax/Tmin Range Test RR' too Large .............       0.85

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 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
   1 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

---

S1. Comment

X-ray structures, of Schiff bases derived from condensation of indole-3-carboxaldehyde and 2-hydroxyacetophenone, have not been investigated. The title compound (Fig. 1) appears to be the first example with the planar indole component is twisted at an angle of 116.3 (10)° with respect to the rest of the molecule. However, compound bis(salicylidene)carbonohydrazide (Dan et al.1987), which was reported previously shows planarity for the whole molecule.

Related literature

For a related compound, see: Dan et al. (1987).

S2. Experimental

Indole-3-carboxaldehyde (0.30 g, 2.07 mmol), carbohydrazide (0.187 g, 2.07 mmol), and 2-Hydroxyacetophenone (0.24 ml, 2.07 mmol) were heated in acidified ethanol (20 ml) for 2 h. The solvent was removed and the product recrystallized from DMSO.

S3. Refinement

Hydrogen atoms were placed at calculated positions (C—H 0.95, N—H 0.88 and O—H 0.84 Å), with U(H) set to 1.2–1.5 times U_eq(C,N,O).

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C18H17N5O2 at 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius

1-[1-(2-hydroxyphenyl)ethylideneamino]-3-(1H-indol-3- ylmethyleneamino)urea

Crystal data

C18H17N5O2	F(000) = 704
Mr = 335.37	Dx = 1.325 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6889 reflections
a = 7.0802 (8) Å	θ = 2.3–30.5°
b = 9.5335 (11) Å	µ = 0.09 mm^−1
c = 25.110 (3) Å	T = 100 K
β = 97.295 (2)°	Irregular, colourless
V = 1681.2 (3) Å^3	0.42 × 0.42 × 0.16 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	4740 independent reflections
Radiation source: fine-focus sealed tube	4145 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ω scans	θmax = 30.6°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→4
Tmin = 0.821, Tmax = 0.986	k = −13→12
11912 measured reflections	l = −34→35

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0656P)^2 + 0.7125P] where P = (Fo^2 + 2Fc^2)/3
4740 reflections	(Δ/σ)max < 0.001
228 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.32 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
N2	0.47231 (13)	0.13948 (10)	0.11232 (3)	0.01593 (18)
O2	0.38944 (12)	0.16315 (8)	−0.02799 (3)	0.01958 (18)
O1	0.22435 (14)	0.47449 (9)	−0.09575 (3)	0.0246 (2)
H1A	0.2598	0.4252	−0.0686	0.037*
N5	0.28865 (13)	0.41919 (9)	0.00270 (3)	0.01540 (18)
N3	0.45872 (14)	0.09630 (10)	0.05941 (4)	0.01774 (19)
H3B	0.4878	0.0099	0.0513	0.021*
C13	0.17966 (15)	0.64221 (11)	−0.02541 (4)	0.0159 (2)
N4	0.35380 (14)	0.31965 (9)	0.03933 (3)	0.01631 (19)
H4B	0.3663	0.3374	0.0740	0.020*
C11	0.25266 (15)	0.54484 (11)	0.01820 (4)	0.0150 (2)
C10	0.39925 (15)	0.19077 (11)	0.02031 (4)	0.0155 (2)
C9	0.57339 (15)	0.06194 (11)	0.14689 (4)	0.0160 (2)
H9	0.6346	−0.0193	0.1354	0.019*
C8	0.59385 (15)	0.09842 (11)	0.20307 (4)	0.0153 (2)
N1	0.69458 (15)	0.09189 (10)	0.29159 (4)	0.0203 (2)
H1B	0.7590	0.0676	0.3225	0.024*
C12	0.28004 (18)	0.59167 (13)	0.07571 (5)	0.0224 (2)
H12A	0.1593	0.5833	0.0907	0.034*
H12B	0.3223	0.6896	0.0777	0.034*
H12C	0.3764	0.5326	0.0963	0.034*
C14	0.16631 (16)	0.60243 (11)	−0.07989 (4)	0.0180 (2)
C15	0.09241 (18)	0.69504 (13)	−0.12025 (5)	0.0237 (2)
H15	0.0813	0.6664	−0.1568	0.028*
C7	0.71448 (17)	0.03294 (12)	0.24298 (4)	0.0192 (2)
H7	0.7986	−0.0418	0.2375	0.023*
C5	0.49227 (15)	0.20425 (11)	0.22913 (4)	0.0147 (2)
C18	0.12097 (18)	0.77799 (12)	−0.01393 (5)	0.0240 (2)
H18	0.1294	0.8076	0.0224	0.029*
C3	0.48431 (17)	0.27906 (12)	0.32274 (5)	0.0208 (2)
H3	0.5303	0.2721	0.3599	0.025*
C1	0.27606 (18)	0.38481 (13)	0.24917 (5)	0.0255 (3)
H1	0.1791	0.4509	0.2376	0.031*
C4	0.55764 (16)	0.19532 (11)	0.28456 (4)	0.0164 (2)
C2	0.34160 (18)	0.37266 (13)	0.30407 (5)	0.0247 (2)
H2	0.2868	0.4299	0.3290	0.030*
C17	0.05073 (19)	0.87046 (13)	−0.05440 (6)	0.0283 (3)
H17	0.0134	0.9625	−0.0457	0.034*
C6	0.35025 (16)	0.30202 (12)	0.21144 (5)	0.0200 (2)
H6	0.3056	0.3114	0.1743	0.024*
C16	0.03524 (18)	0.82812 (13)	−0.10749 (5)	0.0264 (3)
H16	−0.0148	0.8907	−0.1352	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N2	0.0201 (4)	0.0163 (4)	0.0114 (4)	0.0015 (3)	0.0021 (3)	−0.0005 (3)
O2	0.0286 (4)	0.0170 (4)	0.0127 (3)	0.0047 (3)	0.0009 (3)	−0.0006 (3)
O1	0.0389 (5)	0.0196 (4)	0.0140 (4)	0.0084 (4)	−0.0020 (3)	−0.0002 (3)
N5	0.0172 (4)	0.0140 (4)	0.0148 (4)	0.0021 (3)	0.0012 (3)	0.0020 (3)
N3	0.0264 (5)	0.0145 (4)	0.0121 (4)	0.0054 (3)	0.0016 (3)	−0.0001 (3)
C13	0.0141 (4)	0.0142 (4)	0.0192 (5)	0.0006 (4)	0.0015 (4)	0.0011 (4)
N4	0.0228 (5)	0.0140 (4)	0.0118 (4)	0.0046 (3)	0.0008 (3)	0.0009 (3)
C11	0.0144 (4)	0.0146 (4)	0.0162 (4)	0.0004 (4)	0.0027 (3)	−0.0004 (4)
C10	0.0175 (5)	0.0144 (4)	0.0143 (4)	0.0017 (4)	0.0013 (4)	0.0002 (3)
C9	0.0180 (5)	0.0149 (4)	0.0153 (4)	0.0021 (4)	0.0033 (4)	0.0004 (4)
C8	0.0172 (5)	0.0148 (4)	0.0139 (4)	0.0013 (4)	0.0024 (4)	0.0012 (3)
N1	0.0262 (5)	0.0209 (5)	0.0128 (4)	0.0031 (4)	−0.0008 (3)	0.0018 (3)
C12	0.0300 (6)	0.0201 (5)	0.0173 (5)	0.0019 (4)	0.0036 (4)	−0.0036 (4)
C14	0.0173 (5)	0.0162 (5)	0.0197 (5)	0.0010 (4)	−0.0007 (4)	0.0018 (4)
C15	0.0235 (6)	0.0242 (6)	0.0221 (5)	0.0013 (4)	−0.0028 (4)	0.0061 (4)
C7	0.0232 (5)	0.0187 (5)	0.0157 (5)	0.0044 (4)	0.0016 (4)	0.0015 (4)
C5	0.0161 (5)	0.0138 (4)	0.0143 (4)	−0.0022 (4)	0.0027 (3)	−0.0007 (3)
C18	0.0265 (6)	0.0172 (5)	0.0281 (6)	0.0045 (4)	0.0033 (5)	−0.0003 (4)
C3	0.0244 (6)	0.0212 (5)	0.0176 (5)	−0.0058 (4)	0.0052 (4)	−0.0048 (4)
C1	0.0210 (6)	0.0239 (6)	0.0310 (6)	0.0058 (4)	0.0013 (5)	−0.0083 (5)
C4	0.0188 (5)	0.0151 (5)	0.0156 (5)	−0.0030 (4)	0.0030 (4)	−0.0003 (4)
C2	0.0240 (6)	0.0244 (6)	0.0269 (6)	−0.0022 (5)	0.0076 (5)	−0.0108 (5)
C17	0.0284 (6)	0.0161 (5)	0.0402 (7)	0.0068 (4)	0.0034 (5)	0.0046 (5)
C6	0.0189 (5)	0.0199 (5)	0.0208 (5)	0.0031 (4)	0.0002 (4)	−0.0029 (4)
C16	0.0219 (6)	0.0218 (6)	0.0343 (6)	0.0021 (4)	−0.0013 (5)	0.0116 (5)

Geometric parameters (Å, º)

N2—C9	1.2862 (14)	C12—H12A	0.9800
N2—N3	1.3824 (12)	C12—H12B	0.9800
O2—C10	1.2344 (13)	C12—H12C	0.9800
O1—C14	1.3626 (13)	C14—C15	1.3949 (15)
O1—H1A	0.8400	C15—C16	1.3816 (18)
N5—C11	1.2948 (13)	C15—H15	0.9500
N5—N4	1.3608 (12)	C7—H7	0.9500
N3—C10	1.3591 (13)	C5—C6	1.4013 (15)
N3—H3B	0.8800	C5—C4	1.4125 (14)
C13—C18	1.4007 (15)	C18—C17	1.3887 (17)
C13—C14	1.4111 (15)	C18—H18	0.9500
C13—C11	1.4779 (14)	C3—C2	1.3844 (18)
N4—C10	1.3712 (13)	C3—C4	1.3973 (15)
N4—H4B	0.8800	C3—H3	0.9500
C11—C12	1.5003 (15)	C1—C6	1.3866 (16)
C9—C8	1.4424 (14)	C1—C2	1.4024 (18)
C9—H9	0.9500	C1—H1	0.9500
C8—C7	1.3807 (14)	C2—H2	0.9500
C8—C5	1.4431 (14)	C17—C16	1.384 (2)
N1—C7	1.3672 (14)	C17—H17	0.9500
N1—C4	1.3784 (14)	C6—H6	0.9500
N1—H1B	0.8800	C16—H16	0.9500
C9—N2—N3	116.25 (9)	C15—C14—C13	120.46 (10)
C14—O1—H1A	109.5	C16—C15—C14	120.45 (11)
C11—N5—N4	120.31 (9)	C16—C15—H15	119.8
C10—N3—N2	118.31 (9)	C14—C15—H15	119.8
C10—N3—H3B	120.8	N1—C7—C8	109.75 (10)
N2—N3—H3B	120.8	N1—C7—H7	125.1
C18—C13—C14	117.56 (10)	C8—C7—H7	125.1
C18—C13—C11	120.87 (10)	C6—C5—C4	118.98 (10)
C14—C13—C11	121.57 (9)	C6—C5—C8	134.45 (10)
N5—N4—C10	117.64 (9)	C4—C5—C8	106.55 (9)
N5—N4—H4B	121.2	C17—C18—C13	121.61 (12)
C10—N4—H4B	121.2	C17—C18—H18	119.2
N5—C11—C13	114.95 (9)	C13—C18—H18	119.2
N5—C11—C12	123.94 (10)	C2—C3—C4	117.05 (10)
C13—C11—C12	121.10 (9)	C2—C3—H3	121.5
O2—C10—N3	122.82 (10)	C4—C3—H3	121.5
O2—C10—N4	123.15 (9)	C6—C1—C2	121.18 (11)
N3—C10—N4	114.02 (9)	C6—C1—H1	119.4
N2—C9—C8	119.98 (10)	C2—C1—H1	119.4
N2—C9—H9	120.0	N1—C4—C3	129.59 (10)
C8—C9—H9	120.0	N1—C4—C5	107.85 (9)
C7—C8—C9	125.24 (10)	C3—C4—C5	122.54 (10)
C7—C8—C5	106.56 (9)	C3—C2—C1	121.48 (11)
C9—C8—C5	128.18 (9)	C3—C2—H2	119.3
C7—N1—C4	109.28 (9)	C1—C2—H2	119.3
C7—N1—H1B	125.4	C16—C17—C18	119.80 (11)
C4—N1—H1B	125.4	C16—C17—H17	120.1
C11—C12—H12A	109.5	C18—C17—H17	120.1
C11—C12—H12B	109.5	C1—C6—C5	118.75 (11)
H12A—C12—H12B	109.5	C1—C6—H6	120.6
C11—C12—H12C	109.5	C5—C6—H6	120.6
H12A—C12—H12C	109.5	C15—C16—C17	120.09 (11)
H12B—C12—H12C	109.5	C15—C16—H16	120.0
O1—C14—C15	116.97 (10)	C17—C16—H16	120.0
O1—C14—C13	122.57 (9)
C9—N2—N3—C10	−162.57 (10)	C5—C8—C7—N1	−0.35 (13)
C11—N5—N4—C10	−176.52 (10)	C7—C8—C5—C6	−178.47 (12)
N4—N5—C11—C13	−179.00 (9)	C9—C8—C5—C6	−0.3 (2)
N4—N5—C11—C12	0.64 (16)	C7—C8—C5—C4	−0.58 (12)
C18—C13—C11—N5	174.99 (10)	C9—C8—C5—C4	177.62 (10)
C14—C13—C11—N5	−5.00 (15)	C14—C13—C18—C17	0.46 (18)
C18—C13—C11—C12	−4.66 (16)	C11—C13—C18—C17	−179.52 (11)
C14—C13—C11—C12	175.35 (10)	C7—N1—C4—C3	177.00 (11)
N2—N3—C10—O2	177.29 (10)	C7—N1—C4—C5	−1.54 (13)
N2—N3—C10—N4	−1.86 (15)	C2—C3—C4—N1	−178.03 (11)
N5—N4—C10—O2	2.37 (16)	C2—C3—C4—C5	0.33 (17)
N5—N4—C10—N3	−178.48 (9)	C6—C5—C4—N1	179.57 (10)
N3—N2—C9—C8	−179.42 (9)	C8—C5—C4—N1	1.29 (12)
N2—C9—C8—C7	−172.45 (11)	C6—C5—C4—C3	0.90 (16)
N2—C9—C8—C5	9.66 (17)	C8—C5—C4—C3	−177.38 (10)
C18—C13—C14—O1	178.09 (11)	C4—C3—C2—C1	−1.19 (18)
C11—C13—C14—O1	−1.93 (17)	C6—C1—C2—C3	0.8 (2)
C18—C13—C14—C15	−1.62 (16)	C13—C18—C17—C16	0.9 (2)
C11—C13—C14—C15	178.37 (10)	C2—C1—C6—C5	0.44 (18)
O1—C14—C15—C16	−178.26 (11)	C4—C5—C6—C1	−1.26 (16)
C13—C14—C15—C16	1.46 (18)	C8—C5—C6—C1	176.42 (12)
C4—N1—C7—C8	1.19 (13)	C14—C15—C16—C17	−0.10 (19)
C9—C8—C7—N1	−178.62 (10)	C18—C17—C16—C15	−1.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N5	0.84	1.78	2.5121 (11)	145
N3—H3B···O2^i	0.88	1.99	2.8481 (13)	166
N1—H1B···O1^ii	0.88	2.14	2.8803 (13)	142

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