Isatin 3-benzoyl­hydrazone: an ortho­rhom­bic form

The amine N atom of the isatin portion of the title compound (systematic name: 2-oxo-2,3-dihydro-1H-indole-3-carbaldehyde benzoylhydrazone), C₁₅H₁₁N₃O₂, forms a hydrogen bond with the amide O atom of the benzoyl­hydrazone portion of a symmetry-related mol­ecule to give rise to a hydrogen-bonded chain structure that propagates by a twofold screw axis along the a axis of the ortho­rhom­bic unit cell.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.058
• wR factor = 0.191
• Data-to-parameter ratio = 8.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT411_ALERT_2_B Short Inter H...H Contact  H4     ..  H12     ..       2.05 Ang.

Alert level C
CRYSC01_ALERT_1_C The word below has not been recognised as a standard
            identifier.
            Yellowish
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C3     -   C4      ..       5.97 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C3
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          6
PLAT414_ALERT_2_C Short Intra D-H..H-X       H1N    ..  H6      ..       1.96 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.10
           From the CIF: _reflns_number_total               1463
           Count of symmetry unique reflns         1474
           Completeness (_total/calc)             99.25%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 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

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S1. Comment

The preceeding report describes the structure of the monoclinic form of isatin 3-benzoylhydrazone (Ali et al., 2005). In the orthorhombic form, the chain formed by hydrogen-bonded molecules propages by twofold screw axial translations (Fig. 1), whereas in the monoclinic form the chain formed by hydrogen bonded molecules propagates by glide planes. The orthorhombic form is significantly denser (density = 1.467 Mg m⁻³) than the monoclinic form (density = 1.392 Mg m⁻³), as the polymeric chain is more flexible owing to a more adaptable, helical construction.

S2. Experimental

Isatin 3-benzoylhydrazone (0.50 g, 1.9 mmol) and zinc acetate (0.20 g, 0.9 mmol) were refluxed for 5 h. The yellow solid that precipitated was collected and recrystallized from pyridine to give yellow–orange blocks. The color is distinctly different from that of the monoclinic polymorph.

S3. Refinement

The phenyl ring comprising atoms C1–C6 was refined with the C—C distances restrained to 1.390 (5) Å; the 1,4-distances were restrained to 2.780 (5) Å. As there are no heavy scatterers, Friedel pairs were merged. H atoms were placed at calculated positions (C—H = 0.93 Å and N—H = 0.86 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2U_eq(C,N).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of C15H11N3O2. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are shown as spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines.

2-oxo-2,3-dihydro-1H-indole-3-carbaldehyde benzoylhydrazone

Crystal data

C15H11N3O2	F(000) = 552
Mr = 265.27	Dx = 1.467 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 928 reflections
a = 8.0023 (9) Å	θ = 2.5–25.7°
b = 28.549 (3) Å	µ = 0.10 mm^−1
c = 5.2574 (6) Å	T = 295 K
V = 1201.1 (2) Å^3	Block, yellow–orange
Z = 4	0.34 × 0.21 × 0.15 mm

Data collection

Bruker SMART area-detector diffractometer	1176 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Graphite monochromator	θmax = 27.1°, θmin = 1.4°
ϕ and ω scan	h = −8→10
6999 measured reflections	k = −36→36
1463 independent reflections	l = −6→5

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.058	H-atom parameters constrained
wR(F^2) = 0.191	w = 1/[σ^2(Fo^2) + (0.1317P)^2 + 0.2812P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
1463 reflections	Δρmax = 0.53 e Å^−3
181 parameters	Δρmin = −0.29 e Å^−3
10 restraints	Absolute structure: Flack parameter not calculated.
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.9079 (4)	0.64394 (9)	0.5000 (9)	0.0551 (9)
O2	0.5986 (4)	0.71442 (10)	1.2189 (9)	0.0499 (8)
N1	0.7807 (4)	0.67794 (11)	0.8348 (10)	0.0419 (8)
H1n	0.7250	0.6740	0.9730	0.050*
N2	0.8179 (4)	0.72247 (11)	0.7520 (9)	0.0399 (8)
N3	0.6094 (4)	0.79527 (11)	1.1946 (9)	0.0419 (8)
H3n	0.5486	0.8023	1.3239	0.050*
C1	0.7871 (5)	0.59389 (11)	0.8110 (8)	0.0451 (11)
C2	0.8561 (6)	0.55486 (12)	0.6924 (7)	0.0629 (14)
H2	0.9284	0.5584	0.5552	0.075*
C3	0.8157 (7)	0.51022 (13)	0.7820 (10)	0.085 (2)
H3	0.8590	0.4839	0.7010	0.102*
C4	0.7118 (6)	0.50472 (12)	0.9899 (10)	0.0667 (16)
H4	0.6873	0.4749	1.0502	0.080*
C5	0.6448 (6)	0.54334 (14)	1.1072 (7)	0.0759 (18)
H5	0.5736	0.5394	1.2454	0.091*
C6	0.6823 (6)	0.58848 (12)	1.0217 (10)	0.0582 (12)
H6	0.6382	0.6145	1.1038	0.070*
C7	0.8314 (5)	0.64071 (13)	0.6995 (11)	0.0396 (10)
C8	0.7545 (5)	0.75561 (12)	0.8866 (10)	0.0350 (9)
C9	0.6446 (5)	0.75100 (14)	1.1214 (10)	0.0390 (9)
C10	0.6841 (4)	0.82823 (12)	1.0342 (11)	0.0363 (8)
C11	0.6762 (5)	0.87673 (14)	1.0456 (12)	0.0456 (10)
H11	0.6189	0.8920	1.1753	0.055*
C12	0.7573 (6)	0.90155 (14)	0.8557 (12)	0.0494 (11)
H12	0.7518	0.9341	0.8571	0.059*
C13	0.8460 (5)	0.87959 (13)	0.6644 (11)	0.0458 (10)
H13	0.8986	0.8974	0.5397	0.055*
C14	0.8569 (4)	0.83080 (13)	0.6578 (11)	0.0417 (10)
H14	0.9188	0.8157	0.5326	0.050*
C15	0.7734 (5)	0.80574 (13)	0.8417 (10)	0.0374 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.073 (2)	0.0388 (15)	0.053 (2)	−0.0012 (14)	0.0181 (18)	−0.0018 (15)
O2	0.0633 (18)	0.0391 (14)	0.0474 (19)	−0.0043 (12)	0.0125 (17)	0.0069 (14)
N1	0.0498 (17)	0.0287 (15)	0.047 (2)	−0.0036 (13)	0.0079 (17)	0.0020 (16)
N2	0.0459 (17)	0.0290 (15)	0.045 (2)	−0.0013 (13)	0.0022 (16)	−0.0018 (15)
N3	0.0535 (19)	0.0367 (16)	0.035 (2)	0.0060 (13)	0.0046 (17)	−0.0025 (15)
C1	0.046 (2)	0.034 (2)	0.056 (3)	−0.0049 (16)	−0.005 (2)	0.001 (2)
C2	0.081 (3)	0.037 (2)	0.071 (4)	0.000 (2)	−0.001 (3)	−0.005 (3)
C3	0.127 (5)	0.033 (2)	0.096 (6)	0.002 (3)	−0.028 (5)	0.003 (3)
C4	0.090 (3)	0.029 (2)	0.081 (4)	−0.015 (2)	−0.024 (4)	0.018 (3)
C5	0.085 (4)	0.062 (3)	0.081 (5)	−0.023 (3)	−0.006 (3)	0.024 (3)
C6	0.061 (3)	0.044 (2)	0.069 (3)	−0.006 (2)	0.001 (3)	0.011 (3)
C7	0.0409 (19)	0.0311 (18)	0.047 (3)	−0.0011 (14)	−0.001 (2)	0.0017 (18)
C8	0.0385 (18)	0.0281 (17)	0.038 (2)	−0.0004 (15)	0.0001 (18)	−0.0014 (18)
C9	0.043 (2)	0.0364 (18)	0.038 (2)	0.0016 (16)	0.0020 (18)	0.0003 (17)
C10	0.0410 (18)	0.0308 (17)	0.037 (2)	−0.0006 (15)	−0.0051 (18)	−0.0033 (18)
C11	0.054 (2)	0.0359 (19)	0.047 (3)	0.0062 (17)	−0.002 (2)	−0.004 (2)
C12	0.059 (2)	0.0331 (19)	0.056 (3)	−0.0010 (18)	−0.004 (2)	0.000 (2)
C13	0.055 (2)	0.035 (2)	0.048 (3)	−0.0061 (17)	0.003 (2)	0.002 (2)
C14	0.045 (2)	0.0367 (19)	0.044 (2)	−0.0017 (16)	0.000 (2)	−0.001 (2)
C15	0.0429 (18)	0.0327 (17)	0.037 (2)	0.0001 (15)	−0.0041 (17)	−0.0011 (19)

Geometric parameters (Å, º)

O1—C7	1.218 (7)	C4—H4	0.9300
O2—C9	1.220 (5)	C5—C6	1.398 (4)
N1—C7	1.342 (5)	C5—H5	0.9300
N1—N2	1.376 (5)	C6—H6	0.9300
N1—H1n	0.8600	C8—C15	1.458 (5)
N2—C8	1.286 (5)	C8—C9	1.521 (6)
N3—C9	1.351 (5)	C10—C11	1.387 (5)
N3—C10	1.398 (5)	C10—C15	1.395 (6)
N3—H3n	0.8600	C11—C12	1.385 (7)
C1—C2	1.391 (4)	C11—H11	0.9300
C1—C6	1.398 (4)	C12—C13	1.381 (7)
C1—C7	1.502 (5)	C12—H12	0.9300
C2—C3	1.396 (4)	C13—C14	1.396 (5)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.382 (4)	C14—C15	1.376 (6)
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.372 (4)
C7—N1—N2	119.9 (4)	O1—C7—C1	121.5 (4)
C7—N1—H1n	120.0	N1—C7—C1	115.3 (4)
N2—N1—H1n	120.0	N2—C8—C15	126.3 (4)
C8—N2—N1	114.9 (4)	N2—C8—C9	127.7 (3)
C9—N3—C10	111.6 (3)	C15—C8—C9	106.0 (3)
C9—N3—H3n	124.2	O2—C9—N3	128.2 (4)
C10—N3—H3n	124.2	O2—C9—C8	126.1 (4)
C2—C1—C6	120.3 (3)	N3—C9—C8	105.7 (3)
C2—C1—C7	116.4 (3)	C11—C10—C15	120.9 (4)
C6—C1—C7	123.3 (3)	C11—C10—N3	128.8 (4)
C1—C2—C3	119.2 (4)	C15—C10—N3	110.3 (3)
C1—C2—H2	120.4	C12—C11—C10	117.3 (4)
C3—C2—H2	120.4	C12—C11—H11	121.4
C4—C3—C2	120.7 (4)	C10—C11—H11	121.4
C4—C3—H3	119.7	C13—C12—C11	122.2 (4)
C2—C3—H3	119.7	C13—C12—H12	118.9
C5—C4—C3	119.9 (3)	C11—C12—H12	118.9
C5—C4—H4	120.0	C12—C13—C14	120.2 (4)
C3—C4—H4	120.0	C12—C13—H13	119.9
C4—C5—C6	120.8 (4)	C14—C13—H13	119.9
C4—C5—H5	119.6	C15—C14—C13	118.1 (4)
C6—C5—H5	119.6	C15—C14—H14	121.0
C5—C6—C1	119.1 (4)	C13—C14—H14	121.0
C5—C6—H6	120.5	C14—C15—C10	121.3 (3)
C1—C6—H6	120.5	C14—C15—C8	132.4 (4)
O1—C7—N1	123.3 (4)	C10—C15—C8	106.3 (3)
C7—N1—N2—C8	175.8 (4)	C15—C8—C9—O2	179.3 (4)
C6—C1—C2—C3	1.8 (8)	N2—C8—C9—N3	−179.9 (4)
C7—C1—C2—C3	−178.0 (5)	C15—C8—C9—N3	−0.3 (4)
C1—C2—C3—C4	−1.7 (9)	C9—N3—C10—C11	179.4 (4)
C2—C3—C4—C5	1.3 (9)	C9—N3—C10—C15	0.4 (5)
C3—C4—C5—C6	−1.0 (9)	C15—C10—C11—C12	1.4 (6)
C4—C5—C6—C1	1.2 (8)	N3—C10—C11—C12	−177.6 (4)
C2—C1—C6—C5	−1.6 (7)	C10—C11—C12—C13	−1.4 (7)
C7—C1—C6—C5	178.3 (5)	C11—C12—C13—C14	−0.2 (7)
N2—N1—C7—O1	−1.4 (7)	C12—C13—C14—C15	1.8 (6)
N2—N1—C7—C1	178.7 (3)	C13—C14—C15—C10	−1.8 (6)
C2—C1—C7—O1	8.0 (7)	C13—C14—C15—C8	178.1 (4)
C6—C1—C7—O1	−171.9 (4)	C11—C10—C15—C14	0.2 (6)
C2—C1—C7—N1	−172.1 (4)	N3—C10—C15—C14	179.3 (4)
C6—C1—C7—N1	8.0 (6)	C11—C10—C15—C8	−179.7 (4)
N1—N2—C8—C15	−179.8 (4)	N3—C10—C15—C8	−0.6 (4)
N1—N2—C8—C9	−0.3 (6)	N2—C8—C15—C14	0.2 (8)
C10—N3—C9—O2	−179.7 (4)	C9—C8—C15—C14	−179.4 (4)
C10—N3—C9—C8	−0.1 (5)	N2—C8—C15—C10	−179.9 (4)
N2—C8—C9—O2	−0.3 (7)	C9—C8—C15—C10	0.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···O2	0.86	2.01	2.699 (5)	137
N3—H3n···O1^i	0.86	2.12	2.862 (5)	145

Symmetry code: (i) x−1/2, −y+3/2, z+1.