Crystal structure of 2-(5-bromo-2-hy­droxy­benzyl­idene)-2,3-di­hydro-1H-indene-1,3-dione

Abstract

The title mol­ecule, C₁₆H₉BrO₃, deviates slightly from planarity. The benzene ring makes a dihedral angle of 1.02 (9)° with the plane defined by the five-membered ring of the indandione moiety. The latter exhibits a minute twist indicated by the dihedral angle of 0.47 (9)° between the planes of the five- and six-membered rings. An intra­molecular C—H⋯O hydrogen bond between the attached benzene ring with one of the indandione carbonyl O atoms stabilizes the mol­ecular conformation. In the crystal, the mol­ecules form dimers across centres of inversion via pairwise O—H⋯O hydrogen bonds. The dimers form stacks running parallel to [010] and inter­act through π–π inter­actions between the five-membered ring of one mol­ecule and the six-membered rings of the indandione moiety of an adjacent mol­ecule [centroid-to-centroid distance = 3.5454 (10) Å].

Related literature  

Indan-1,3-dione and its analogues are synthons for building highly inter­esting compounds with a wide range of applications in both pharmaceutical and industrial chemistry (Kuhn & Rae, 1971 ▸; Junek & Sterk, 1968 ▸; Kunz & Polansky, 1969 ▸; Aldersley et al., 1983 ▸). For chemical reactions and bio-activities of 3-substituted indan-1,3-diones, see: Hochrainer & Wessely (1966 ▸); Zargar & Khan (2015 ▸).

Experimental  

Crystal data  

• C₁₆H₉BrO₃

• M _r = 329.14

• Monoclinic,

• a = 13.8820 (4) Å

• b = 3.8695 (1) Å

• c = 24.0068 (5) Å

• β = 102.483 (1)°

• V = 1259.07 (6) ų

• Z = 4

• Cu Kα radiation

• μ = 4.50 mm⁻¹

• T = 150 K

• 0.22 × 0.07 × 0.04 mm

Data collection  

• Bruker D8 VENTURE PHOTON 100 CMOS diffractometer

• Absorption correction: numerical (SADABS; Bruker, 2014 ▸) T _min = 0.67, T _max = 0.84

• 8943 measured reflections

• 2510 independent reflections

• 2386 reflections with I > 2σ(I)

• R _int = 0.020

Refinement  

• R[F ² > 2σ(F ²)] = 0.021

• wR(F ²) = 0.056

• S = 1.09

• 2510 reflections

• 181 parameters

• H-atom parameters constrained

• Δρ_max = 0.36 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: DIAMOND (Brandenburg & Putz, 2012 ▸); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▸).

Supplementary Material

CCDC reference: 1059869

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C6H6O3	0.95	2.15	2.994(2)	148
O1H1O2i	0.84	1.83	2.6641(16)	173

Symmetry code: (i) .

supplementary crystallographic information

S1. Experimental

A mixture of 1 mmol (146 mg) of 1H-indene-1,3(2H)-dione and 1 mmol (201 mg) of 5-bromo-2-hydroxybenzaldehyde in 30 ml ethanol was refluxed for 30 min. The resulting solid product was collected under vacuum and re-crystallized from ethanol to afford yellow needles suitable for X-ray diffraction in 83% yield.

S2. Refinement

H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 Å) while that attached to oxygen was placed in a location derived from a difference map and its coordinates adjusted to give a distance O—H = 0.84 Å. All H atoms were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms.

Figures

Fig. 1.

The title molecule with labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. The intramolecular C—H···O interaction is shown as a dotted line.

Fig. 2.

Crystal packing of the title compound viewed down [010]. Intermolecular O—H···O hydrogen bonds are shown as dotted lines.

Crystal data

C16H9BrO3	F(000) = 656
Mr = 329.14	Dx = 1.736 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 13.8820 (4) Å	Cell parameters from 7789 reflections
b = 3.8695 (1) Å	θ = 3.3–74.5°
c = 24.0068 (5) Å	µ = 4.50 mm−1
β = 102.483 (1)°	T = 150 K
V = 1259.07 (6) Å3	Needle, yellow
Z = 4	0.22 × 0.07 × 0.04 mm

Data collection

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	2510 independent reflections
Radiation source: INCOATEC IµS micro–focus source	2386 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.020
Detector resolution: 10.4167 pixels mm-1	θmax = 74.5°, θmin = 3.3°
ω scans	h = −16→17
Absorption correction: numerical (SADABS; Bruker, 2014)	k = −4→4
Tmin = 0.67, Tmax = 0.84	l = −29→29
8943 measured reflections

Refinement

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)] = 0.021	Hydrogen site location: mixed
wR(F2) = 0.056	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0301P)2 + 0.6412P] where P = (Fo2 + 2Fc2)/3
2510 reflections	(Δ/σ)max = 0.003
181 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.25 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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 Å) while that attached to oxygen was placed in a location derived from a difference map and its coordinates adjusted to give O—H = 0.84 Å. All were included as riding contributions with isotropic displacement parameters 1.2 times those of the attached atoms.

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

	x	y	z	Uiso*/Ueq
Br1	0.74761 (2)	0.32460 (5)	0.72665 (2)	0.02597 (8)
O1	1.00458 (9)	−0.0525 (4)	0.56417 (5)	0.0324 (3)
H1	1.0561	−0.1618	0.5789	0.039*
O2	0.82877 (9)	0.4018 (4)	0.39794 (5)	0.0275 (3)
O3	0.63542 (9)	0.6391 (4)	0.53435 (5)	0.0331 (3)
C1	0.85867 (12)	0.2074 (4)	0.57969 (6)	0.0188 (3)
C2	0.94845 (11)	0.0308 (4)	0.60120 (6)	0.0216 (3)
C3	0.97616 (11)	−0.0550 (4)	0.65901 (6)	0.0227 (3)
H3	1.0370	−0.1702	0.6731	0.027*
C4	0.91553 (12)	0.0270 (4)	0.69553 (6)	0.0215 (3)
H4	0.9339	−0.0334	0.7348	0.026*
C5	0.82703 (12)	0.1991 (4)	0.67450 (6)	0.0195 (3)
C6	0.79773 (12)	0.2902 (4)	0.61786 (6)	0.0195 (3)
H6	0.7370	0.4079	0.6046	0.023*
C7	0.83772 (12)	0.2944 (4)	0.51956 (6)	0.0196 (3)
H7	0.8883	0.2221	0.5011	0.024*
C8	0.76223 (11)	0.4559 (4)	0.48379 (6)	0.0193 (3)
C9	0.76467 (11)	0.4982 (4)	0.42218 (6)	0.0195 (3)
C10	0.67288 (11)	0.6780 (4)	0.39402 (7)	0.0191 (3)
C11	0.64124 (13)	0.7720 (4)	0.33723 (7)	0.0235 (3)
H11	0.6801	0.7253	0.3100	0.028*
C12	0.55046 (13)	0.9372 (4)	0.32177 (7)	0.0262 (3)
H12	0.5268	1.0061	0.2833	0.031*
C13	0.49331 (12)	1.0039 (5)	0.36193 (7)	0.0269 (3)
H13	0.4315	1.1172	0.3502	0.032*
C14	0.52519 (12)	0.9075 (5)	0.41869 (7)	0.0243 (3)
H14	0.4862	0.9515	0.4459	0.029*
C15	0.61626 (12)	0.7441 (4)	0.43405 (7)	0.0202 (3)
C16	0.66754 (12)	0.6133 (4)	0.49114 (7)	0.0216 (3)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.03096 (11)	0.02856 (12)	0.02164 (10)	0.00308 (7)	0.01281 (7)	−0.00170 (6)
O1	0.0248 (6)	0.0525 (8)	0.0217 (5)	0.0200 (6)	0.0089 (4)	0.0075 (6)
O2	0.0239 (6)	0.0394 (7)	0.0207 (5)	0.0109 (5)	0.0084 (4)	0.0042 (5)
O3	0.0278 (6)	0.0513 (8)	0.0223 (6)	0.0172 (6)	0.0102 (5)	0.0053 (5)
C1	0.0181 (7)	0.0208 (8)	0.0175 (7)	0.0013 (6)	0.0038 (6)	−0.0007 (6)
C2	0.0193 (7)	0.0260 (8)	0.0200 (7)	0.0031 (7)	0.0057 (6)	0.0000 (6)
C3	0.0193 (7)	0.0266 (8)	0.0208 (7)	0.0037 (7)	0.0012 (6)	0.0023 (6)
C4	0.0236 (7)	0.0225 (8)	0.0172 (6)	−0.0010 (7)	0.0019 (6)	0.0004 (6)
C5	0.0206 (7)	0.0203 (8)	0.0193 (7)	−0.0011 (6)	0.0079 (6)	−0.0030 (6)
C6	0.0186 (7)	0.0201 (8)	0.0199 (7)	0.0023 (6)	0.0042 (6)	−0.0011 (6)
C7	0.0193 (7)	0.0217 (8)	0.0189 (7)	0.0021 (6)	0.0062 (6)	−0.0013 (6)
C8	0.0190 (7)	0.0208 (7)	0.0184 (7)	0.0014 (6)	0.0049 (5)	−0.0006 (6)
C9	0.0190 (7)	0.0201 (7)	0.0189 (7)	0.0011 (6)	0.0032 (5)	0.0006 (6)
C10	0.0181 (7)	0.0173 (7)	0.0215 (7)	−0.0004 (6)	0.0033 (6)	−0.0010 (5)
C11	0.0262 (8)	0.0230 (8)	0.0207 (7)	0.0017 (7)	0.0039 (6)	0.0016 (6)
C12	0.0299 (8)	0.0222 (8)	0.0224 (7)	0.0013 (7)	−0.0033 (6)	0.0022 (6)
C13	0.0218 (8)	0.0230 (8)	0.0317 (8)	0.0043 (7)	−0.0032 (6)	−0.0005 (7)
C14	0.0191 (7)	0.0259 (8)	0.0271 (8)	0.0039 (7)	0.0031 (6)	−0.0019 (7)
C15	0.0181 (7)	0.0203 (7)	0.0211 (7)	0.0010 (6)	0.0019 (6)	−0.0010 (6)
C16	0.0196 (7)	0.0238 (8)	0.0211 (7)	0.0040 (6)	0.0037 (6)	0.0005 (6)

Geometric parameters (Å, º)

Br1—C5	1.9014 (15)	C7—H7	0.9500
O1—C2	1.3418 (19)	C8—C16	1.493 (2)
O1—H1	0.8400	C8—C9	1.4956 (19)
O2—C9	1.2221 (19)	C9—C10	1.481 (2)
O3—C16	1.218 (2)	C10—C11	1.387 (2)
C1—C6	1.412 (2)	C10—C15	1.390 (2)
C1—C2	1.417 (2)	C11—C12	1.390 (2)
C1—C7	1.449 (2)	C11—H11	0.9500
C2—C3	1.398 (2)	C12—C13	1.399 (3)
C3—C4	1.377 (2)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.390 (2)
C4—C5	1.393 (2)	C13—H13	0.9500
C4—H4	0.9500	C14—C15	1.390 (2)
C5—C6	1.378 (2)	C14—H14	0.9500
C6—H6	0.9500	C15—C16	1.490 (2)
C7—C8	1.355 (2)
C2—O1—H1	113.9	O2—C9—C10	124.70 (14)
C6—C1—C2	118.43 (14)	O2—C9—C8	127.73 (14)
C6—C1—C7	125.05 (14)	C10—C9—C8	107.57 (13)
C2—C1—C7	116.51 (14)	C11—C10—C15	121.66 (15)
O1—C2—C3	121.74 (14)	C11—C10—C9	129.07 (15)
O1—C2—C1	117.73 (13)	C15—C10—C9	109.27 (13)
C3—C2—C1	120.53 (14)	C10—C11—C12	117.32 (15)
C4—C3—C2	120.16 (14)	C10—C11—H11	121.3
C4—C3—H3	119.9	C12—C11—H11	121.3
C2—C3—H3	119.9	C11—C12—C13	121.16 (15)
C3—C4—C5	119.47 (14)	C11—C12—H12	119.4
C3—C4—H4	120.3	C13—C12—H12	119.4
C5—C4—H4	120.3	C14—C13—C12	121.23 (15)
C6—C5—C4	121.94 (14)	C14—C13—H13	119.4
C6—C5—Br1	119.65 (12)	C12—C13—H13	119.4
C4—C5—Br1	118.37 (11)	C13—C14—C15	117.44 (15)
C5—C6—C1	119.46 (14)	C13—C14—H14	121.3
C5—C6—H6	120.3	C15—C14—H14	121.3
C1—C6—H6	120.3	C14—C15—C10	121.19 (15)
C8—C7—C1	134.39 (15)	C14—C15—C16	128.67 (15)
C8—C7—H7	112.8	C10—C15—C16	110.15 (14)
C1—C7—H7	112.8	O3—C16—C15	124.43 (15)
C7—C8—C16	133.85 (14)	O3—C16—C8	128.87 (14)
C7—C8—C9	119.83 (14)	C15—C16—C8	106.70 (13)
C16—C8—C9	106.32 (13)
C6—C1—C2—O1	178.65 (15)	C8—C9—C10—C11	−179.35 (16)
C7—C1—C2—O1	−2.4 (2)	O2—C9—C10—C15	179.00 (16)
C6—C1—C2—C3	−0.7 (2)	C8—C9—C10—C15	−0.22 (18)
C7—C1—C2—C3	178.19 (15)	C15—C10—C11—C12	0.3 (2)
O1—C2—C3—C4	−178.38 (17)	C9—C10—C11—C12	179.34 (16)
C1—C2—C3—C4	1.0 (3)	C10—C11—C12—C13	−0.3 (3)
C2—C3—C4—C5	−0.7 (3)	C11—C12—C13—C14	0.0 (3)
C3—C4—C5—C6	0.1 (3)	C12—C13—C14—C15	0.4 (3)
C3—C4—C5—Br1	−177.54 (13)	C13—C14—C15—C10	−0.4 (3)
C4—C5—C6—C1	0.1 (2)	C13—C14—C15—C16	−179.70 (17)
Br1—C5—C6—C1	177.74 (12)	C11—C10—C15—C14	0.1 (3)
C2—C1—C6—C5	0.2 (2)	C9—C10—C15—C14	−179.15 (15)
C7—C1—C6—C5	−178.61 (15)	C11—C10—C15—C16	179.48 (15)
C6—C1—C7—C8	−1.5 (3)	C9—C10—C15—C16	0.27 (19)
C2—C1—C7—C8	179.65 (18)	C14—C15—C16—O3	−1.4 (3)
C1—C7—C8—C16	−0.2 (3)	C10—C15—C16—O3	179.24 (17)
C1—C7—C8—C9	−179.21 (17)	C14—C15—C16—C8	179.14 (17)
C7—C8—C9—O2	0.1 (3)	C10—C15—C16—C8	−0.22 (19)
C16—C8—C9—O2	−179.12 (17)	C7—C8—C16—O3	1.5 (3)
C7—C8—C9—C10	179.33 (15)	C9—C8—C16—O3	−179.35 (18)
C16—C8—C9—C10	0.08 (17)	C7—C8—C16—C15	−179.02 (18)
O2—C9—C10—C11	−0.1 (3)	C9—C8—C16—C15	0.08 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3	0.95	2.15	2.994 (2)	148
O1—H1···O2i	0.84	1.83	2.6641 (16)	173

Symmetry code: (i) −x+2, −y, −z+1.