Crystal structures of 6-chloro­indan-1-one and 6-bromo­indan-1-one exhibit different inter­molecular packing inter­actions

Caruso, A.; Blair, B.; Tanski, J.M.

doi:10.1107/S2056989016015371

research communications

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Volume 72| Part 11| November 2016| Pages 1536-1540

https://doi.org/10.1107/S2056989016015371

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Crystal structures of 6-chloroindan-1-one and 6-bromoindan-1-one exhibit different intermolecular packing interactions

Alessio Caruso,^a Benjamin Blair ^a and Joseph M. Tanski ^a ^*

^aDepartment of Chemistry, Vassar College, Poughkeepsie, NY 12604, USA
^*Correspondence e-mail: jotanski@vassar.edu

Edited by J. Simpson, University of Otago, New Zealand (Received 28 September 2016; accepted 29 September 2016; online 7 October 2016)

The two title compounds are analogs of 1-indanone that are substituted at the 6-position with chlorine and bromine. Although very similar in molecular structure, the crystal structures are not isomorphous and reveal that 6-chloroindan-1-one, C₉H₇ClO (I), and 6-bromoindan-1-one, C₉H₇BrO (II), exhibit unique intermolecular packing motifs. The molecules of the chloro analog (I) pack with a herringbone packing motif of C—H⋯O interactions, whereas the bromo derivative (II) packs with offset face-to-face π-stacking, C—H⋯O, C—H⋯Br and Br⋯O interactions. Compound (II) was refined as a two-component non-merohedral twin, BASF 0.0762 (5).

Keywords: crystal structure; haloindanones; π-stacking; C—H⋯X interactions.

CCDC references: 1507437; 1507436

1. Chemical context

Halogenated derivatives of the common bicyclic organic framework 1-indanone have been shown to be useful in a variety of synthetic and biologically related applications (Ruiz et al., 2004 ). A search of the Cambridge Structural Database (Version 5.31, September 2016 with updates; Groom et al., 2016 ) returns four simple arylhalide substituted 1-indanones, although several more are commercially available. The title compounds represent two analogs of 6-haloindan-1-one that are notably not isomorphous. In addition, they are not isomorphous with the fluorine derivative 6-fluoroindan-1-one, which is one of the four that has previously been reported (Slaw & Tanski, 2014 ). In the chloro analog, 6-chloroindan-1-one (I), the molecules pack together via a series of C—H⋯O interactions. C—H⋯X interactions are common and have been discussed in the literature (Desiraju & Steiner, 1999 ), as well as specifically in the case of 1-indanone itself (Ruiz et al., 2004). The bromo derivative 6-bromoindan-1-one (II) packs with offset face-to-face π-stacking (Hunter & Saunders, 1990 ; Lueckheide et al., 2013 ) and several different intermolecular contacts including C—H⋯O, C—H⋯Br weak hydrogen bonds and Br⋯O interactions.

The compounds 6-chloroindan-1-one (I) and 6-bromoindan-1-one (II) may be synthesized by the microwave or ultrasound-aided ring closure of 4-chloro- or 4-bromobenzenepropanoic acid, respectively, catalyzed by triflic acid in dichloromethane (Oliverio et al., 2014 ). 6-Haloindan-1-ones have featured in the synthesis of biologically or pharmacologically active compounds. In recent examples, 6-chloroindan-1-one (I) has been employed in the total synthesis of the anticancer natural product chartarin (Unzner et al., 2016 ), and in the synthesis of triazole-quinoline derivatives that are acetylcholinesterase inhibitors relevant to the treatment of Alzheimer's disease (Mantoani et al., 2016 ). 6-Bromoindan-1-one has been used as the starting material for the synthesis of small molecules that inhibit cell entry by HIV-1 (Melillo et al., 2016 ), and both 6-chloroindan-1-one and 6-bromoindan-1-one have been used as the starting material for the preparation of C-7 substituted 3,4-dihydroisoquinolin-1(2H)-one analogues that selectively inhibit unique poly-ADP-ribose polymerases (Morgan et al., 2015 ).

2. Structural commentary

The molecular features of 6-chloroindan-1-one (I) (Fig. 1) and 6-bromoindan-1-one (II) (Fig. 2) are similar to those reported for the analogous structure 6-fluoroindan-1-one (Slaw & Tanski, 2014), although the analogues are not isomorphous and exhibit different intermolecular packing. In the chloro derivative (I), the aryl C—Cl bond length, 1.7435 (11) Å, is similar to that found in the isomeric compound 5-chloroindan-1-one [C—Cl = 1.735 (2) Å; Ruiz et al., 2006 ]. The aryl C—Br bond length in the bromo analog (II), 1.907 (3) Å, is similar to that found in the isomeric compound 4-bromoindan-1-one [1.894 (1) Å; Aldeborgh et al., 2014 ]. The C=O bond lengths in 6-chloroindan-1-one (I), 1.2200 (12) Å, and 6-bromoindan-1-one (II), 1.216 (3) Å, are also very similar to those found in the other four reported structures of simple arylhalide-substituted 1-indanones: 6-fluoroindan-1-one, 1.2172 (13) Å (Slaw & Tanski, 2014); 5-fluoroindan-1-one, 1.218 (2) Å (Garcia et al.,1995 ); 5-chloroindan-1-one, 1.210 (3) Å (Ruiz et al., 2006); 4-bromoindan-1-one, 1.215 (2) Å (Aldeborgh et al., 2014). These carbonyl C=O bond lengths are also similar to that found in the structure of the parent compound, 1-indanone, 1.217 (2) Å (Ruiz et al., 2004). With the exception of the methylene hydrogen atoms, both (I) and (II) are nearly planar, with r.m.s. deviations from the mean planes of all non-H atoms of 0.0460 and 0.0107 Å, respectively.

Figure 1
A view of 6-chloroindan-1-one (I)

with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level.

Figure 2
A view of 6-bromoindan-1-one (II)

with the atom-numbering scheme. Displacement ellipsoids are shown at the 50% probability level.

3. Supramolecular features

In the crystal structure of 6-chloroindan-1-one (I), the molecules pack together via van der Waals contacts, specifically C—H⋯O interactions, without any π-stacking. The C—H⋯O interactions (Fig. 3 and Table 1) connect the indanone oxygen atom with methylene hydrogen atoms on neighboring molecules into a two-molecule-thick sheet parallel to the (100) plane (Fig. 4). These sheets further pack together without any notable intermolecular contacts. The closest Cl⋯Cl contact between the sheets, 3.728 Å, is somewhat longer than the sum of the van der Waals radii of chlorine, 3.50 Å (Bondi, 1964 ).

Table 1
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.99	2.56	3.1933 (15)	121
C2—H2B⋯O1ⁱⁱ	0.99	2.59	3.5448 (14)	161
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y+2, -z.

Figure 3
A view of the intermolecular C—H⋯O contacts in 6-chloroindan-1-one (I)

. See Table 1

for symmetry codes (i) and (ii). In this and subsequent figures the C—H⋯X interactions are shown as dashed lines.

Figure 4
A view of the sheet structure in 6-chloroindan-1-one (I)

formed by C—H⋯O contacts. See Table 1

for symmetry codes (i) and (ii).

The molecular packing in the bromo analog, 6-bromoindan-1-one (II), is distinct from that found in (I). The notable intermolecular interactions observed include π-stacking, Br⋯O, C—H⋯O, and C—H⋯Br interactions. The offset face-to-face π-stacking can be seen to extend along the crystallographic c axis (Fig. 5), with the molecules stacking in an alternating head-to-tail fashion featuring a C—H⋯Br interaction with an H⋯Br distance of 3.05 Å (Fig. 5 and Table 2). The π-stacking is characterized by a centroid-to-centroid distance of 3.850 (3) Å, centroid-to-plane distances of 3.530 (2) and 3.603 (2) Å, and ring offsets of 1.358 (3) and 1.536 (3) Å that result in a plane-to-plane angle of 3.1 (1)°. The π-stacked chains of (II) are linked into a three-dimensional lattice by C—H⋯O interactions and a Br⋯O contact (Fig. 6 and Table 2). The Br⋯O contact, at a distance of 3.018 (2) Å, is slightly shorter than the sum of the van der Waals radii, 3.37 Å (Bondi 1964). This interaction is even shorter than the Br⋯O contact in the isomeric 4-bromoindan-1-one [3.129 (1) Å; Aldeborgh et al., 2014].

Table 2
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3B⋯O1ⁱ	0.99	2.45	3.408 (4)	162
C5—H5A⋯O1ⁱⁱ	0.95	2.55	3.253 (4)	131
C2—H2B⋯Br1ⁱⁱⁱ	0.99	3.05	3.898 (3)	145
Symmetry codes: (i) x-1, y, z; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 5
A view of the alternating offset face-to-face π-stacking and C—H⋯Br interaction in 6-bromoindan-1-one (II)

with the thick black line indicating a centroid-to-centroid interaction. See Table 2

for symmetry code (iii).

Figure 6
A view of the intermolecular C—H⋯O and Br⋯O contacts (dashed lines) in 6-bromoindan-1-one (II)

. See Table 2

for symmetry codes (i) and (ii).

4. Database survey

A survey of the Cambridge Structural Database reveals that in addition to the two structures reported here, there are four other simple arylhalide-substituted 1-indanone structures known. These include 6-fluoroindan-1-one (Slaw & Tanski, 2014), 5-fluoroindan-1-one (Garcia et al., 1995), 5-chloroindan-1-one (Ruiz et al., 2006) and 4-bromoindan-1-one (Aldeborgh et al., 2014). The crystal structure of 1-indanone itself was first reported in 1974 (Morin et al., 1974 ) and was later described in a more detailed structural and spectroscopic analysis (Ruiz et al., 2004).

5. Synthesis and crystallization

6-Chloroindan-1-one (96%) and 6-bromoindan-1-one (98%) were purchased from Aldrich Chemical Company, USA, and were used as received.

6. Analytical data

6-Chloroindan-1-one (I): ¹H NMR (Bruker Avance 300 MHz, CDCl₃): δ 2.72 (t, 2 H, J = 5.9 Hz, CH₂), 3.12 (t, 2H, J = 5.9 Hz, CH₂), 7.42 (d, 1 H, J_ortho = 8.2 Hz, C_arylH), 7.53 (dd, 1H, J_meta = 1.6 Hz, J_ortho = 8.1 Hz, C_arylH), 7.69 (s, 1 H, C_arylH). ¹³C NMR (¹³C{¹H}, 75.5 MHz, CDCl₃): δ 25.37 (CH₂), 36.57 (CH₂), 123.45 (C_arylH), 127.85 (C_arylH), 133.63 (C_aryl), 134.50 (C_arylH), 138.49 (C_aryl), 153.07 (C_aryl), 205.43 (C=O). IR (Thermo Nicolet iS50, KBr pellet, cm⁻¹): 3391 (w), 3076 (w), 3051 (w), 2964 (w), 2935 (w), 1702 (vs, C=O str), 1595 (w), 1576 (w), 1466 (m), 1435 (m), 1409 (m), 1318 (w), 1285 (w), 1276 (w), 1250 (m), 1214 (w), 1187 (m), 1173 (m), 1115 (m), 1037 (w), 895 (m), 854 (m), 836 (s), 815 (m), 678 (m), 623 (m), 561 (m), 518 (w), 484 (m). GC/MS (Hewlett-Packard MS 5975/GC 7890): M⁺ = 166 (calculated exact mass 166.02).

6-Bromoindan-1-one (II): ¹H NMR (Bruker Avance 300 MHz, CDCl₃): δ 2.71 (t, 2 H, J = 5.8 Hz, CH₂), 3.09 (t, 2H, J = 5.9 Hz, CH₂), 7.37 (d, 1 H, J_ortho = 8.1 Hz, C_arylH), 7.65 (dd, 1H, J_meta = 1.9 Hz, J_ortho = 8.1 Hz, C_arylH), 7.83 (s, 1 H, C_arylH). ¹³C NMR (¹³C{¹H}, 75.5 MHz, CDCl₃): δ 25.37 (CH₂), 36.34 (CH₂), 121.35 (C_aryl), 126.46 (C_arylH), 128.16 (C_arylH), 137.14 (C_arylH), 138.73 (C_aryl), 153.47 (C_aryl), 205.19 (C=O). IR (Thermo Nicolet iS50, ATR, cm⁻¹): 3394 (w), 3066 (w), 2962 (w), 2925 (w), 1698 (vs, C=O str), 1598 (w), 1577 (w), 1468 (w), 1438 (s), 1417 (w), 1398 (m), 1322 (w), 1295 (w), 1279 (w), 1253 (m), 1238 (m), 1213 (w), 1191 (s), 1171 (w), 1112 (m), 1038 (w), 978 (w), 887 (w), 829 (s), 668 (m), 609 (w), 557 (m), 509 (w), 478 (m). GC/MS (Hewlett-Packard MS 5975/GC 7890): M⁺ = 210 (calculated exact mass 209.97).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. After indexing with Cell_Now (Sheldrick, 2008 ), 6-bromoindan-1-one (II) was refined as a two-component non-merohedral twin, BASF 0.0762 (5). Carbon-bound hydrogen atoms were included in calculated positions and refined using a riding model at C—H = 0.95 and 0.99 Å and U_iso(H) = 1.2U_eq(C) of the aryl and methylene C atoms, respectively.

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₉H₇ClO	C₉H₇BrO
M_r	166.60	211.06
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c
Temperature (K)	125	125
a, b, c (Å)	16.319 (6), 6.024 (2), 7.745 (3)	6.489 (2), 17.101 (6), 7.224 (3)
β (°)	99.524 (5)	102.964 (5)
V (Å³)	750.9 (5)	781.2 (5)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.44	5.19
Crystal size (mm)	0.28 × 0.25 × 0.14	0.40 × 0.21 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2013 )	Multi-scan (TWINABS; Bruker 2013)
T_min, T_max	0.84, 0.94	0.55, 0.78
No. of measured, independent and observed [I > 2σ(I)] reflections	18572, 2291, 2158	4453, 4453, 3600
R_int	0.027	0.046
(sin θ/λ)_max (Å⁻¹)	0.716	0.716

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.083, 1.08	0.030, 0.152, 1.03
No. of reflections	2291	4453
No. of parameters	100	101
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.23	1.15, −1.15
Computer programs: APEX2 and SAINT (Bruker, 2013), SHELXS and SHELXTL2014 (Sheldrick, 2008), SHELXL2014/6 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC references: 1507437; 1507436

Crystal structure: contains datablocks global, I, II. DOI: https://doi.org/10.1107/S2056989016015371/sj5508sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016015371/sj5508Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989016015371/sj5508IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989016015371/sj5508Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989016015371/sj5508IIsup5.cml

checkCIF report

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: SHELXTL2014 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL2014 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008).

(I) 6-Chloroindan-1-one top

Crystal data top

C₉H₇ClO	F(000) = 344
M_r = 166.60	D_x = 1.474 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.319 (6) Å	Cell parameters from 9875 reflections
b = 6.024 (2) Å	θ = 2.5–30.5°
c = 7.745 (3) Å	µ = 0.44 mm⁻¹
β = 99.524 (5)°	T = 125 K
V = 750.9 (5) Å³	Block, colourless
Z = 4	0.28 × 0.25 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	2291 independent reflections
Radiation source: fine-focus sealed tube	2158 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.6°, θ_min = 2.5°
φ and ω scans	h = −23→23
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −8→8
T_min = 0.84, T_max = 0.94	l = −11→11
18572 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0439P)² + 0.2902P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2291 reflections	Δρ_max = 0.47 e Å⁻³
100 parameters	Δρ_min = −0.23 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.44180 (2)	0.68505 (5)	0.30384 (4)	0.02625 (9)
O1	0.09308 (5)	0.71579 (13)	0.08199 (10)	0.02037 (16)
C1	0.12100 (5)	0.87485 (15)	0.17008 (11)	0.01444 (17)
C2	0.07137 (6)	1.06661 (17)	0.22843 (12)	0.01704 (18)
H2A	0.035	1.0136	0.3102	0.02*
H2B	0.0363	1.1363	0.1262	0.02*
C3	0.13555 (6)	1.23410 (17)	0.32015 (14)	0.02079 (19)
H3A	0.1328	1.3753	0.254	0.025*
H3B	0.1257	1.2653	0.4405	0.025*
C4	0.21867 (6)	1.12199 (16)	0.32313 (12)	0.01535 (17)
C5	0.29771 (6)	1.19687 (16)	0.39740 (13)	0.01873 (19)
H5A	0.3046	1.3374	0.4536	0.022*
C6	0.36615 (6)	1.06251 (17)	0.38780 (13)	0.01935 (19)
H6A	0.4203	1.1114	0.4374	0.023*
C7	0.35530 (6)	0.85462 (17)	0.30482 (13)	0.01715 (18)
C8	0.27767 (6)	0.77850 (16)	0.22694 (12)	0.01593 (17)
H8A	0.2708	0.6394	0.1685	0.019*
C9	0.21000 (5)	0.91673 (15)	0.23876 (11)	0.01374 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01319 (12)	0.03164 (15)	0.03279 (15)	0.00500 (8)	0.00046 (9)	−0.00599 (10)
O1	0.0170 (3)	0.0196 (3)	0.0230 (3)	−0.0015 (3)	−0.0012 (3)	−0.0029 (3)
C1	0.0134 (4)	0.0153 (4)	0.0143 (4)	0.0008 (3)	0.0012 (3)	0.0028 (3)
C2	0.0153 (4)	0.0186 (4)	0.0174 (4)	0.0039 (3)	0.0033 (3)	0.0016 (3)
C3	0.0202 (4)	0.0180 (4)	0.0233 (4)	0.0050 (4)	0.0013 (4)	−0.0045 (4)
C4	0.0174 (4)	0.0145 (4)	0.0138 (4)	0.0008 (3)	0.0017 (3)	0.0006 (3)
C5	0.0211 (4)	0.0158 (4)	0.0181 (4)	−0.0026 (3)	−0.0001 (3)	−0.0020 (3)
C6	0.0164 (4)	0.0208 (4)	0.0197 (4)	−0.0041 (3)	−0.0004 (3)	−0.0003 (3)
C7	0.0124 (4)	0.0203 (4)	0.0184 (4)	0.0012 (3)	0.0014 (3)	0.0000 (3)
C8	0.0138 (4)	0.0161 (4)	0.0175 (4)	0.0007 (3)	0.0015 (3)	−0.0017 (3)
C9	0.0133 (4)	0.0142 (4)	0.0134 (4)	0.0000 (3)	0.0011 (3)	0.0003 (3)

Geometric parameters (Å, º) top

Cl1—C7	1.7435 (11)	C4—C9	1.3947 (13)
O1—C1	1.2200 (12)	C4—C5	1.3974 (14)
C1—C9	1.4834 (13)	C5—C6	1.3913 (15)
C1—C2	1.5218 (13)	C5—H5A	0.95
C2—C3	1.5406 (15)	C6—C7	1.4054 (14)
C2—H2A	0.99	C6—H6A	0.95
C2—H2B	0.99	C7—C8	1.3880 (13)
C3—C4	1.5120 (14)	C8—C9	1.3981 (13)
C3—H3A	0.99	C8—H8A	0.95
C3—H3B	0.99

O1—C1—C9	125.95 (9)	C5—C4—C3	128.81 (9)
O1—C1—C2	126.46 (9)	C6—C5—C4	119.00 (9)
C9—C1—C2	107.58 (8)	C6—C5—H5A	120.5
C1—C2—C3	106.23 (8)	C4—C5—H5A	120.5
C1—C2—H2A	110.5	C5—C6—C7	120.09 (9)
C3—C2—H2A	110.5	C5—C6—H6A	120.0
C1—C2—H2B	110.5	C7—C6—H6A	120.0
C3—C2—H2B	110.5	C8—C7—C6	122.01 (9)
H2A—C2—H2B	108.7	C8—C7—Cl1	119.08 (8)
C4—C3—C2	104.73 (8)	C6—C7—Cl1	118.90 (7)
C4—C3—H3A	110.8	C7—C8—C9	116.67 (9)
C2—C3—H3A	110.8	C7—C8—H8A	121.7
C4—C3—H3B	110.8	C9—C8—H8A	121.7
C2—C3—H3B	110.8	C4—C9—C8	122.60 (8)
H3A—C3—H3B	108.9	C4—C9—C1	109.64 (8)
C9—C4—C5	119.62 (9)	C8—C9—C1	127.76 (9)
C9—C4—C3	111.57 (8)

O1—C1—C2—C3	−174.57 (9)	Cl1—C7—C8—C9	177.06 (7)
C9—C1—C2—C3	5.05 (10)	C5—C4—C9—C8	0.96 (14)
C1—C2—C3—C4	−4.48 (10)	C3—C4—C9—C8	−178.67 (9)
C2—C3—C4—C9	2.39 (11)	C5—C4—C9—C1	−179.59 (8)
C2—C3—C4—C5	−177.19 (9)	C3—C4—C9—C1	0.78 (11)
C9—C4—C5—C6	−1.02 (14)	C7—C8—C9—C4	0.33 (14)
C3—C4—C5—C6	178.54 (9)	C7—C8—C9—C1	−179.02 (9)
C4—C5—C6—C7	−0.18 (15)	O1—C1—C9—C4	175.91 (9)
C5—C6—C7—C8	1.53 (15)	C2—C1—C9—C4	−3.71 (10)
C5—C6—C7—Cl1	−177.11 (8)	O1—C1—C9—C8	−4.67 (15)
C6—C7—C8—C9	−1.57 (14)	C2—C1—C9—C8	175.71 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.99	2.56	3.1933 (15)	121
C2—H2B···O1ⁱⁱ	0.99	2.59	3.5448 (14)	161

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

(II) 6-Bromoindan-1-one top

Crystal data top

C₉H₇BrO	F(000) = 416
M_r = 211.06	D_x = 1.794 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.489 (2) Å	Cell parameters from 9955 reflections
b = 17.101 (6) Å	θ = 2.4–30.6°
c = 7.224 (3) Å	µ = 5.19 mm⁻¹
β = 102.964 (5)°	T = 125 K
V = 781.2 (5) Å³	Block, colourless
Z = 4	0.40 × 0.21 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	4453 independent reflections
Radiation source: fine-focus sealed tube	3600 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 8.3333 pixels mm^-1	θ_max = 30.6°, θ_min = 2.4°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (TWINABS; Bruker 2013)	k = 0→24
T_min = 0.55, T_max = 0.78	l = 0→10
4453 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.1149P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4453 reflections	Δρ_max = 1.15 e Å⁻³
101 parameters	Δρ_min = −1.15 e Å⁻³

Special details top

Experimental. BASF 0.0762 (5)

Refinement. Refined as a 2-component twin

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.34409 (5)	0.45945 (2)	0.19485 (4)	0.02009 (16)
O1	0.4929 (3)	0.12531 (11)	0.2717 (4)	0.0233 (5)
C1	0.3083 (4)	0.14135 (17)	0.2062 (4)	0.0159 (5)
C2	0.1260 (4)	0.08352 (17)	0.1453 (4)	0.0179 (5)
H2A	0.1117	0.0502	0.2537	0.021*
H2B	0.1515	0.0494	0.0419	0.021*
C3	−0.0764 (5)	0.13304 (17)	0.0755 (4)	0.0192 (6)
H3A	−0.1424	0.1212	−0.0589	0.023*
H3B	−0.1806	0.1229	0.1539	0.023*
C4	−0.0002 (4)	0.21670 (16)	0.0973 (4)	0.0154 (5)
C5	−0.1162 (5)	0.28574 (17)	0.0538 (4)	0.0194 (5)
H5A	−0.2646	0.2838	0.0039	0.023*
C6	−0.0119 (4)	0.35734 (17)	0.0842 (4)	0.0178 (5)
H6A	−0.0895	0.4045	0.0544	0.021*
C7	0.2070 (4)	0.36019 (16)	0.1585 (4)	0.0158 (5)
C8	0.3257 (4)	0.29262 (17)	0.2034 (4)	0.0155 (5)
H8A	0.474	0.2947	0.2538	0.019*
C9	0.2184 (4)	0.22114 (15)	0.1714 (4)	0.0143 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0266 (2)	0.0106 (2)	0.0232 (2)	−0.00221 (8)	0.00597 (15)	−0.00020 (8)
O1	0.0173 (10)	0.0158 (10)	0.0356 (13)	0.0027 (8)	0.0034 (9)	−0.0001 (9)
C1	0.0176 (11)	0.0125 (12)	0.0182 (13)	−0.0028 (9)	0.0054 (10)	−0.0013 (9)
C2	0.0192 (12)	0.0131 (12)	0.0217 (13)	−0.0026 (10)	0.0052 (10)	−0.0006 (10)
C3	0.0195 (13)	0.0168 (13)	0.0209 (13)	−0.0060 (10)	0.0035 (11)	−0.0010 (10)
C4	0.0165 (11)	0.0153 (12)	0.0144 (11)	−0.0011 (9)	0.0033 (9)	0.0006 (9)
C5	0.0157 (11)	0.0193 (13)	0.0220 (13)	0.0006 (10)	0.0015 (10)	0.0025 (10)
C6	0.0194 (12)	0.0145 (12)	0.0192 (13)	0.0043 (10)	0.0038 (10)	0.0026 (10)
C7	0.0184 (12)	0.0132 (11)	0.0161 (12)	−0.0018 (9)	0.0042 (10)	0.0002 (9)
C8	0.0155 (11)	0.0130 (13)	0.0177 (13)	−0.0011 (9)	0.0033 (10)	0.0002 (9)
C9	0.0156 (11)	0.0122 (11)	0.0151 (11)	−0.0010 (9)	0.0036 (9)	−0.0001 (9)

Geometric parameters (Å, º) top

Br1—C7	1.907 (3)	C4—C5	1.398 (4)
O1—C1	1.216 (3)	C4—C9	1.401 (4)
C1—C9	1.483 (4)	C5—C6	1.392 (4)
C1—C2	1.529 (4)	C5—H5A	0.95
C2—C3	1.549 (4)	C6—C7	1.402 (4)
C2—H2A	0.99	C6—H6A	0.95
C2—H2B	0.99	C7—C8	1.386 (4)
C3—C4	1.510 (4)	C8—C9	1.400 (4)
C3—H3A	0.99	C8—H8A	0.95
C3—H3B	0.99

O1—C1—C9	126.1 (3)	C9—C4—C3	111.8 (2)
O1—C1—C2	126.6 (3)	C6—C5—C4	119.3 (3)
C9—C1—C2	107.3 (2)	C6—C5—H5A	120.4
C1—C2—C3	106.6 (2)	C4—C5—H5A	120.4
C1—C2—H2A	110.4	C5—C6—C7	120.4 (3)
C3—C2—H2A	110.4	C5—C6—H6A	119.8
C1—C2—H2B	110.4	C7—C6—H6A	119.8
C3—C2—H2B	110.4	C8—C7—C6	121.5 (3)
H2A—C2—H2B	108.6	C8—C7—Br1	119.5 (2)
C4—C3—C2	104.5 (2)	C6—C7—Br1	119.0 (2)
C4—C3—H3A	110.9	C7—C8—C9	117.3 (2)
C2—C3—H3A	110.9	C7—C8—H8A	121.3
C4—C3—H3B	110.9	C9—C8—H8A	121.3
C2—C3—H3B	110.9	C8—C9—C4	122.3 (2)
H3A—C3—H3B	108.9	C8—C9—C1	127.8 (2)
C5—C4—C9	119.2 (2)	C4—C9—C1	109.9 (2)
C5—C4—C3	129.0 (2)

O1—C1—C2—C3	179.0 (3)	Br1—C7—C8—C9	−179.01 (19)
C9—C1—C2—C3	−0.8 (3)	C7—C8—C9—C4	−0.1 (4)
C1—C2—C3—C4	0.7 (3)	C7—C8—C9—C1	179.6 (3)
C2—C3—C4—C5	179.3 (3)	C5—C4—C9—C8	−0.1 (4)
C2—C3—C4—C9	−0.4 (3)	C3—C4—C9—C8	179.6 (2)
C9—C4—C5—C6	0.3 (4)	C5—C4—C9—C1	−179.8 (2)
C3—C4—C5—C6	−179.4 (3)	C3—C4—C9—C1	−0.1 (3)
C4—C5—C6—C7	−0.3 (4)	O1—C1—C9—C8	1.1 (5)
C5—C6—C7—C8	0.1 (4)	C2—C1—C9—C8	−179.2 (3)
C5—C6—C7—Br1	179.2 (2)	O1—C1—C9—C4	−179.2 (3)
C6—C7—C8—C9	0.0 (4)	C2—C1—C9—C4	0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3B···O1ⁱ	0.99	2.45	3.408 (4)	162
C5—H5A···O1ⁱⁱ	0.95	2.55	3.253 (4)	131
C2—H2B···Br1ⁱⁱⁱ	0.99	3.05	3.898 (3)	145

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

Acknowledgements

This work was supported by Vassar College. X-ray facilities were provided by the US National Science Foundation (Grant No. 0521237 to JMT). We acknowledge the Salmon Fund of Vassar College for funding publication expenses.

References

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Volume 72| Part 11| November 2016| Pages 1536-1540

https://doi.org/10.1107/S2056989016015371

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structures of 6-chloro­indan-1-one and 6-bromo­indan-1-one exhibit different inter­molecular packing inter­actions

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Analytical data

7. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structures of 6-chloroindan-1-one and 6-bromoindan-1-one exhibit different intermolecular packing interactions

3. Supramolecular features