The role of different nonspecific inter­actions and halogen contacts in the crystal structure organization of 5-chloro­isatoic anhydride

The crystal structure of 6-chloro-2,4-di­hydro-1H-3,1-benzoxazine-2,4-dione (5-chloro­isatoic anhydride), C₈H₄ClNO₃, has been determined and analysed in terms of connectivity and packing patterns. The compound crystallizes in the noncentrosymmetric space group Pna2₁ with one mol­ecule in the asymmetric unit. The role of different weak inter­actions is discussed with respect to three-dimensional network organization. Mol­ecules are extended into one-dimensional helical arrangements, making use of N—H...O hydrogen bonds and π–π inter­actions. The helices are further organized into monolayers via weak C—H...O and lone pair–π inter­actions, and the monolayers are packed into a noncentrosymmetric three-dimensional architecture by C—Cl...π inter­actions and C—H...Cl and Cl...Cl contacts. A Hirshfeld surface (HS) analysis was carried out and two-dimensional (2D) fingerprint plots were generated to visualize the inter­molecular inter­actions and to provide qu­anti­tative data for their relative contributions. In addition, tests of the anti­microbial activity and in vitro cytotoxity effects against fitoblast L929 were performed and are discussed.

Computing details

Data collection: CrysAlis CCD (Rigaku OD, 2015); cell refinement: CrysAlis RED (Rigaku OD, 2015); data reduction: CrysAlis RED (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

6-Chloro-2,4-dihydro-1H-3,1-benzoxazine-2,4-dione

Crystal data

C8H4ClNO3	Dx = 1.744 Mg m^−3 Dm = 1.74 Mg m^−3 Dm measured by floatation
Mr = 197.57	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21	Cell parameters from 2601 reflections
a = 24.3852 (12) Å	θ = 3.5–29.7°
b = 6.0502 (4) Å	µ = 0.47 mm^−1
c = 5.100 (3) Å	T = 100 K
V = 752.4 (4) Å^3	Parallelepiped, colourless
Z = 4	0.29 × 0.26 × 0.21 mm
F(000) = 400

Data collection

Kuma KM-4 with a CCD detector diffractometer	1960 independent reflections
Radiation source: fine-focus sealed X-ray tube	1787 reflections with I > 2σ(I)
Detector resolution: 10.6249 pixels mm^-1	Rint = 0.026
ω scan	θmax = 30.3°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −34→34
Tmin = 0.995, Tmax = 1.000	k = −8→7
5402 measured reflections	l = −7→6

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.065	w = 1/[σ^2(Fo^2) + (0.0286P)^2 + 0.1626P] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max = 0.001
1960 reflections	Δρmax = 0.28 e Å^−3
121 parameters	Δρmin = −0.28 e Å^−3
1 restraint	Absolute structure: Flack x determined using 679 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (4)

Special details

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.

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 > 2sigma(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	0.73998 (2)	0.46467 (10)	0.03899 (16)	0.01858 (15)
O1	0.55064 (7)	0.5058 (3)	0.9024 (4)	0.0127 (4)
O2	0.60770 (7)	0.2246 (3)	0.8457 (4)	0.0146 (4)
O3	0.48982 (7)	0.7725 (3)	0.9623 (3)	0.0163 (4)
N1	0.55052 (9)	0.8105 (3)	0.6269 (4)	0.0117 (4)
H1N	0.5362 (11)	0.935 (5)	0.589 (6)	0.014*
C1	0.52823 (10)	0.7053 (4)	0.8323 (5)	0.0124 (5)
C2	0.59392 (10)	0.4030 (4)	0.7695 (5)	0.0111 (5)
C3	0.61786 (9)	0.5301 (4)	0.5543 (6)	0.0106 (4)
C4	0.66301 (10)	0.4465 (4)	0.4176 (5)	0.0128 (5)
H4	0.6785	0.3077	0.4632	0.015*
C5	0.68442 (10)	0.5697 (4)	0.2154 (5)	0.0129 (5)
C6	0.66260 (10)	0.7760 (4)	0.1468 (5)	0.0136 (5)
H6	0.6783	0.8585	0.0072	0.016*
C7	0.61817 (10)	0.8589 (4)	0.2830 (5)	0.0121 (5)
H7	0.6031	0.9986	0.2382	0.015*
C8	0.59563 (10)	0.7343 (4)	0.4878 (5)	0.0107 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0138 (2)	0.0226 (3)	0.0193 (3)	0.0013 (2)	0.0053 (3)	−0.0022 (3)
O1	0.0166 (9)	0.0096 (7)	0.0118 (9)	0.0009 (7)	0.0040 (7)	0.0021 (7)
O2	0.0171 (9)	0.0122 (8)	0.0146 (9)	0.0003 (7)	−0.0010 (8)	0.0027 (8)
O3	0.0170 (9)	0.0143 (8)	0.0177 (10)	0.0007 (7)	0.0060 (8)	−0.0016 (7)
N1	0.0129 (11)	0.0089 (9)	0.0133 (10)	0.0022 (8)	0.0014 (8)	0.0015 (8)
C1	0.0128 (12)	0.0101 (10)	0.0144 (13)	−0.0018 (9)	−0.0024 (11)	−0.0013 (10)
C2	0.0113 (11)	0.0110 (10)	0.0110 (12)	−0.0009 (9)	−0.0025 (9)	−0.0021 (10)
C3	0.0114 (9)	0.0110 (9)	0.0094 (11)	−0.0016 (8)	−0.0021 (11)	0.0003 (11)
C4	0.0113 (11)	0.0125 (11)	0.0147 (13)	−0.0006 (10)	−0.0021 (9)	0.0000 (10)
C5	0.0088 (11)	0.0170 (12)	0.0128 (12)	0.0005 (9)	0.0013 (9)	−0.0047 (10)
C6	0.0130 (11)	0.0165 (11)	0.0114 (12)	−0.0052 (10)	0.0006 (10)	0.0019 (10)
C7	0.0140 (12)	0.0102 (11)	0.0123 (13)	−0.0008 (9)	−0.0035 (10)	0.0014 (10)
C8	0.0102 (10)	0.0101 (10)	0.0118 (13)	−0.0019 (8)	−0.0005 (8)	−0.0020 (9)

Geometric parameters (Å, º)

Cl1—C5	1.746 (3)	C3—C8	1.392 (3)
O1—C1	1.372 (3)	C3—C4	1.398 (3)
O1—C2	1.400 (3)	C4—C5	1.375 (4)
O2—C2	1.196 (3)	C4—H4	0.9500
O3—C1	1.217 (3)	C5—C6	1.401 (3)
N1—C1	1.341 (3)	C6—C7	1.381 (3)
N1—C8	1.388 (3)	C6—H6	0.9500
N1—H1N	0.86 (3)	C7—C8	1.400 (3)
C2—C3	1.462 (4)	C7—H7	0.9500
C1—O1—C2	124.4 (2)	C5—C4—H4	120.8
C1—N1—C8	124.3 (2)	C3—C4—H4	120.8
C1—N1—H1N	116 (2)	C4—C5—C6	121.7 (2)
C8—N1—H1N	120 (2)	C4—C5—Cl1	118.92 (19)
O3—C1—N1	125.3 (2)	C6—C5—Cl1	119.34 (19)
O3—C1—O1	117.3 (2)	C7—C6—C5	119.7 (2)
N1—C1—O1	117.4 (2)	C7—C6—H6	120.1
O2—C2—O1	117.1 (2)	C5—C6—H6	120.1
O2—C2—C3	127.4 (2)	C6—C7—C8	119.2 (2)
O1—C2—C3	115.52 (19)	C6—C7—H7	120.4
C8—C3—C4	120.4 (2)	C8—C7—H7	120.4
C8—C3—C2	119.6 (2)	N1—C8—C3	118.6 (2)
C4—C3—C2	119.9 (2)	N1—C8—C7	120.9 (2)
C5—C4—C3	118.5 (2)	C3—C8—C7	120.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3^i	0.86 (3)	1.98 (3)	2.835 (3)	172 (3)
C7—H7···O2^ii	0.95	2.43	3.152 (4)	133

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