Crystal structure and C—H...F hydrogen bonding in the fluorinated bis-benzoxazine: 3,3′-(ethane-1,2-di­yl)bis­(6-fluoro-3,4-di­hydro-2H-1,3-benzoxazine)

The packing of the title benzoxazine derivative features C—H...F hydrogen bonds, which form a sheet structure further linked via weak C—H...π hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.101
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........    <I>CG</
PLAT717_ALERT_1_C D...A   Unknown or Inconsistent Label ..........    <I>CG</
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      7.249 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          3 Report

Alert level G
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           2 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of OMIT records in Embedded RES .........          2 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density           9 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   4 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

3,3'-(Ethane-1,2-diyl)bis(6-fluoro-3,4-dihydro-2H-1,3-benzoxazine)

Crystal data

C18H18F2N2O2	F(000) = 348
Mr = 332.34	Dx = 1.470 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.0242 (6) Å	Cell parameters from 7746 reflections
b = 6.2316 (6) Å	θ = 3.5–27.8°
c = 17.1574 (15) Å	µ = 0.11 mm^−1
β = 91.473 (7)°	T = 173 K
V = 750.77 (12) Å^3	Plate, colourless
Z = 2	0.17 × 0.13 × 0.04 mm

Data collection

Stoe IPDS II two-circle diffractometer	1285 reflections with I > 2σ(I)
Radiation source: Genix 3D IµS microfocus X-ray source	Rint = 0.036
ω scans	θmax = 26.4°, θmin = 3.5°
Absorption correction: multi-scan (X-AREA; Stoe & Cie, 2001)	h = −8→8
Tmin = 0.362, Tmax = 1.000	k = −7→7
7746 measured reflections	l = −20→21
1532 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.101	w = 1/[σ^2(Fo^2) + (0.0538P)^2 + 0.1464P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1532 reflections	Δρmax = 0.18 e Å^−3
109 parameters	Δρmin = −0.16 e Å^−3

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.

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

	x	y	z	Uiso*/Ueq
F1	0.80087 (14)	0.60837 (18)	0.86796 (5)	0.0408 (3)
O1	0.69940 (16)	0.06550 (17)	0.61834 (6)	0.0293 (3)
N1	0.73058 (17)	0.3605 (2)	0.52754 (7)	0.0256 (3)
C1	0.5232 (2)	0.3961 (2)	0.52148 (8)	0.0260 (3)
H1A	0.4706	0.4020	0.5744	0.031*
H1B	0.4624	0.2743	0.4934	0.031*
C2	0.7756 (2)	0.1410 (3)	0.54504 (9)	0.0294 (4)
H2A	0.9158	0.1242	0.5471	0.035*
H2B	0.7249	0.0493	0.5022	0.035*
C3	0.72790 (19)	0.2069 (2)	0.67944 (8)	0.0237 (3)
C4	0.79289 (19)	0.4168 (2)	0.66810 (8)	0.0228 (3)
C5	0.8283 (2)	0.4965 (3)	0.58624 (8)	0.0267 (3)
H5A	0.7820	0.6459	0.5809	0.032*
H5B	0.9668	0.4961	0.5770	0.032*
C6	0.81932 (19)	0.5507 (3)	0.73252 (8)	0.0250 (3)
H6	0.8647	0.6931	0.7263	0.030*
C7	0.7786 (2)	0.4732 (3)	0.80519 (8)	0.0273 (3)
C8	0.7114 (2)	0.2675 (3)	0.81752 (9)	0.0293 (4)
H8	0.6837	0.2193	0.8685	0.035*
C9	0.6854 (2)	0.1337 (3)	0.75374 (9)	0.0269 (3)
H9	0.6386	−0.0079	0.7606	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0442 (6)	0.0526 (7)	0.0255 (5)	−0.0053 (5)	0.0007 (4)	−0.0122 (4)
O1	0.0393 (6)	0.0227 (6)	0.0258 (6)	−0.0001 (4)	0.0008 (4)	−0.0013 (4)
N1	0.0251 (6)	0.0299 (7)	0.0217 (6)	0.0008 (5)	0.0008 (4)	0.0007 (5)
C1	0.0248 (7)	0.0289 (8)	0.0243 (7)	−0.0015 (6)	0.0006 (5)	0.0018 (6)
C2	0.0338 (8)	0.0310 (8)	0.0233 (7)	0.0046 (6)	0.0025 (6)	−0.0032 (6)
C3	0.0227 (7)	0.0253 (8)	0.0231 (7)	0.0034 (6)	−0.0003 (5)	0.0000 (6)
C4	0.0202 (6)	0.0264 (8)	0.0220 (7)	0.0014 (5)	0.0008 (5)	0.0018 (6)
C5	0.0273 (7)	0.0296 (8)	0.0232 (7)	−0.0033 (6)	0.0000 (5)	0.0032 (6)
C6	0.0210 (6)	0.0269 (8)	0.0271 (7)	−0.0004 (5)	0.0000 (5)	0.0003 (6)
C7	0.0245 (7)	0.0351 (9)	0.0223 (7)	0.0020 (6)	−0.0019 (5)	−0.0057 (6)
C8	0.0262 (7)	0.0399 (9)	0.0218 (7)	0.0026 (6)	0.0036 (6)	0.0059 (7)
C9	0.0252 (7)	0.0269 (8)	0.0287 (8)	0.0014 (6)	0.0024 (6)	0.0060 (6)

Geometric parameters (Å, º)

F1—C7	1.3731 (17)	C3—C4	1.401 (2)
O1—C3	1.3803 (18)	C4—C6	1.393 (2)
O1—C2	1.4574 (18)	C4—C5	1.5161 (19)
N1—C2	1.434 (2)	C5—H5A	0.9900
N1—C5	1.4721 (19)	C5—H5B	0.9900
N1—C1	1.4746 (18)	C6—C7	1.374 (2)
C1—C1^i	1.522 (3)	C6—H6	0.9500
C1—H1A	0.9900	C7—C8	1.384 (2)
C1—H1B	0.9900	C8—C9	1.384 (2)
C2—H2A	0.9900	C8—H8	0.9500
C2—H2B	0.9900	C9—H9	0.9500
C3—C9	1.393 (2)
C3—O1—C2	113.57 (12)	C6—C4—C5	121.16 (14)
C2—N1—C5	108.03 (12)	C3—C4—C5	119.75 (13)
C2—N1—C1	111.72 (12)	N1—C5—C4	111.15 (12)
C5—N1—C1	113.84 (12)	N1—C5—H5A	109.4
N1—C1—C1^i	111.15 (14)	C4—C5—H5A	109.4
N1—C1—H1A	109.4	N1—C5—H5B	109.4
C1^i—C1—H1A	109.4	C4—C5—H5B	109.4
N1—C1—H1B	109.4	H5A—C5—H5B	108.0
C1^i—C1—H1B	109.4	C7—C6—C4	118.88 (15)
H1A—C1—H1B	108.0	C7—C6—H6	120.6
N1—C2—O1	113.88 (12)	C4—C6—H6	120.6
N1—C2—H2A	108.8	F1—C7—C6	118.28 (15)
O1—C2—H2A	108.8	F1—C7—C8	118.74 (13)
N1—C2—H2B	108.8	C6—C7—C8	122.95 (14)
O1—C2—H2B	108.8	C7—C8—C9	118.40 (13)
H2A—C2—H2B	107.7	C7—C8—H8	120.8
O1—C3—C9	117.09 (14)	C9—C8—H8	120.8
O1—C3—C4	122.16 (13)	C8—C9—C3	119.93 (15)
C9—C3—C4	120.75 (14)	C8—C9—H9	120.0
C6—C4—C3	119.07 (13)	C3—C9—H9	120.0
C2—N1—C1—C1^i	−161.85 (15)	C1—N1—C5—C4	75.31 (15)
C5—N1—C1—C1^i	75.45 (18)	C6—C4—C5—N1	−160.16 (12)
C5—N1—C2—O1	65.92 (15)	C3—C4—C5—N1	18.20 (18)
C1—N1—C2—O1	−60.03 (16)	C3—C4—C6—C7	−0.8 (2)
C3—O1—C2—N1	−45.71 (17)	C5—C4—C6—C7	177.62 (13)
C2—O1—C3—C9	−170.60 (12)	C4—C6—C7—F1	−178.47 (12)
C2—O1—C3—C4	10.67 (19)	C4—C6—C7—C8	−0.3 (2)
O1—C3—C4—C6	−179.71 (12)	F1—C7—C8—C9	178.65 (13)
C9—C3—C4—C6	1.6 (2)	C6—C7—C8—C9	0.5 (2)
O1—C3—C4—C5	1.9 (2)	C7—C8—C9—C3	0.4 (2)
C9—C3—C4—C5	−176.79 (13)	O1—C3—C9—C8	179.82 (13)
C2—N1—C5—C4	−49.39 (15)	C4—C3—C9—C8	−1.4 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

Cg2 is the centroid of the C3/C4/C6/C7/C8/C9 ring

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···F1^ii	0.99	2.44	3.300 (2)	145
C6—H6···Cg2^iii	0.95	2.88	3.527 (2)	126
C9—H9···Cg2^iv	0.95	2.90	3.577 (2)	129

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