Hydro­gen bonding and C—H...X interactions in 3-fluoro-2-[1-(1-naph­thyl)ethyl]benzoic acid

The title acid, C₁₉H₁₅FO₂, crystallized in the centrosymmetric space group P with one mol­ecule as the asymmetric unit. There is a single hydrogen bond, with an O_D...O_A distance of 2.632 (2) Å and an O_D—H...O_A angle of 177 (3)°, which forms an R(8) cyclic dimer about a center of symmetry. There is a single leading intermolecular C—H...X interaction, with an H...F distance of 2.49 Å and a C—H...F angle of 147°. Three leading intramolecular C—H...X interactions appear to play a significant role in determining the orientation of the methyl and carboxyl groups.

S1. Comment

This report on the title acid, (I), is one of a series on hydrogen bonding in carboxylic acids. It follows a report on the somewhat similar ortho-(1-naphthoyl)benzoic acid (Gerkin, 1998). (I) crystallized in the centrosymmetric space group P-1 with one molecule as the asymmetric unit. The refined molecule and the labelling scheme are shown in Fig. 1. In the carboxyl group the O atoms are ordered, as shown by the carboxyl C—O distances (Table 1), as is the carboxylic H atom. There is a single hydrogen bond in this structure, whose geometric parameters are given in Table 2. This forms a first-level (Bernstein et al., 1995) cyclic dimer, with descriptor R₂²(8), about a center of symmetry. In addition, there is a single leading intermolecular C—H···X interaction and three leading intramolecular C—H···X interactions (Taylor & Kennard, 1982; Steiner & Desiraju, 1998), whose geometric parameters are also given in Table 2. The intermolecular C—H···X interaction produces, at first-level, a C(9) chain propagating along [100]. The second-level graph involving the two tabulated intermolecular interactions is a ring, R₄⁴(34)[R₂²(8)]. The stereodiagram, Fig. 2, shows a central molecule and the three neighbors to which it is linked directly by these two interactions. Two of the intramolecular C—H···X interactions involve the two carboxyl-O atoms, whose distances O1—H6, O1—C6, O2—H8, O2—C8 and O2—C2 are less than the corresponding Bondi (1964) van der Waals radius sums. Significantly, a (small) counterclockwise rotation of the carboxyl group about an axis directed from C1 to C7 would reduce each of these deficits without simultaneously causing any of the carboxyl group atoms to move closer than the relevant van der Waals radius sum to any other atoms. [The closest atoms and their present distances are: H12ⁱⁱⁱ (iii = x − 1, y − 1, z), 2.73 Å from H1 and 2.86 Å from O1; and C7ⁱ (i = −x, 1 − y, 1 − z), 3.34 Å from O2. These distances are, respectively, 1/3, 0.16 and 0.14 Å greater than the corresponding van der Waals sums.] These facts indicate that the C—H···O interactions are, in sum, attractive and significant in determining the dihedral angle between the carboxyl group plane and that of the benzene ring to which it is attached. Thus, the present situation differs from that for 2- nitrobenzaldehyde, for which an attractive C—H···O interaction was excluded (Coppens, 1964). The remaining tabulated intramolecular C—H···X interaction in (I) involves the methyl group C atom, C19, H19B and F1, and undoubtedly plays a role in determining the observed orientation of the fully refined methyl group. \sch

The benzene ring in (I) is slightly rumpled, the maximum deviation of any of its atoms from the best-fit plane describing them being 0.026 (2) Å, while the average deviation is 0.018 (9) Å. The dihedral angle between this best-fit plane and that of the carboxyl group is 22.7 (3)°. The naphthalene ring is also slightly rumpled, the maximum deviation of any of its atoms from the best-fit plane describing them being 0.029 (2) Å, while the average deviation is 0.017 (9) Å. The dihedral angle between the planes of the benzene and naphthalene rings is 88.79 (8)°. This near-perpendicularity is apparent in Fig. 2.

Selected distances and angles are given in Table 1. For structural comparisons, two similar 3-fluoro-acids are available: 3-fluorobenzoic acid itself [hereafter (II)] (Taga et al., 1985) and potassium hydrogen 3- fluorophthalate [hereafter (III)] (Mattes & Dorau, 1986). As expected for benzene rings carrying such substituents, a significant range of benzene C—C distances and C—C—C angles is displayed by these three molecules. The range of C—C distances for the three is very similar: 1.370 (2) to 1.403 (2) Å in (I), 1.363 (3) to 1.389 (3) Å in (II) and 1.372 (7) to 1.399 (6) Å in (III). However, the values for corresponding individual bonds differ by as much as 0.021 Å for (I) versus (II) and (III), and by 0.024 Å for (II) versus (III). These deviations are undoubtedly due, in part, to the difference in substituents at the 2-position: a substituted ethyl group in (I), an H atom in (II) and a carboxylate ion in (III). Similarly, the most-widely different interior ring-angle is that at the 2-position: 114.6 (2) in (I), 118.0 (2) and 118.0 (4) ° in (II) and (III). The significantly-largest interior ring- angle occurs at C3, the fluorine-substituted C atom, in each case, being 125.4 (2) ° in (I), 122.9 (2) and 123.2 (5) ° in (II) and (III). The C—F bond distance in (I), 1.364 (2) Å, agrees well with the values 1.358 (3) and 1.369 (5) Å for (II) and (III), and very well with the mean value for C—F distances for monofluoroarenes tabulated by Allen et al. (1987), 1.363 (8) Å. Further good agreement among (I), (II) and (III) is seen for the length of the other common bond exterior to the benzene ring, namely C1—C7 (present nomenclature), whose values are 1.487 (2), 1.485 (2) and 1.483 (6) Å, respectively. All remaining distances and angles in (I) fall within normal ranges. Excluding pairs of atoms in hydrogen-bonded carboxyl groups or in the tabulated C—H···X interactions, the closest intermolecular approaches are between C5 and H13^iv (iv = x, y − 1, z), and are 0.14 Å less than the corresponding Bondi (1964) van der Waals radius sum.

S2. Experimental

The title acid, whose synthesis is described by Newman & Khanna (1979), was obtained from a sample in Dr. M. S. Newman's chemical collection. An irregular chunk found there became the experimental sample.

S3. Refinement

COOH And methyl H atoms were refined isotropically. C—H distances were in the range 0.989 (17)–1.026 (17) Å. For calculated H atoms, C—H = 0.98 Å, and U_iso = 1.2U_eq for the bonded C atom.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: TEXSAN; molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN and PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of (I) showing the labelling scheme and with displacement ellipsoids at the 50% probability level.
	Fig. 2. Stereodiagram of (I), with displacement ellipsoids at the 50% probability level. The finer interatomic lines depict the intermolecular interactions given in Table 2.

(I)

Crystal data

C19H15FO2	Z = 2
Mr = 294.32	F(000) = 308
Triclinic, P1	Dx = 1.302 Mg m^−3
a = 7.5402 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4339 (12) Å	Cell parameters from 25 reflections
c = 10.8160 (11) Å	θ = 14.4–17.5°
α = 113.796 (8)°	µ = 0.09 mm^−1
β = 91.867 (8)°	T = 296 K
γ = 103.108 (9)°	Irregular chunk, colorless
V = 750.92 (14) Å^3	0.38 × 0.27 × 0.19 mm

Data collection

AFC5S diffractometer	Rint = 0.019
Radiation source: X-ray tube	θmax = 27.6°, θmin = 2.1°
Graphite monochromator	h = 0→9
ω scans	k = −13→13
3729 measured reflections	l = −14→14
3464 independent reflections	6 standard reflections every 150 reflections
1938 reflections with I > 2.0σI	intensity decay: 1.7%

Refinement

Refinement on F^2	215 parameters
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.050	w = 1/[σ^2cs + (0.004I)^2]
wR(F^2) = 0.067	(Δ/σ)max = 0.0002
S = 1.70	Δρmax = 0.33 e Å^−3
3464 reflections	Δρmin = −0.32 e Å^−3

Special details

Experimental. Scan widths were (1.60 + 0.30 tanθ)° in ω, with background/scan time-ratio of 0.5. The data were corrected for Lorentz and polarization effects. A linear decay correction was applied. The Laue group assignment and centrosymmetric intensity statistics indicated space group P-1 (No. 2). Since refinement proceeded well, it was adopted.

Geometry. TABLE of LEAST SQUARES PLANES

————– Plane number 1 —————

Atoms Defining Plane Distance e.s.d. C1 (1) 0.0243 0.0017 C2 (1) −0.0257 0.0016 C3 (1) 0.0125 0.0019 C4 (1) 0.0173 0.0020 C5 (1) −0.0243 0.0020 C6 (1) −0.0006 0.0019

Additional Atoms Distance F1 (1) 0.0401 C7 (1) 0.2140 C8 (1) −0.1364

Mean deviation from plane is 0.0175 angstroms Chi-squared: 620.4

————– Plane number 2 —————

Atoms Defining Plane Distance e.s.d. O1 (1) 0.0000 O2 (1) 0.0000 C7 (1) 0.0000

Mean deviation from plane is 0.0000 angstroms Chi-squared: 0.0

Dihedral angles between least-squares planes plane plane angle 2 1 22.73

————– Plane number 3 —————

Atoms Defining Plane Distance e.s.d. C9 (1) 0.0084 0.0016 C10 (1) 0.0033 0.0019 C11 (1) −0.0128 0.0021 C12 (1) 0.0025 0.0019 C17 (1) −0.0142 0.0015 C18 (1) 0.0101 0.0016

Mean deviation from plane is 0.0086 angstroms Chi-squared: 179.3

Dihedral angles between least-squares planes plane plane angle 3 1 89.26 3 2 68.88

————– Plane number 4 —————

Atoms Defining Plane Distance e.s.d. C13 (1) 0.0005 0.0019 C14 (1) 0.0086 0.0022 C15 (1) −0.0037 0.0020 C16 (1) −0.0061 0.0017 C17 (1) 0.0095 0.0015 C18 (1) −0.0081 0.0016

Mean deviation from plane is 0.0061 angstroms Chi-squared: 89.5

Dihedral angles between least-squares planes plane plane angle 4 1 88.23 4 2 67.62 4 3 1.74

————– Plane number 5 —————

Atoms Defining Plane Distance e.s.d. C9 (1) 0.0275 0.0016 C10 (1) 0.0067 0.0019 C11 (1) −0.0286 0.0021 C12 (1) −0.0167 0.0019 C13 (1) 0.0230 0.0019 C14 (1) 0.0177 0.0022 C15 (1) −0.0168 0.0020 C16 (1) −0.0275 0.0017 C17 (1) 0.0015 0.0015 C18 (1) 0.0064 0.0016

Mean deviation from plane is 0.0172 angstroms Chi-squared: 1184.9

Dihedral angles between least-squares planes plane plane angle 5 1 88.84 5 2 68.34 5 3 0.83 5 4 0.92

Refinement. Fourier difference methods were used to locate initial H atom positions, and the H atoms were then refined isotropically. Refined C—H distances ranged from 0.96 (2) to 1.02 (2) Å, with a mean value 0.99 (2) Å. Subsequently, atoms H4- H16 were made canonical with C—H = 0.98 Å and U_iso = 1.2 × U_eq of the attached C atom; the methyl H atoms were refined. In late stages of refinement, the extinction coefficient was predicted to be negative, and was not included in the model. The maximum positive residual peak is located \sim 1.9 Å from C4; the maximum negative peak is located ~0.06 Å from O1.

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

	x	y	z	Uiso*/Ueq
F1	0.75184 (16)	0.62018 (12)	0.21384 (12)	0.0751 (4)
O1	−0.0040 (2)	0.41004 (17)	0.31795 (15)	0.0834 (6)
O2	0.20757 (19)	0.57595 (14)	0.48626 (14)	0.0714 (5)
C1	0.2941 (3)	0.47344 (18)	0.26447 (17)	0.0445 (6)
C2	0.4628 (3)	0.57598 (18)	0.28789 (17)	0.0420 (6)
C3	0.5811 (3)	0.5299 (2)	0.1942 (2)	0.0530 (7)
C4	0.5413 (3)	0.3997 (2)	0.0809 (2)	0.0633 (7)
C5	0.3704 (3)	0.3064 (2)	0.05664 (19)	0.0637 (7)
C6	0.2484 (3)	0.34166 (19)	0.14852 (19)	0.0556 (6)
C7	0.1622 (3)	0.4934 (2)	0.3656 (2)	0.0507 (6)
C8	0.5188 (2)	0.72890 (18)	0.40410 (17)	0.0432 (5)
C9	0.5776 (2)	0.84632 (18)	0.35202 (17)	0.0415 (5)
C10	0.7558 (3)	0.9292 (2)	0.3786 (2)	0.0574 (7)
C11	0.8097 (3)	1.0374 (2)	0.3307 (2)	0.0662 (7)
C12	0.6876 (3)	1.0613 (2)	0.2545 (2)	0.0589 (7)
C13	0.3729 (3)	1.0028 (2)	0.1435 (2)	0.0616 (8)
C14	0.1941 (3)	0.9270 (3)	0.1155 (2)	0.0701 (8)
C15	0.1343 (3)	0.8239 (2)	0.1675 (2)	0.0613 (7)
C16	0.2560 (3)	0.79814 (18)	0.24468 (18)	0.0464 (6)
C17	0.4449 (2)	0.87288 (17)	0.27459 (17)	0.0388 (5)
C18	0.5026 (3)	0.97963 (18)	0.22347 (18)	0.0454 (6)
C19	0.6597 (4)	0.7348 (3)	0.5128 (2)	0.0641 (8)
H1	−0.085 (4)	0.412 (3)	0.394 (3)	0.189 (13)*
H4	0.6325	0.3742	0.0191	0.076*
H5	0.3354	0.2150	−0.0259	0.076*
H6	0.1278	0.2734	0.1324	0.067*
H8	0.4087	0.7448	0.4472	0.052*
H10	0.8481	0.9126	0.4323	0.069*
H11	0.9376	1.0960	0.3532	0.079*
H12	0.7275	1.1356	0.2204	0.071*
H13	0.4131	1.0753	0.1073	0.074*
H14	0.1065	0.9443	0.0589	0.084*
H15	0.0044	0.7700	0.1482	0.074*
H16	0.2115	0.7259	0.2805	0.056*
H19A	0.600 (3)	0.6624 (19)	0.5461 (18)	0.084 (8)*
H19B	0.774 (3)	0.7085 (18)	0.4716 (17)	0.071 (7)*
H19C	0.700 (3)	0.8344 (19)	0.5888 (18)	0.081 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.0653 (8)	0.0728 (9)	0.0857 (9)	0.0210 (7)	0.0372 (7)	0.0284 (7)
O1	0.0642 (11)	0.0941 (12)	0.0581 (10)	−0.0118 (9)	0.0176 (9)	0.0152 (9)
O2	0.0750 (11)	0.0657 (10)	0.0493 (9)	−0.0025 (8)	0.0268 (8)	0.0098 (8)
C1	0.0579 (13)	0.0408 (11)	0.0385 (11)	0.0145 (10)	0.0141 (10)	0.0191 (9)
C2	0.0551 (12)	0.0409 (11)	0.0380 (10)	0.0202 (10)	0.0149 (9)	0.0198 (9)
C3	0.0594 (14)	0.0511 (12)	0.0563 (13)	0.0177 (11)	0.0216 (11)	0.0277 (11)
C4	0.0884 (17)	0.0575 (14)	0.0550 (13)	0.0382 (13)	0.0341 (13)	0.0226 (11)
C5	0.0984 (19)	0.0432 (12)	0.0481 (13)	0.0238 (12)	0.0204 (13)	0.0144 (10)
C6	0.0730 (15)	0.0411 (11)	0.0471 (12)	0.0098 (11)	0.0140 (11)	0.0152 (10)
C7	0.0646 (15)	0.0388 (11)	0.0472 (12)	0.0083 (10)	0.0151 (11)	0.0188 (10)
C8	0.0448 (11)	0.0457 (11)	0.0390 (10)	0.0136 (9)	0.0086 (9)	0.0166 (9)
C9	0.0414 (11)	0.0377 (10)	0.0390 (11)	0.0095 (9)	0.0096 (9)	0.0100 (9)
C10	0.0442 (12)	0.0554 (13)	0.0625 (14)	0.0060 (10)	0.0014 (11)	0.0189 (11)
C11	0.0499 (14)	0.0492 (13)	0.0806 (17)	−0.0080 (11)	0.0114 (12)	0.0196 (12)
C12	0.0647 (15)	0.0387 (11)	0.0655 (14)	0.0032 (11)	0.0216 (12)	0.0189 (11)
C13	0.0811 (17)	0.0573 (14)	0.0611 (14)	0.0265 (13)	0.0238 (13)	0.0341 (12)
C14	0.0739 (17)	0.0817 (17)	0.0721 (16)	0.0315 (14)	0.0080 (13)	0.0439 (14)
C15	0.0445 (13)	0.0714 (15)	0.0718 (15)	0.0161 (11)	0.0057 (11)	0.0337 (12)
C16	0.0433 (12)	0.0467 (11)	0.0530 (12)	0.0135 (10)	0.0129 (10)	0.0234 (10)
C17	0.0417 (11)	0.0352 (10)	0.0369 (10)	0.0117 (9)	0.0134 (9)	0.0112 (8)
C18	0.0553 (13)	0.0367 (10)	0.0448 (11)	0.0150 (10)	0.0166 (10)	0.0153 (9)
C19	0.0703 (18)	0.0740 (18)	0.0513 (15)	0.0231 (15)	0.0033 (13)	0.0278 (14)

Geometric parameters (Å, º)

F1—C3	1.364 (2)	C10—C11	1.409 (3)
O1—C7	1.302 (2)	C10—H10	0.98
O1—H1	1.04 (3)	C11—C12	1.345 (3)
O2—C7	1.2217 (19)	C11—H11	0.98
C1—C2	1.403 (2)	C12—C18	1.409 (2)
C1—C6	1.395 (2)	C12—H12	0.98
C1—C7	1.487 (2)	C13—C14	1.353 (3)
C2—C3	1.383 (2)	C13—C18	1.408 (3)
C2—C8	1.531 (2)	C13—H13	0.98
C3—C4	1.373 (2)	C14—C15	1.400 (3)
C4—C5	1.371 (3)	C14—H14	0.98
C4—H4	0.98	C15—C16	1.362 (2)
C5—C6	1.374 (2)	C15—H15	0.98
C5—H5	0.98	C16—C17	1.416 (2)
C6—H6	0.98	C16—H16	0.98
C8—C9	1.530 (2)	C17—C18	1.424 (2)
C8—C19	1.531 (3)	C19—H19A	0.989 (17)
C8—H8	0.98	C19—H19B	1.026 (17)
C9—C10	1.372 (2)	C19—H19C	0.999 (17)
C9—C17	1.428 (2)
C7—O1—H1	112.7 (14)	C9—C10—H10	119.1
C2—C1—C6	121.05 (16)	C11—C10—H10	119.1
C2—C1—C7	122.28 (16)	C10—C11—C12	120.78 (19)
C6—C1—C7	116.50 (17)	C10—C11—H11	119.6
C1—C2—C3	114.57 (16)	C12—C11—H11	119.6
C1—C2—C8	125.21 (16)	C11—C12—C18	120.17 (19)
C3—C2—C8	120.21 (16)	C11—C12—H12	119.9
F1—C3—C2	118.27 (17)	C18—C12—H12	119.9
F1—C3—C4	116.30 (18)	C14—C13—C18	121.40 (19)
C2—C3—C4	125.43 (19)	C14—C13—H13	119.3
C3—C4—C5	118.17 (18)	C18—C13—H13	119.3
C3—C4—H4	120.9	C13—C14—C15	120.0 (2)
C5—C4—H4	120.9	C13—C14—H14	120.0
C4—C5—C6	119.73 (18)	C15—C14—H14	120.0
C4—C5—H5	120.1	C14—C15—C16	120.20 (19)
C6—C5—H5	120.1	C14—C15—H15	119.9
C1—C6—C5	120.82 (18)	C16—C15—H15	119.9
C1—C6—H6	119.6	C15—C16—C17	121.82 (17)
C5—C6—H6	119.6	C15—C16—H16	119.1
O1—C7—O2	121.96 (18)	C17—C16—H16	119.1
O1—C7—C1	115.07 (18)	C9—C17—C16	123.52 (16)
O2—C7—C1	122.85 (19)	C9—C17—C18	119.28 (16)
C2—C8—C9	112.25 (14)	C16—C17—C18	117.20 (17)
C2—C8—C19	109.62 (17)	C12—C18—C13	120.97 (19)
C2—C8—H8	106.6	C12—C18—C17	119.67 (18)
C9—C8—C19	114.76 (17)	C13—C18—C17	119.35 (18)
C9—C8—H8	106.6	C8—C19—H19A	106.9 (11)
C19—C8—H8	106.6	C8—C19—H19B	110.7 (10)
C8—C9—C10	121.84 (18)	C8—C19—H19C	111.0 (11)
C8—C9—C17	119.89 (15)	H19A—C19—H19B	109.2 (15)
C10—C9—C17	118.27 (17)	H19A—C19—H19C	111.4 (15)
C9—C10—C11	121.77 (19)	H19B—C19—H19C	107.7 (15)
F1—C3—C2—C1	−176.56 (16)	C8—C9—C10—C11	−179.90 (17)
F1—C3—C2—C8	4.3 (3)	C8—C9—C17—C16	1.7 (2)
F1—C3—C4—C5	−179.31 (18)	C8—C9—C17—C18	−178.23 (15)
O1—C7—C1—C2	163.85 (18)	C9—C10—C11—C12	−1.3 (3)
O1—C7—C1—C6	−20.9 (3)	C9—C17—C16—C15	−178.27 (18)
O2—C7—C1—C2	−20.1 (3)	C9—C17—C18—C12	−2.5 (2)
O2—C7—C1—C6	155.19 (19)	C9—C17—C18—C13	178.03 (17)
C1—C2—C3—C4	3.9 (3)	C10—C9—C8—C19	13.3 (3)
C1—C2—C8—C9	−125.36 (18)	C10—C9—C17—C16	−177.74 (17)
C1—C2—C8—C19	105.9 (2)	C10—C9—C17—C18	2.4 (2)
C1—C6—C5—C4	2.0 (3)	C10—C11—C12—C18	1.2 (3)
C2—C1—C6—C5	2.5 (3)	C11—C10—C9—C17	−0.5 (3)
C2—C3—C4—C5	0.3 (3)	C11—C12—C18—C13	−179.8 (2)
C2—C8—C9—C10	−112.68 (19)	C11—C12—C18—C17	0.7 (3)
C2—C8—C9—C17	67.9 (2)	C12—C18—C13—C14	−178.6 (2)
C3—C2—C1—C6	−5.1 (3)	C12—C18—C17—C16	177.59 (17)
C3—C2—C1—C7	169.94 (17)	C13—C14—C15—C16	−0.9 (3)
C3—C2—C8—C9	53.6 (2)	C13—C18—C17—C16	−1.9 (2)
C3—C2—C8—C19	−75.1 (2)	C14—C13—C18—C17	0.8 (3)
C3—C4—C5—C6	−3.3 (3)	C14—C15—C16—C17	−0.3 (3)
C4—C3—C2—C8	−175.25 (18)	C15—C14—C13—C18	0.6 (3)
C5—C6—C1—C7	−172.86 (19)	C15—C16—C17—C18	1.6 (3)
C6—C1—C2—C8	173.94 (17)	C17—C9—C8—C19	−166.05 (17)
C7—C1—C2—C8	−11.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^i	1.04 (3)	1.60 (3)	2.632 (2)	177 (3)
C15—H15···F1^ii	0.98	2.49	3.355 (2)	147
C8—H8···O2	0.98	2.24	2.903 (2)	124
C6—H6···O1	0.98	2.35	2.698 (2)	100
C19—H19B···F1	1.03 (2)	2.54 (2)	3.126 (3)	115 (2)

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