Boron–π inter­actions in two 3-(di­hydroxy­bor­yl)anilinium salts analyzed by crystallographic studies and supported by the noncovalent inter­actions (NCI) index theoretical approach

In the title com­pounds, 3-(di­hydroxy­bor­yl)anilinium bis­ulfate monohydrate, C₆H₉BNO₂⁺·HSO₄⁻·H₂O (I), and 3-(di­hydroxy­bor­yl)anilinium methyl sulfate, C₆H₉BNO₂⁺·CH₃SO₄⁻ (II), the almost planar boronic acid mol­ecules are linked by pairs of O—H...O hydro­gen bonds, forming centrosymmetric motifs that can be described by the graph-set R₂²(8) motif. In both crystals, the B(OH)₂ group acquires a syn–anti conformation (with respect to the H atoms). The presence of the hydro­gen-bonding functional groups B(OH)₂, NH₃⁺, HSO₄⁻, CH₃SO₄⁻ and H₂O generates three-dimensional hydro­gen-bonded networks, in which the bis­ulfate (HSO₄⁻) and methyl sulfate (CH₃SO₄⁻) counter-ions act as the central building blocks within the crystal structures. Furthermore, in both structures, the packing is stabilized by weak boron–π inter­actions, as shown by noncovalent inter­actions (NCI) index calculations.

Computing details

For both structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

3-(Dihydroxyboryl)anilinium hydrogen sulfate monohydrate (I)

Crystal data

C6H9BNO2^+·HSO4^−·H2O	Dx = 1.582 Mg m^−3
Mr = 253.04	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, Pbca	Cell parameters from 2687 reflections
a = 14.1807 (6) Å	θ = 4.3–72.3°
b = 7.4675 (3) Å	µ = 2.96 mm^−1
c = 20.0702 (8) Å	T = 293 K
V = 2125.32 (15) Å^3	Block, clear yellowish yellow
Z = 8	0.34 × 0.2 × 0.16 mm
F(000) = 1056

Data collection

Agilent SuperNova Dual Source diffractometer with an Eos detector	1914 reflections with I > 2σ(I)
Detector resolution: 8.0769 pixels mm^-1	Rint = 0.040
ω scans	θmax = 72.7°, θmin = 4.4°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −17→9
Tmin = 0.589, Tmax = 1.000	k = −9→7
4648 measured reflections	l = −23→24
2071 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.0922P)^2 + 0.8783P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2071 reflections	Δρmax = 0.74 e Å^−3
177 parameters	Δρmin = −0.82 e Å^−3
8 restraints

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
C1	0.39986 (14)	0.5777 (3)	0.55191 (9)	0.0136 (4)
C2	0.40815 (14)	0.5262 (3)	0.61859 (9)	0.0134 (4)
H2	0.435219	0.603948	0.649307	0.016*
C3	0.37619 (14)	0.3597 (3)	0.63916 (9)	0.0130 (4)
C4	0.33477 (16)	0.2402 (3)	0.59484 (11)	0.0165 (4)
H4	0.313501	0.128960	0.609284	0.020*
C5	0.32584 (16)	0.2906 (3)	0.52852 (10)	0.0180 (4)
H5	0.298259	0.212551	0.498100	0.022*
C6	0.35800 (14)	0.4573 (3)	0.50738 (10)	0.0153 (4)
H6	0.351547	0.489258	0.462826	0.018*
B1	0.43950 (17)	0.7658 (3)	0.53047 (12)	0.0142 (5)
N1	0.38825 (13)	0.3073 (2)	0.70905 (8)	0.0136 (4)
H1D	0.4285 (14)	0.222 (2)	0.7134 (13)	0.019 (7)*
H1B	0.3392 (11)	0.264 (3)	0.7284 (12)	0.015 (6)*
H1C	0.405 (2)	0.394 (2)	0.7347 (12)	0.032 (8)*
O1	0.49180 (11)	0.8560 (2)	0.57635 (7)	0.0180 (4)
H1A	0.509 (3)	0.953 (2)	0.5618 (15)	0.055 (11)*
O2	0.42498 (11)	0.8431 (2)	0.46978 (7)	0.0180 (4)
H2A	0.3939 (17)	0.791 (3)	0.4412 (10)	0.026 (7)*
O3	0.31753 (11)	0.7391 (2)	0.36457 (7)	0.0165 (4)
O4	0.43779 (11)	0.8888 (2)	0.29739 (7)	0.0179 (4)
O5	0.28937 (11)	0.8106 (2)	0.24853 (7)	0.0205 (4)
O6	0.40248 (11)	0.5799 (2)	0.27829 (8)	0.0214 (4)
H6A	0.390 (3)	0.510 (4)	0.3084 (12)	0.073 (14)*
O7	0.37303 (11)	0.3040 (2)	0.34654 (8)	0.0182 (4)
H7A	0.4087 (18)	0.257 (4)	0.3736 (12)	0.036 (9)*
H7B	0.3234 (12)	0.270 (4)	0.3633 (15)	0.045 (11)*
S1	0.35902 (4)	0.76286 (7)	0.29823 (2)	0.0129 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0127 (10)	0.0194 (10)	0.0086 (9)	0.0008 (7)	0.0001 (6)	−0.0002 (7)
C2	0.0118 (9)	0.0203 (10)	0.0080 (9)	−0.0004 (7)	0.0001 (6)	−0.0019 (7)
C3	0.0106 (9)	0.0208 (10)	0.0077 (9)	0.0008 (7)	0.0011 (7)	0.0021 (7)
C4	0.0163 (10)	0.0198 (10)	0.0135 (10)	−0.0030 (7)	0.0006 (9)	0.0006 (7)
C5	0.0196 (11)	0.0233 (10)	0.0110 (9)	−0.0048 (9)	−0.0008 (8)	−0.0032 (8)
C6	0.0171 (10)	0.0218 (10)	0.0072 (9)	−0.0004 (7)	−0.0008 (7)	−0.0001 (7)
B1	0.0132 (11)	0.0203 (11)	0.0092 (10)	0.0000 (8)	−0.0011 (9)	−0.0005 (8)
N1	0.0129 (8)	0.0198 (9)	0.0081 (8)	−0.0009 (7)	0.0007 (6)	0.0022 (6)
O1	0.0233 (8)	0.0199 (7)	0.0109 (7)	−0.0057 (6)	−0.0053 (6)	0.0033 (5)
O2	0.0225 (8)	0.0220 (8)	0.0095 (7)	−0.0063 (6)	−0.0054 (6)	0.0021 (6)
O3	0.0158 (8)	0.0265 (8)	0.0072 (7)	0.0007 (6)	−0.0006 (5)	−0.0002 (5)
O4	0.0135 (8)	0.0196 (8)	0.0207 (8)	−0.0028 (6)	−0.0018 (5)	0.0021 (5)
O5	0.0147 (7)	0.0357 (9)	0.0111 (7)	−0.0034 (7)	−0.0028 (6)	0.0049 (6)
O6	0.0243 (8)	0.0210 (8)	0.0187 (8)	−0.0005 (6)	0.0081 (6)	−0.0007 (6)
O7	0.0173 (8)	0.0243 (8)	0.0130 (7)	−0.0006 (6)	−0.0021 (6)	0.0031 (6)
S1	0.0114 (3)	0.0192 (3)	0.0083 (3)	−0.00132 (17)	−0.00057 (15)	0.00027 (16)

Geometric parameters (Å, º)

C1—C2	1.397 (3)	B1—O2	1.364 (3)
C1—C6	1.400 (3)	N1—H1D	0.8600 (10)
C1—B1	1.573 (3)	N1—H1B	0.8600 (11)
C2—H2	0.9300	N1—H1C	0.8601 (11)
C2—C3	1.386 (3)	O1—H1A	0.8200 (11)
C3—C4	1.390 (3)	O2—H2A	0.8200 (11)
C3—N1	1.466 (2)	O3—S1	1.4665 (15)
C4—H4	0.9300	O4—S1	1.4604 (16)
C4—C5	1.389 (3)	O5—S1	1.4482 (15)
C5—H5	0.9300	O6—H6A	0.8200 (10)
C5—C6	1.392 (3)	O6—S1	1.5510 (16)
C6—H6	0.9300	O7—H7A	0.8200 (10)
B1—O1	1.361 (3)	O7—H7B	0.8200 (11)
C2—C1—C6	118.06 (19)	O1—B1—O2	118.48 (19)
C2—C1—B1	118.54 (18)	O2—B1—C1	124.66 (19)
C6—C1—B1	123.39 (18)	C3—N1—H1D	111.9 (18)
C1—C2—H2	119.9	C3—N1—H1B	116.0 (18)
C3—C2—C1	120.30 (18)	C3—N1—H1C	113.9 (19)
C3—C2—H2	119.9	H1D—N1—H1B	102 (2)
C2—C3—C4	121.55 (18)	H1D—N1—H1C	108 (3)
C2—C3—N1	119.06 (18)	H1B—N1—H1C	104 (3)
C4—C3—N1	119.38 (19)	B1—O1—H1A	111 (2)
C3—C4—H4	120.7	B1—O2—H2A	120 (2)
C5—C4—C3	118.55 (19)	S1—O6—H6A	107 (3)
C5—C4—H4	120.7	H7A—O7—H7B	97 (3)
C4—C5—H5	119.9	O3—S1—O6	106.70 (9)
C4—C5—C6	120.29 (19)	O4—S1—O3	113.27 (9)
C6—C5—H5	119.9	O4—S1—O6	105.09 (9)
C1—C6—H6	119.4	O5—S1—O3	112.42 (9)
C5—C6—C1	121.24 (18)	O5—S1—O4	110.81 (9)
C5—C6—H6	119.4	O5—S1—O6	108.05 (10)
O1—B1—C1	116.85 (18)
C1—C2—C3—C4	−0.4 (3)	C4—C5—C6—C1	0.0 (3)
C1—C2—C3—N1	178.29 (18)	C6—C1—C2—C3	0.5 (3)
C2—C1—C6—C5	−0.3 (3)	C6—C1—B1—O1	−169.55 (19)
C2—C1—B1—O1	9.3 (3)	C6—C1—B1—O2	10.5 (3)
C2—C1—B1—O2	−170.6 (2)	B1—C1—C2—C3	−178.42 (18)
C2—C3—C4—C5	0.1 (3)	B1—C1—C6—C5	178.56 (19)
C3—C4—C5—C6	0.1 (3)	N1—C3—C4—C5	−178.59 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···O4^i	0.86 (2)	2.08 (1)	2.872 (2)	153 (1)
N1—H1B···O5^ii	0.86 (2)	1.95 (1)	2.783 (2)	163 (2)
N1—H1B···O7^iii	0.86 (2)	2.47 (2)	2.89 (2)	111 (1)
N1—H1C···O4^iv	0.86 (2)	2.11 (1)	2.964 (2)	177 (3)
O1—H1A···O2^v	0.82 (2)	1.90 (3)	2.702 (2)	168 (4)
O2—H2A···O3	0.82 (2)	1.92 (2)	2.717 (2)	163 (2)
O6—H6A···O7	0.82 (3)	1.74 (3)	2.509 (2)	157 (3)
O7—H7A···O1^i	0.82 (3)	1.93 (3)	2.738 (2)	170 (2)
O7—H7B···O3^vi	0.82 (2)	2.01 (1)	2.769 (2)	153 (3)
C2—H2···O1	0.93	2.52	2.862 (3)	102

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

3-(Dihydroxyboryl)anilinium methyl sulfate (II)

Crystal data

C6H9BNO2^+·CH3SO4^−	F(000) = 520
Mr = 249.05	Dx = 1.582 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 10.97561 (18) Å	Cell parameters from 2836 reflections
b = 7.22452 (11) Å	θ = 5.9–72.5°
c = 13.5494 (2) Å	µ = 2.93 mm^−1
β = 103.3430 (15)°	T = 293 K
V = 1045.38 (3) Å^3	Plate, clear yellowish yellow
Z = 4	0.34 × 0.3 × 0.14 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Eos detector	1965 reflections with I > 2σ(I)
Detector resolution: 8.0769 pixels mm^-1	Rint = 0.014
ω scans	θmax = 72.8°, θmin = 4.7°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −12→13
Tmin = 0.726, Tmax = 1.000	k = −8→6
3631 measured reflections	l = −16→15
2017 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.079	w = 1/[σ^2(Fo^2) + (0.0367P)^2 + 0.659P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
2017 reflections	Δρmax = 0.35 e Å^−3
166 parameters	Δρmin = −0.40 e Å^−3
5 restraints

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
C1	0.96725 (14)	0.5585 (2)	0.36273 (11)	0.0132 (3)
C2	1.05927 (14)	0.5033 (2)	0.31245 (11)	0.0131 (3)
H2	1.127996	0.579241	0.313674	0.016*
C3	1.04875 (14)	0.3366 (2)	0.26100 (11)	0.0129 (3)
C4	0.94961 (15)	0.2183 (2)	0.25800 (12)	0.0173 (3)
H4	0.944115	0.106501	0.223217	0.021*
C5	0.85795 (16)	0.2701 (2)	0.30822 (13)	0.0214 (4)
H5	0.790476	0.191837	0.307551	0.026*
C6	0.86641 (15)	0.4380 (2)	0.35948 (12)	0.0174 (3)
H6	0.803909	0.470984	0.392239	0.021*
C7	0.39900 (15)	0.8002 (2)	0.57398 (13)	0.0190 (3)
H7A	0.417983	0.924214	0.598060	0.029*
H7B	0.409833	0.717256	0.630717	0.029*
H7C	0.313911	0.794339	0.535444	0.029*
B1	0.98218 (17)	0.7522 (2)	0.41861 (13)	0.0143 (3)
N1	1.14551 (13)	0.28718 (19)	0.20638 (10)	0.0142 (3)
H1B	1.149 (2)	0.368 (2)	0.1603 (11)	0.028 (6)*
H1C	1.131 (2)	0.1802 (13)	0.1782 (14)	0.026 (5)*
H1D	1.2181 (10)	0.287 (3)	0.2475 (14)	0.038 (7)*
O1	1.08772 (11)	0.84897 (16)	0.41822 (9)	0.0179 (3)
H1A	1.092 (2)	0.9469 (15)	0.4495 (14)	0.034 (6)*
O2	0.89447 (11)	0.82604 (16)	0.46424 (9)	0.0174 (2)
H2A	0.8312 (12)	0.766 (3)	0.4643 (18)	0.034 (6)*
O3	0.67631 (11)	0.64619 (17)	0.48249 (8)	0.0202 (3)
O4	0.67689 (11)	0.89182 (16)	0.60384 (9)	0.0202 (3)
O5	0.62808 (11)	0.58524 (16)	0.64640 (8)	0.0191 (3)
O6	0.48264 (10)	0.74674 (17)	0.51004 (8)	0.0185 (3)
S1	0.62503 (3)	0.71551 (5)	0.56395 (3)	0.01183 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0159 (7)	0.0125 (7)	0.0108 (6)	0.0009 (6)	0.0021 (5)	−0.0005 (6)
C2	0.0150 (7)	0.0116 (7)	0.0127 (7)	−0.0015 (6)	0.0032 (5)	0.0004 (6)
C3	0.0158 (7)	0.0136 (7)	0.0094 (6)	0.0026 (6)	0.0029 (5)	0.0008 (6)
C4	0.0228 (8)	0.0125 (8)	0.0170 (8)	−0.0018 (6)	0.0053 (6)	−0.0051 (6)
C5	0.0216 (8)	0.0177 (8)	0.0269 (9)	−0.0075 (7)	0.0099 (7)	−0.0067 (7)
C6	0.0176 (8)	0.0173 (8)	0.0191 (8)	−0.0010 (6)	0.0078 (6)	−0.0044 (6)
C7	0.0157 (8)	0.0224 (9)	0.0197 (8)	0.0019 (6)	0.0059 (6)	0.0016 (7)
B1	0.0174 (8)	0.0120 (8)	0.0134 (8)	0.0006 (7)	0.0037 (6)	−0.0004 (7)
N1	0.0166 (7)	0.0137 (7)	0.0122 (6)	0.0015 (5)	0.0032 (5)	−0.0026 (5)
O1	0.0199 (6)	0.0125 (6)	0.0234 (6)	−0.0033 (5)	0.0090 (5)	−0.0074 (5)
O2	0.0179 (6)	0.0137 (6)	0.0226 (6)	−0.0035 (5)	0.0092 (5)	−0.0067 (5)
O3	0.0203 (6)	0.0254 (6)	0.0176 (5)	−0.0027 (5)	0.0098 (4)	−0.0072 (5)
O4	0.0198 (6)	0.0157 (6)	0.0261 (6)	−0.0034 (5)	0.0076 (5)	−0.0057 (5)
O5	0.0222 (6)	0.0168 (6)	0.0196 (6)	0.0031 (5)	0.0075 (5)	0.0073 (5)
O6	0.0147 (6)	0.0271 (6)	0.0133 (5)	0.0012 (5)	0.0025 (4)	0.0006 (5)
S1	0.01295 (19)	0.0115 (2)	0.01144 (19)	−0.00018 (13)	0.00369 (13)	0.00016 (13)

Geometric parameters (Å, º)

C1—C2	1.400 (2)	C7—H7C	0.9600
C1—C6	1.401 (2)	C7—O6	1.4524 (19)
C1—B1	1.581 (2)	B1—O1	1.354 (2)
C2—H2	0.9300	B1—O2	1.367 (2)
C2—C3	1.383 (2)	N1—H1B	0.8601 (10)
C3—C4	1.377 (2)	N1—H1C	0.8601 (10)
C3—N1	1.4716 (19)	N1—H1D	0.8600 (10)
C4—H4	0.9300	O1—H1A	0.8200 (10)
C4—C5	1.390 (2)	O2—H2A	0.8199 (11)
C5—H5	0.9300	O3—S1	1.4396 (11)
C5—C6	1.390 (2)	O4—S1	1.4480 (12)
C6—H6	0.9300	O5—S1	1.4552 (11)
C7—H7A	0.9600	O6—S1	1.5811 (11)
C7—H7B	0.9600
C2—C1—C6	117.43 (14)	O6—C7—H7A	109.5
C2—C1—B1	118.59 (14)	O6—C7—H7B	109.5
C6—C1—B1	123.98 (14)	O6—C7—H7C	109.5
C1—C2—H2	119.7	O1—B1—C1	116.69 (14)
C3—C2—C1	120.53 (14)	O1—B1—O2	119.53 (14)
C3—C2—H2	119.7	O2—B1—C1	123.77 (14)
C2—C3—N1	118.60 (14)	C3—N1—H1B	110.9 (14)
C4—C3—C2	121.93 (14)	C3—N1—H1C	111.2 (15)
C4—C3—N1	119.46 (14)	C3—N1—H1D	110.0 (16)
C3—C4—H4	120.8	H1B—N1—H1C	108.6 (19)
C3—C4—C5	118.36 (15)	H1B—N1—H1D	106 (2)
C5—C4—H4	120.8	H1C—N1—H1D	110 (2)
C4—C5—H5	119.8	B1—O1—H1A	113.1 (16)
C4—C5—C6	120.47 (15)	B1—O2—H2A	118.6 (16)
C6—C5—H5	119.8	C7—O6—S1	117.11 (10)
C1—C6—H6	119.4	O3—S1—O4	113.74 (7)
C5—C6—C1	121.29 (14)	O3—S1—O5	114.82 (7)
C5—C6—H6	119.4	O3—S1—O6	102.42 (6)
H7A—C7—H7B	109.5	O4—S1—O5	110.18 (7)
H7A—C7—H7C	109.5	O4—S1—O6	107.96 (7)
H7B—C7—H7C	109.5	O5—S1—O6	106.98 (7)
C1—C2—C3—C4	−0.8 (2)	C6—C1—B1—O1	177.38 (15)
C1—C2—C3—N1	177.95 (13)	C6—C1—B1—O2	−4.0 (2)
C2—C1—C6—C5	−0.1 (2)	C7—O6—S1—O3	174.01 (12)
C2—C1—B1—O1	−3.2 (2)	C7—O6—S1—O4	−65.67 (13)
C2—C1—B1—O2	175.46 (15)	C7—O6—S1—O5	52.90 (13)
C2—C3—C4—C5	0.2 (2)	B1—C1—C2—C3	−178.78 (13)
C3—C4—C5—C6	0.4 (3)	B1—C1—C6—C5	179.39 (15)
C4—C5—C6—C1	−0.5 (3)	N1—C3—C4—C5	−178.53 (15)
C6—C1—C2—C3	0.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O6^i	0.86 (1)	2.58 (1)	2.959 (2)	108 (1)
N1—H1B···O4^ii	0.86 (1)	1.95 (1)	2.765 (2)	158 (1)
N1—H1C···O5^iii	0.86 (1)	1.96 (1)	2.804 (2)	165 (1)
N1—H1D···O4^iv	0.86 (1)	2.45 (1)	3.126 (2)	136 (1)
N1—H1D···O5^iv	0.86 (1)	2.16 (1)	2.952 (2)	154 (1)
O1—H1A···O2^v	0.82 (1)	2.00 (1)	2.818 (2)	176 (1)
O2—H2A···O3	0.82 (2)	1.97 (1)	2.785 (2)	171 (2)
C2—H2···O1	0.93	2.51	2.860 (2)	103
C6—H6···O3	0.93	2.42	3.316 (2)	162
C7—H7B···O5	0.96	2.54	2.925 (2)	104

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