Bis[N-(2-hydroxy­ethyl)ethyl­enediamine-κ³N,N′,O]nickel(II) squarate monohydrate

In the title compound, [Ni(C₄H₁₂N₂O)₂](C₄O₄)·H₂O or [Ni(Hydet-en)₂](Sq)·H₂O, where Hydet-en is N-(2-hydroxy­ethyl)ethyl­enediamine and Sq is the squarate dianion, the Ni^II centre has a distorted octa­hedral coordination geometry comprising four amine N and two hydroxyl O atoms from two tridentate Hydet-en ligands. All the O atoms of the squarate dianion are involved in N—H...O and O—H...O hydrogen bonding.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](C-C) = 0.004 Å
• H-atom completeness 97%
• Disorder in solvent or counterion
• R factor = 0.042
• wR factor = 0.094
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT430_ALERT_2_B Short Inter D...A Contact  O5     ..  O7      ..       2.70 Ang.
PLAT430_ALERT_2_B Short Inter D...A Contact  O6     ..  O7      ..       2.63 Ang.

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.19
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      10.00 Perc.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C12 H26 N4 Ni1 O7
            Atom count from the _atom_site data:  C12 H25 N4 Ni1 O7
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C12 H26 N4 Ni O7
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         48.00     48.00    0.00
           H        104.00    100.00    4.00
           N         16.00     16.00    0.00
           Ni         4.00      4.00    0.00
           O         28.00     28.00    0.00

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

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

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Bis[N-(2-hydroxyethyl)ethylenediamine-κ³N,N',O]nickel(II) squarate monohydrate

Crystal data

[Ni(C4H12N2O)2](C4O4)·H2O	F(000) = 840
Mr = 397.08	Dx = 1.500 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5487 reflections
a = 11.9740 (8) Å	θ = 2.3–28.0°
b = 8.7618 (4) Å	µ = 1.14 mm^−1
c = 16.9051 (12) Å	T = 297 K
β = 97.454 (6)°	Prism, violet
V = 1758.59 (19) Å^3	0.30 × 0.28 × 0.16 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	4128 independent reflections
Radiation source: fine-focus sealed tube	3478 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
Detector resolution: 6.67 pixels mm^-1	θmax = 27.8°, θmin = 2.4°
ω scans	h = −15→15
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→11
Tmin = 0.659, Tmax = 0.763	l = −22→22
28256 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0321P)^2 + 1.2308P] where P = (Fo^2 + 2Fc^2)/3
4128 reflections	(Δ/σ)max = 0.004
250 parameters	Δρmax = 0.48 e Å^−3
3 restraints	Δρmin = −0.65 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	Occ. (<1)
C1	0.1482 (3)	0.3552 (3)	0.14839 (18)	0.0505 (6)
H1A	0.1396	0.3367	0.0914	0.061*
H1B	0.1037	0.2801	0.1727	0.061*
C2	0.2709 (3)	0.3417 (3)	0.18295 (18)	0.0528 (7)
H2A	0.2790	0.3525	0.2405	0.063*
H2B	0.3002	0.2427	0.1703	0.063*
C3	0.4475 (2)	0.4920 (4)	0.1870 (2)	0.0629 (8)
H3A	0.4953	0.4048	0.1804	0.076*
H3B	0.4470	0.5094	0.2436	0.076*
C4	0.4911 (3)	0.6302 (5)	0.1490 (2)	0.0747 (10)
H4A	0.5627	0.6609	0.1782	0.090*
H4B	0.5028	0.6072	0.0945	0.090*
C5	0.1261 (3)	0.8248 (3)	0.01590 (17)	0.0536 (7)
H5A	0.0492	0.7917	0.0176	0.064*
H5B	0.1306	0.8708	−0.0358	0.064*
C6	0.1595 (3)	0.9401 (3)	0.08124 (17)	0.0535 (7)
H6A	0.2341	0.9799	0.0770	0.064*
H6B	0.1067	1.0246	0.0767	0.064*
C7	0.2093 (3)	0.9424 (3)	0.23007 (17)	0.0517 (7)
H7A	0.1633	1.0294	0.2405	0.062*
H7B	0.2838	0.9790	0.2230	0.062*
C8	0.2168 (3)	0.8323 (3)	0.29851 (17)	0.0558 (7)
H8A	0.2570	0.8785	0.3461	0.067*
H8B	0.1420	0.8046	0.3095	0.067*
C9	0.1494 (2)	0.3266 (3)	0.37272 (15)	0.0458 (6)
C10	0.1670 (2)	0.1909 (3)	0.42371 (14)	0.0400 (5)
C11	0.2775 (2)	0.2510 (3)	0.45657 (15)	0.0441 (6)
C12	0.2595 (2)	0.3832 (3)	0.40525 (16)	0.0472 (6)
N1	0.10912 (17)	0.5102 (2)	0.16446 (13)	0.0407 (4)
H1C	0.0908	0.5161	0.2144	0.049*
H1D	0.0480	0.5343	0.1299	0.049*
N2	0.33288 (18)	0.4630 (3)	0.14809 (13)	0.0425 (5)
N3	0.20283 (19)	0.6935 (3)	0.02770 (12)	0.0437 (5)
H3C	0.2661	0.7124	0.0059	0.052*
H3D	0.1697	0.6099	0.0043	0.052*
N4	0.1586 (2)	0.8623 (2)	0.15808 (13)	0.0402 (4)
O1	0.27553 (18)	0.7001 (2)	0.27665 (11)	0.0496 (5)
O2	0.41059 (17)	0.7518 (3)	0.14956 (14)	0.0570 (5)
O3	0.07164 (17)	0.3762 (3)	0.32267 (13)	0.0711 (7)
O4	0.11124 (17)	0.0759 (2)	0.43492 (12)	0.0553 (5)
O5	0.35550 (17)	0.2085 (3)	0.50836 (13)	0.0664 (6)
O6	0.3149 (2)	0.5016 (3)	0.39384 (14)	0.0715 (7)
O7	0.4344 (4)	0.6832 (8)	0.4959 (3)	0.0913 (19)	0.50
O8	0.5368 (4)	0.5355 (6)	0.4022 (3)	0.0672 (13)	0.50
H8C	0.480 (4)	0.517 (9)	0.424 (4)	0.10 (3)*	0.50
H8D	0.571 (5)	0.609 (6)	0.426 (4)	0.08 (2)*	0.50
Ni1	0.24129 (3)	0.65868 (3)	0.150954 (18)	0.03395 (9)
H4	0.092 (3)	0.842 (4)	0.1614 (19)	0.053 (9)*
H1	0.282 (3)	0.628 (5)	0.318 (2)	0.079 (12)*
H2	0.421 (3)	0.831 (5)	0.121 (2)	0.080 (13)*
H3	0.338 (2)	0.440 (3)	0.0999 (17)	0.039 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0629 (17)	0.0320 (12)	0.0559 (16)	−0.0090 (12)	0.0056 (13)	0.0006 (11)
C2	0.0663 (18)	0.0365 (13)	0.0555 (16)	0.0102 (13)	0.0067 (13)	0.0065 (12)
C3	0.0426 (15)	0.070 (2)	0.072 (2)	0.0173 (14)	−0.0091 (13)	−0.0101 (16)
C4	0.0363 (15)	0.100 (3)	0.087 (2)	−0.0009 (17)	0.0070 (15)	−0.018 (2)
C5	0.0635 (17)	0.0514 (16)	0.0426 (14)	−0.0022 (13)	−0.0056 (12)	0.0148 (12)
C6	0.0659 (18)	0.0377 (13)	0.0547 (16)	0.0010 (12)	−0.0007 (13)	0.0132 (12)
C7	0.0701 (18)	0.0333 (12)	0.0509 (15)	0.0027 (12)	0.0052 (13)	−0.0068 (11)
C8	0.076 (2)	0.0487 (15)	0.0438 (14)	0.0080 (14)	0.0105 (13)	−0.0056 (12)
C9	0.0378 (12)	0.0596 (16)	0.0395 (12)	−0.0040 (11)	0.0034 (10)	0.0100 (11)
C10	0.0382 (12)	0.0449 (13)	0.0369 (12)	−0.0021 (10)	0.0048 (9)	0.0004 (10)
C11	0.0368 (12)	0.0570 (16)	0.0377 (12)	−0.0044 (11)	0.0024 (9)	0.0101 (11)
C12	0.0428 (13)	0.0545 (15)	0.0427 (13)	−0.0097 (12)	−0.0004 (10)	0.0103 (11)
N1	0.0387 (10)	0.0371 (10)	0.0456 (11)	−0.0011 (8)	0.0029 (8)	0.0032 (8)
N2	0.0425 (11)	0.0436 (11)	0.0404 (11)	0.0070 (9)	0.0015 (9)	−0.0044 (9)
N3	0.0461 (12)	0.0477 (12)	0.0368 (10)	−0.0027 (9)	0.0034 (9)	−0.0012 (9)
N4	0.0431 (12)	0.0301 (10)	0.0467 (11)	0.0014 (9)	0.0036 (9)	0.0045 (8)
O1	0.0666 (13)	0.0425 (10)	0.0388 (9)	0.0066 (9)	0.0030 (8)	0.0032 (8)
O2	0.0466 (11)	0.0615 (13)	0.0627 (13)	−0.0134 (10)	0.0064 (9)	0.0026 (11)
O3	0.0416 (10)	0.1067 (19)	0.0618 (13)	−0.0049 (11)	−0.0054 (9)	0.0405 (13)
O4	0.0489 (11)	0.0507 (11)	0.0636 (12)	−0.0129 (9)	−0.0021 (9)	0.0069 (9)
O5	0.0414 (10)	0.0929 (16)	0.0607 (12)	−0.0123 (11)	−0.0090 (9)	0.0363 (12)
O6	0.0632 (13)	0.0741 (15)	0.0714 (14)	−0.0289 (12)	−0.0130 (10)	0.0310 (12)
O7	0.053 (3)	0.131 (5)	0.093 (4)	−0.014 (3)	0.019 (3)	−0.047 (4)
O8	0.040 (2)	0.074 (3)	0.088 (3)	−0.007 (2)	0.010 (2)	−0.039 (3)
Ni1	0.03465 (15)	0.03061 (14)	0.03573 (15)	0.00025 (12)	0.00133 (10)	0.00017 (12)

Geometric parameters (Å, º)

C1—N1	1.473 (3)	C8—H8A	0.97
C1—C2	1.514 (4)	C8—H8B	0.97
C1—H1A	0.97	C9—O3	1.252 (3)
C1—H1B	0.97	C9—C12	1.449 (4)
C2—N2	1.463 (4)	C9—C10	1.467 (4)
C2—H2A	0.97	C10—O4	1.237 (3)
C2—H2B	0.97	C10—C11	1.465 (3)
C3—N2	1.465 (3)	C11—O5	1.251 (3)
C3—C4	1.497 (5)	C11—C12	1.447 (4)
C3—H3A	0.97	C12—O6	1.259 (3)
C3—H3B	0.97	N1—Ni1	2.084 (2)
C4—O2	1.438 (4)	N1—H1C	0.90
C4—H4A	0.97	N1—H1D	0.90
C4—H4B	0.97	N2—Ni1	2.039 (2)
C5—N3	1.470 (4)	N2—H3	0.85 (3)
C5—C6	1.512 (4)	N3—Ni1	2.097 (2)
C5—H5A	0.97	N3—H3C	0.90
C5—H5B	0.97	N3—H3D	0.90
C6—N4	1.469 (3)	N4—Ni1	2.051 (2)
C6—H6A	0.97	N4—H4	0.82 (3)
C6—H6B	0.97	O1—Ni1	2.1422 (19)
C7—N4	1.467 (3)	O1—H1	0.93 (4)
C7—C8	1.500 (4)	O2—Ni1	2.188 (2)
C7—H7A	0.97	O2—H2	0.87 (4)
C7—H7B	0.97	O8—H8C	0.836 (10)
C8—O1	1.428 (3)	O8—H8D	0.836 (10)
N1—C1—C2	108.4 (2)	C11—C10—C9	89.2 (2)
N1—C1—H1A	110.0	O5—C11—C12	134.2 (2)
C2—C1—H1A	110.0	O5—C11—C10	135.6 (3)
N1—C1—H1B	110.0	C12—C11—C10	90.17 (19)
C2—C1—H1B	110.0	O6—C12—C11	135.3 (2)
H1A—C1—H1B	108.4	O6—C12—C9	134.1 (2)
N2—C2—C1	107.8 (2)	C11—C12—C9	90.6 (2)
N2—C2—H2A	110.1	C1—N1—Ni1	106.96 (16)
C1—C2—H2A	110.1	C1—N1—H1C	110.3
N2—C2—H2B	110.1	Ni1—N1—H1C	110.3
C1—C2—H2B	110.1	C1—N1—H1D	110.3
H2A—C2—H2B	108.5	Ni1—N1—H1D	110.3
N2—C3—C4	107.8 (3)	H1C—N1—H1D	108.6
N2—C3—H3A	110.1	C2—N2—C3	116.1 (2)
C4—C3—H3A	110.1	C2—N2—Ni1	107.39 (17)
N2—C3—H3B	110.1	C3—N2—Ni1	108.58 (18)
C4—C3—H3B	110.1	C2—N2—H3	108.4 (19)
H3A—C3—H3B	108.5	C3—N2—H3	107.1 (19)
O2—C4—C3	109.0 (3)	Ni1—N2—H3	109.1 (19)
O2—C4—H4A	109.9	C5—N3—Ni1	107.56 (16)
C3—C4—H4A	109.9	C5—N3—H3C	110.2
O2—C4—H4B	109.9	Ni1—N3—H3C	110.2
C3—C4—H4B	109.9	C5—N3—H3D	110.2
H4A—C4—H4B	108.3	Ni1—N3—H3D	110.2
N3—C5—C6	108.8 (2)	H3C—N3—H3D	108.5
N3—C5—H5A	109.9	C7—N4—C6	117.5 (2)
C6—C5—H5A	109.9	C7—N4—Ni1	108.31 (16)
N3—C5—H5B	109.9	C6—N4—Ni1	107.04 (17)
C6—C5—H5B	109.9	C7—N4—H4	110 (2)
H5A—C5—H5B	108.3	C6—N4—H4	106 (2)
N4—C6—C5	107.7 (2)	Ni1—N4—H4	107 (2)
N4—C6—H6A	110.2	C8—O1—Ni1	110.90 (16)
C5—C6—H6A	110.2	C8—O1—H1	111 (2)
N4—C6—H6B	110.2	Ni1—O1—H1	128 (2)
C5—C6—H6B	110.2	C4—O2—Ni1	110.29 (19)
H6A—C6—H6B	108.5	C4—O2—H2	117 (3)
N4—C7—C8	108.0 (2)	Ni1—O2—H2	120 (3)
N4—C7—H7A	110.1	H8C—O8—H8D	109 (3)
C8—C7—H7A	110.1	N2—Ni1—N4	176.12 (9)
N4—C7—H7B	110.1	N2—Ni1—N1	84.03 (9)
C8—C7—H7B	110.1	N4—Ni1—N1	99.04 (9)
H7A—C7—H7B	108.4	N2—Ni1—N3	98.52 (9)
O1—C8—C7	107.7 (2)	N4—Ni1—N3	83.48 (9)
O1—C8—H8A	110.2	N1—Ni1—N3	97.34 (9)
C7—C8—H8A	110.2	N2—Ni1—O1	97.57 (8)
O1—C8—H8B	110.2	N4—Ni1—O1	79.99 (8)
C7—C8—H8B	110.2	N1—Ni1—O1	92.71 (8)
H8A—C8—H8B	108.5	N3—Ni1—O1	161.81 (8)
O3—C9—C12	134.2 (3)	N2—Ni1—O2	79.14 (9)
O3—C9—C10	135.7 (3)	N4—Ni1—O2	97.54 (9)
C12—C9—C10	90.0 (2)	N1—Ni1—O2	162.13 (9)
O4—C10—C11	135.5 (2)	N3—Ni1—O2	91.11 (9)
O4—C10—C9	135.3 (2)	O1—Ni1—O2	83.64 (8)
N1—C1—C2—N2	−56.2 (3)	C2—N2—Ni1—N3	−115.36 (18)
N2—C3—C4—O2	51.7 (4)	C3—N2—Ni1—N3	118.4 (2)
N3—C5—C6—N4	−55.9 (3)	C2—N2—Ni1—O1	73.15 (18)
N4—C7—C8—O1	54.0 (3)	C3—N2—Ni1—O1	−53.1 (2)
O3—C9—C10—O4	0.8 (6)	C2—N2—Ni1—O2	155.14 (18)
C12—C9—C10—O4	179.7 (3)	C3—N2—Ni1—O2	28.9 (2)
O3—C9—C10—C11	−178.3 (4)	C7—N4—Ni1—N1	115.06 (19)
C12—C9—C10—C11	0.6 (2)	C6—N4—Ni1—N1	−117.35 (18)
O4—C10—C11—O5	−0.7 (6)	C7—N4—Ni1—N3	−148.51 (19)
C9—C10—C11—O5	178.3 (4)	C6—N4—Ni1—N3	−20.92 (18)
O4—C10—C11—C12	−179.7 (3)	C7—N4—Ni1—O1	23.88 (18)
C9—C10—C11—C12	−0.6 (2)	C6—N4—Ni1—O1	151.47 (19)
O5—C11—C12—O6	0.4 (7)	C7—N4—Ni1—O2	−58.25 (19)
C10—C11—C12—O6	179.4 (4)	C6—N4—Ni1—O2	69.34 (18)
O5—C11—C12—C9	−178.4 (4)	C1—N1—Ni1—N2	−11.02 (17)
C10—C11—C12—C9	0.6 (2)	C1—N1—Ni1—N4	171.36 (17)
O3—C9—C12—O6	−0.5 (7)	C1—N1—Ni1—N3	86.84 (17)
C10—C9—C12—O6	−179.4 (4)	C1—N1—Ni1—O1	−108.35 (17)
O3—C9—C12—C11	178.3 (4)	C1—N1—Ni1—O2	−30.7 (4)
C10—C9—C12—C11	−0.6 (2)	C5—N3—Ni1—N2	174.72 (17)
C2—C1—N1—Ni1	38.1 (3)	C5—N3—Ni1—N4	−8.63 (18)
C1—C2—N2—C3	166.4 (2)	C5—N3—Ni1—N1	89.69 (18)
C1—C2—N2—Ni1	44.7 (3)	C5—N3—Ni1—O1	−33.3 (4)
C4—C3—N2—C2	−173.5 (3)	C5—N3—Ni1—O2	−106.09 (18)
C4—C3—N2—Ni1	−52.5 (3)	C8—O1—Ni1—N2	−177.7 (2)
C6—C5—N3—Ni1	36.1 (3)	C8—O1—Ni1—N4	5.33 (19)
C8—C7—N4—C6	−170.4 (2)	C8—O1—Ni1—N1	−93.4 (2)
C8—C7—N4—Ni1	−49.0 (3)	C8—O1—Ni1—N3	30.3 (4)
C5—C6—N4—C7	168.3 (2)	C8—O1—Ni1—O2	104.2 (2)
C5—C6—N4—Ni1	46.3 (3)	C4—O2—Ni1—N2	−1.1 (2)
C7—C8—O1—Ni1	−32.6 (3)	C4—O2—Ni1—N4	176.9 (2)
C3—C4—O2—Ni1	−26.4 (3)	C4—O2—Ni1—N1	18.9 (4)
C2—N2—Ni1—N1	−18.80 (17)	C4—O2—Ni1—N3	−99.5 (2)
C3—N2—Ni1—N1	−145.1 (2)	C4—O2—Ni1—O1	97.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3	0.90	2.24	3.007 (3)	143
N1—H1D···O4^i	0.90	2.10	2.994 (3)	170
N3—H3C···O7^ii	0.90	2.24	3.087 (6)	157
N3—H3D···O4^iii	0.90	2.07	2.965 (3)	170
O8—H8C···O6	0.84 (1)	1.97 (5)	2.659 (5)	139 (7)
O8—H8C···O7	0.84 (1)	2.02 (6)	2.488 (7)	115 (5)
O8—H8D···O5^iv	0.84 (1)	2.08 (1)	2.910 (5)	174 (6)
N4—H4···O3^i	0.82 (3)	2.04 (3)	2.820 (3)	159 (3)
O1—H1···O6	0.93 (4)	1.71 (4)	2.633 (3)	172 (4)
O2—H2···O8^v	0.87 (4)	1.91 (4)	2.735 (5)	158 (4)
O2—H2···O7^ii	0.87 (4)	2.14 (4)	2.711 (6)	123 (3)
N2—H3···O5^iii	0.85 (3)	2.05 (3)	2.842 (3)	154 (3)

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