Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806030017/ng2054sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806030017/ng2054Isup2.hkl |
CCDC reference: 624925
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.007 Å
- Disorder in main residue
- R factor = 0.028
- wR factor = 0.067
- Data-to-parameter ratio = 16.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT030_ALERT_1_C _diffrn_reflns_number .LE. _reflns_number_total ?
Author Response: Omitted 2 reflections because of OFF Center. |
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C14
Author Response: Explained in _publ_section_exptl_refinement |
PLAT301_ALERT_3_C Main Residue Disorder ......................... 21.00 Perc.
Author Response: Explained in _publ_section_exptl_refinement |
Alert level G ABSTM02_ALERT_3_G The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.431 0.533 Tmin and Tmax expected: 0.229 0.360 RR = 1.271 Please check that your absorption correction is appropriate.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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
Data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97-2 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97-2 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97-2.
[Ir(C11H8N)2(C7H9O2)]·CH2Cl2 | F(000) = 1392 |
Mr = 710.64 | Dx = 1.727 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -c_2yc | Cell parameters from 32 reflections |
a = 12.094 (1) Å | θ = 9.5–10.4° |
b = 14.889 (2) Å | µ = 5.11 mm−1 |
c = 15.287 (2) Å | T = 298 K |
β = 96.743 (9)° | Block, yellow |
V = 2733.7 (6) Å3 | 0.50 × 0.25 × 0.20 mm |
Z = 4 |
Stoe Stadi-4 diffractometer | 2873 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 27.5°, θmin = 2.2° |
ω–2θ scans | h = −15→15 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1996) | k = 0→19 |
Tmin = 0.431, Tmax = 0.533 | l = 0→19 |
3137 measured reflections | 3 standard reflections every 60 min |
3137 independent reflections | intensity decay: 3.2% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.028 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0313P)2 + 8.9226P] where P = (Fo2 + 2Fc2)/3 |
3137 reflections | (Δ/σ)max < 0.001 |
192 parameters | Δρmax = 0.70 e Å−3 |
52 restraints | Δρmin = −0.53 e Å−3 |
Experimental. Spectroscopic analysis: 1H NMR (300 MHz, CDCl3): δ 8.51 (d, 2H, J = 5.1), 7.85 (d, 2H, J = 7.8), 7.51 (t, 2H, J = 7.2), 7.54 (d, 2H, J = 7.5), 7.13 (t, 2H, J = 7.2), 6.80 (t, 2H, J = 7.2), 6.68 (t, 2H, J = 7.5), 6.26 (d, 2H, J = 7.8), 2.17(s, 3H), 1.78 (s, 6H). HRMS (EI, m/z): Calcd for C29H25IrN2O2: 625.74. Found: 626.26. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ir1 | 0.5000 | 0.041705 (14) | 0.7500 | 0.03459 (8) | |
Cl1 | 0.0917 (2) | 0.1471 (2) | 0.8175 (2) | 0.1550 (11) | |
N1 | 0.3730 (3) | 0.0338 (2) | 0.6496 (2) | 0.0399 (7) | |
C1 | 0.2776 (4) | 0.0809 (3) | 0.6458 (3) | 0.0517 (11) | |
H1 | 0.2687 | 0.1219 | 0.6904 | 0.062* | |
C2 | 0.1925 (5) | 0.0704 (4) | 0.5781 (4) | 0.0620 (13) | |
H2 | 0.1272 | 0.1035 | 0.5772 | 0.074* | |
C3 | 0.2061 (5) | 0.0103 (4) | 0.5123 (4) | 0.0606 (13) | |
H3 | 0.1500 | 0.0024 | 0.4658 | 0.073* | |
C4 | 0.3033 (4) | −0.0385 (3) | 0.5153 (3) | 0.0517 (11) | |
H4 | 0.3132 | −0.0793 | 0.4708 | 0.062* | |
C5 | 0.3866 (4) | −0.0264 (3) | 0.5852 (3) | 0.0400 (9) | |
C6 | 0.4932 (4) | −0.0747 (3) | 0.5984 (3) | 0.0388 (9) | |
C7 | 0.5259 (4) | −0.1374 (3) | 0.5388 (3) | 0.0498 (11) | |
H7 | 0.4801 | −0.1494 | 0.4869 | 0.060* | |
C8 | 0.6266 (5) | −0.1816 (3) | 0.5568 (3) | 0.0561 (12) | |
H8 | 0.6478 | −0.2245 | 0.5178 | 0.067* | |
C9 | 0.6958 (4) | −0.1618 (3) | 0.6332 (3) | 0.0542 (12) | |
H9 | 0.7636 | −0.1914 | 0.6454 | 0.065* | |
C10 | 0.6639 (4) | −0.0977 (3) | 0.6916 (3) | 0.0468 (10) | |
H10 | 0.7119 | −0.0844 | 0.7421 | 0.056* | |
C11 | 0.5619 (4) | −0.0524 (3) | 0.6769 (3) | 0.0374 (8) | |
O1 | 0.5641 (19) | 0.1484 (6) | 0.6800 (15) | 0.040 (3) | 0.50 |
O2 | 0.4112 (19) | 0.1432 (7) | 0.8213 (15) | 0.040 (3) | 0.50 |
C12 | 0.5497 (12) | 0.2314 (5) | 0.6892 (9) | 0.0456 (18) | 0.50 |
C13 | 0.6028 (11) | 0.3035 (7) | 0.6398 (8) | 0.058 (2) | 0.50 |
H13A | 0.6812 | 0.3098 | 0.6613 | 0.069* | 0.50 |
H13B | 0.5955 | 0.2904 | 0.5772 | 0.069* | 0.50 |
C14 | 0.5404 (11) | 0.3856 (6) | 0.6576 (8) | 0.088 (4) | 0.50 |
H14A | 0.4778 | 0.3941 | 0.6125 | 0.106* | 0.50 |
H14B | 0.5883 | 0.4379 | 0.6585 | 0.106* | 0.50 |
C15 | 0.5011 (18) | 0.3721 (4) | 0.7447 (11) | 0.079 (3) | 0.50 |
H15A | 0.4313 | 0.4034 | 0.7476 | 0.095* | 0.50 |
H15B | 0.5555 | 0.3947 | 0.7911 | 0.095* | 0.50 |
C16 | 0.4856 (9) | 0.2723 (4) | 0.7546 (8) | 0.053 (3) | 0.50 |
C17 | 0.4264 (10) | 0.2266 (6) | 0.8103 (8) | 0.0456 (18) | 0.50 |
C18 | 0.3663 (10) | 0.2824 (8) | 0.8734 (8) | 0.058 (2) | 0.50 |
H18A | 0.2928 | 0.2966 | 0.8461 | 0.087* | 0.50 |
H18B | 0.4069 | 0.3369 | 0.8874 | 0.087* | 0.50 |
H18C | 0.3612 | 0.2488 | 0.9264 | 0.087* | 0.50 |
C19 | 0.0000 | 0.2116 (7) | 0.7500 | 0.098 (3) | |
H19A | −0.0414 | 0.2499 | 0.7858 | 0.118* | 0.50 |
H19B | 0.0414 | 0.2499 | 0.7142 | 0.118* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir1 | 0.04410 (13) | 0.03187 (11) | 0.02759 (11) | 0.000 | 0.00327 (8) | 0.000 |
Cl1 | 0.130 (2) | 0.174 (3) | 0.165 (3) | 0.044 (2) | 0.0382 (19) | 0.045 (2) |
N1 | 0.0456 (18) | 0.0395 (18) | 0.0336 (16) | 0.0014 (15) | 0.0006 (14) | 0.0038 (14) |
C1 | 0.053 (3) | 0.052 (3) | 0.049 (3) | 0.009 (2) | 0.004 (2) | −0.002 (2) |
C2 | 0.052 (3) | 0.067 (3) | 0.065 (3) | 0.011 (2) | −0.003 (2) | 0.001 (3) |
C3 | 0.059 (3) | 0.065 (3) | 0.052 (3) | 0.003 (3) | −0.015 (2) | 0.001 (2) |
C4 | 0.064 (3) | 0.049 (2) | 0.039 (2) | −0.001 (2) | −0.005 (2) | −0.0028 (19) |
C5 | 0.053 (2) | 0.035 (2) | 0.0309 (19) | −0.0063 (17) | 0.0011 (17) | 0.0025 (15) |
C6 | 0.050 (2) | 0.0325 (18) | 0.034 (2) | −0.0034 (17) | 0.0070 (17) | 0.0007 (16) |
C7 | 0.067 (3) | 0.047 (2) | 0.036 (2) | −0.003 (2) | 0.011 (2) | −0.0063 (19) |
C8 | 0.072 (3) | 0.047 (3) | 0.054 (3) | 0.006 (2) | 0.023 (2) | −0.009 (2) |
C9 | 0.055 (3) | 0.054 (3) | 0.056 (3) | 0.014 (2) | 0.014 (2) | 0.001 (2) |
C10 | 0.050 (2) | 0.047 (2) | 0.043 (2) | 0.009 (2) | 0.0042 (19) | 0.0034 (19) |
C11 | 0.048 (2) | 0.034 (2) | 0.0307 (18) | 0.0020 (17) | 0.0089 (16) | 0.0043 (15) |
O1 | 0.044 (8) | 0.0399 (18) | 0.0377 (16) | −0.001 (3) | 0.006 (4) | 0.002 (3) |
O2 | 0.044 (8) | 0.0399 (18) | 0.0377 (16) | −0.001 (3) | 0.006 (4) | 0.002 (3) |
C12 | 0.043 (5) | 0.041 (2) | 0.046 (2) | 0.004 (3) | −0.020 (3) | −0.003 (5) |
C13 | 0.065 (6) | 0.036 (4) | 0.072 (4) | 0.008 (3) | 0.006 (4) | 0.003 (3) |
C14 | 0.089 (7) | 0.061 (6) | 0.113 (8) | −0.005 (6) | 0.007 (6) | 0.027 (6) |
C15 | 0.075 (5) | 0.045 (4) | 0.115 (7) | −0.003 (10) | −0.001 (5) | 0.004 (9) |
C16 | 0.047 (6) | 0.043 (4) | 0.065 (5) | −0.024 (4) | −0.006 (4) | −0.027 (5) |
C17 | 0.043 (5) | 0.041 (2) | 0.046 (2) | 0.004 (3) | −0.020 (3) | −0.003 (5) |
C18 | 0.065 (6) | 0.036 (4) | 0.072 (4) | 0.008 (3) | 0.006 (4) | 0.003 (3) |
C19 | 0.123 (9) | 0.066 (6) | 0.119 (9) | 0.000 | 0.065 (7) | 0.000 |
Ir1—C11 | 1.992 (4) | C9—C10 | 1.394 (6) |
Ir1—C11i | 1.992 (4) | C9—H9 | 0.9300 |
Ir1—N1 | 2.044 (3) | C10—C11 | 1.400 (6) |
Ir1—N1i | 2.044 (3) | C10—H10 | 0.9300 |
Ir1—O1 | 2.11 (2) | O1—C12 | 1.258 (7) |
Ir1—O1i | 2.11 (2) | O2—C17 | 1.269 (8) |
Ir1—O2 | 2.21 (2) | C12—C16 | 1.468 (8) |
Ir1—O2i | 2.21 (2) | C12—C13 | 1.500 (9) |
Cl1—C19 | 1.717 (6) | C13—C14 | 1.478 (8) |
N1—C1 | 1.345 (6) | C13—H13A | 0.9700 |
N1—C5 | 1.355 (5) | C13—H13B | 0.9700 |
C1—C2 | 1.380 (7) | C14—C15 | 1.479 (9) |
C1—H1 | 0.9300 | C14—H14A | 0.9700 |
C2—C3 | 1.371 (8) | C14—H14B | 0.9700 |
C2—H2 | 0.9300 | C15—C16 | 1.507 (7) |
C3—C4 | 1.377 (7) | C15—H15A | 0.9700 |
C3—H3 | 0.9300 | C15—H15B | 0.9700 |
C4—C5 | 1.392 (6) | C16—C17 | 1.358 (8) |
C4—H4 | 0.9300 | C17—C18 | 1.521 (9) |
C5—C6 | 1.470 (6) | C18—H18A | 0.9600 |
C6—C7 | 1.393 (6) | C18—H18B | 0.9600 |
C6—C11 | 1.417 (6) | C18—H18C | 0.9600 |
C7—C8 | 1.384 (7) | C19—Cl1ii | 1.717 (6) |
C7—H7 | 0.9300 | C19—H19A | 0.9700 |
C8—C9 | 1.386 (7) | C19—H19B | 0.9700 |
C8—H8 | 0.9300 | ||
C11—Ir1—C11i | 90.6 (2) | C8—C7—H7 | 120.0 |
C11—Ir1—N1 | 80.64 (16) | C6—C7—H7 | 120.0 |
C11i—Ir1—N1 | 94.70 (15) | C7—C8—C9 | 119.8 (4) |
C11—Ir1—N1i | 94.70 (15) | C7—C8—H8 | 120.1 |
C11i—Ir1—N1i | 80.64 (16) | C9—C8—H8 | 120.1 |
N1—Ir1—N1i | 173.42 (19) | C8—C9—C10 | 120.0 (4) |
C11—Ir1—O1 | 93.5 (5) | C8—C9—H9 | 120.0 |
C11i—Ir1—O1 | 175.8 (5) | C10—C9—H9 | 120.0 |
N1—Ir1—O1 | 87.2 (6) | C9—C10—C11 | 122.2 (4) |
N1i—Ir1—O1 | 97.8 (6) | C9—C10—H10 | 118.9 |
C11—Ir1—O1i | 175.8 (5) | C11—C10—H10 | 118.9 |
C11i—Ir1—O1i | 93.5 (5) | C10—C11—C6 | 116.2 (4) |
N1—Ir1—O1i | 97.8 (6) | C10—C11—Ir1 | 129.1 (3) |
N1i—Ir1—O1i | 87.2 (6) | C6—C11—Ir1 | 114.7 (3) |
O1—Ir1—O1i | 82.5 (9) | C12—O1—Ir1 | 128.2 (17) |
C11—Ir1—O2 | 172.9 (5) | C17—O2—Ir1 | 121.0 (16) |
C11i—Ir1—O2 | 88.2 (4) | O1—C12—C16 | 125.1 (15) |
N1—Ir1—O2 | 92.5 (6) | O1—C12—C13 | 125.0 (15) |
N1i—Ir1—O2 | 92.0 (6) | C16—C12—C13 | 109.7 (5) |
O1—Ir1—O2 | 88.0 (2) | C14—C13—C12 | 103.9 (6) |
O1i—Ir1—O2 | 7.8 (9) | C14—C13—H13A | 111.0 |
C11—Ir1—O2i | 88.2 (4) | C12—C13—H13A | 111.0 |
C11i—Ir1—O2i | 172.9 (5) | C14—C13—H13B | 111.0 |
N1—Ir1—O2i | 92.0 (6) | C12—C13—H13B | 111.0 |
N1i—Ir1—O2i | 92.5 (6) | H13A—C13—H13B | 109.0 |
O1—Ir1—O2i | 7.8 (9) | C13—C14—C15 | 106.2 (6) |
O1i—Ir1—O2i | 88.0 (2) | C13—C14—H14A | 110.5 |
O2—Ir1—O2i | 93.9 (7) | C15—C14—H14A | 110.5 |
C1—N1—C5 | 119.4 (4) | C13—C14—H14B | 110.5 |
C1—N1—Ir1 | 124.6 (3) | C15—C14—H14B | 110.5 |
C5—N1—Ir1 | 116.0 (3) | H14A—C14—H14B | 108.7 |
N1—C1—C2 | 122.2 (5) | C14—C15—C16 | 106.4 (6) |
N1—C1—H1 | 118.9 | C14—C15—H15A | 110.5 |
C2—C1—H1 | 118.9 | C16—C15—H15A | 110.5 |
C3—C2—C1 | 118.8 (5) | C14—C15—H15B | 110.5 |
C3—C2—H2 | 120.6 | C16—C15—H15B | 110.5 |
C1—C2—H2 | 120.6 | H15A—C15—H15B | 108.6 |
C2—C3—C4 | 119.7 (5) | C17—C16—C12 | 125.3 (6) |
C2—C3—H3 | 120.2 | C17—C16—C15 | 129.7 (8) |
C4—C3—H3 | 120.2 | C12—C16—C15 | 105.0 (6) |
C3—C4—C5 | 119.7 (5) | O2—C17—C16 | 132.0 (15) |
C3—C4—H4 | 120.2 | O2—C17—C18 | 111.2 (15) |
C5—C4—H4 | 120.2 | C16—C17—C18 | 116.7 (8) |
N1—C5—C4 | 120.3 (4) | Cl1ii—C19—Cl1 | 112.0 (6) |
N1—C5—C6 | 113.8 (4) | Cl1ii—C19—H19A | 109.2 |
C4—C5—C6 | 125.9 (4) | Cl1—C19—H19A | 109.2 |
C7—C6—C11 | 121.9 (4) | Cl1ii—C19—H19B | 109.2 |
C7—C6—C5 | 123.4 (4) | Cl1—C19—H19B | 109.2 |
C11—C6—C5 | 114.8 (4) | H19A—C19—H19B | 107.9 |
C8—C7—C6 | 120.0 (4) | ||
C11—Ir1—N1—C1 | 177.5 (4) | N1—Ir1—C11—C10 | 179.3 (4) |
C11i—Ir1—N1—C1 | 87.7 (4) | N1i—Ir1—C11—C10 | −5.4 (4) |
O1—Ir1—N1—C1 | −88.5 (6) | O1—Ir1—C11—C10 | 92.7 (7) |
O1i—Ir1—N1—C1 | −6.5 (6) | O2i—Ir1—C11—C10 | 86.9 (7) |
O2—Ir1—N1—C1 | −0.6 (5) | C11i—Ir1—C11—C6 | 95.3 (3) |
O2i—Ir1—N1—C1 | −94.7 (5) | N1—Ir1—C11—C6 | 0.6 (3) |
C11—Ir1—N1—C5 | 0.4 (3) | N1i—Ir1—C11—C6 | 176.0 (3) |
C11i—Ir1—N1—C5 | −89.5 (3) | O1—Ir1—C11—C6 | −85.9 (6) |
O1—Ir1—N1—C5 | 94.4 (5) | O2i—Ir1—C11—C6 | −91.7 (6) |
O1i—Ir1—N1—C5 | 176.4 (5) | C11—Ir1—O1—C12 | 175.5 (14) |
O2—Ir1—N1—C5 | −177.8 (5) | N1—Ir1—O1—C12 | 95.1 (15) |
O2i—Ir1—N1—C5 | 88.2 (5) | N1i—Ir1—O1—C12 | −89.3 (15) |
C5—N1—C1—C2 | −0.3 (7) | O1i—Ir1—O1—C12 | −3.2 (9) |
Ir1—N1—C1—C2 | −177.4 (4) | O2—Ir1—O1—C12 | 2.4 (19) |
N1—C1—C2—C3 | −0.4 (9) | O2i—Ir1—O1—C12 | −137 (9) |
C1—C2—C3—C4 | 0.4 (9) | C11i—Ir1—O2—C17 | 172.6 (11) |
C2—C3—C4—C5 | 0.1 (8) | N1—Ir1—O2—C17 | −92.8 (11) |
C1—N1—C5—C4 | 0.8 (6) | N1i—Ir1—O2—C17 | 92.0 (11) |
Ir1—N1—C5—C4 | 178.2 (3) | O1—Ir1—O2—C17 | −5.7 (16) |
C1—N1—C5—C6 | −178.6 (4) | O1i—Ir1—O2—C17 | 40 (7) |
Ir1—N1—C5—C6 | −1.2 (4) | O2i—Ir1—O2—C17 | −0.7 (7) |
C3—C4—C5—N1 | −0.8 (7) | Ir1—O1—C12—C16 | 1.9 (17) |
C3—C4—C5—C6 | 178.6 (5) | Ir1—O1—C12—C13 | 176.8 (14) |
N1—C5—C6—C7 | −177.8 (4) | O1—C12—C13—C14 | 167.0 (12) |
C4—C5—C6—C7 | 2.9 (7) | C16—C12—C13—C14 | −17.4 (12) |
N1—C5—C6—C11 | 1.8 (5) | C12—C13—C14—C15 | 28.5 (16) |
C4—C5—C6—C11 | −177.6 (4) | C13—C14—C15—C16 | −29.5 (16) |
C11—C6—C7—C8 | 1.9 (7) | O1—C12—C16—C17 | −4.9 (9) |
C5—C6—C7—C8 | −178.6 (4) | C13—C12—C16—C17 | 179.6 (8) |
C6—C7—C8—C9 | −1.6 (7) | O1—C12—C16—C15 | 175.3 (8) |
C7—C8—C9—C10 | 0.1 (8) | C13—C12—C16—C15 | −0.3 (9) |
C8—C9—C10—C11 | 1.1 (7) | C14—C15—C16—C17 | −161.8 (12) |
C9—C10—C11—C6 | −0.8 (6) | C14—C15—C16—C12 | 18.1 (12) |
C9—C10—C11—Ir1 | −179.4 (3) | Ir1—O2—C17—C16 | 5.5 (13) |
C7—C6—C11—C10 | −0.7 (6) | Ir1—O2—C17—C18 | −173.9 (12) |
C5—C6—C11—C10 | 179.7 (4) | C12—C16—C17—O2 | 0.4 (7) |
C7—C6—C11—Ir1 | 178.1 (3) | C15—C16—C17—O2 | −179.8 (4) |
C5—C6—C11—Ir1 | −1.5 (5) | C12—C16—C17—C18 | 179.8 (3) |
C11i—Ir1—C11—C10 | −86.1 (4) | C15—C16—C17—C18 | −0.4 (5) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x, y, −z+3/2. |