The heteroscorpionate ligand 2,2-bis­(3,5-di­methyl­pyrazol-1-yl)-1,1-di­phenyl­ethanol and an easy preparation of its tungsten complex

The heteroscorpionate ligand 2,2-bis­(3,5-di­methyl­pyrazol-1-yl)-1,1-di­phenyl­ethanol, C₂₄H₂₆N₄O, features in the solid state an intra­molecular O—H...N hydrogen bond. A heteroscorpionate tungsten complex, cis-[2,2-bis­(3,5-di­methyl­pyrazol­yl)-1,1-di­phenyl­ethano­lato]chlorido­dioxidotungsten(VI) tetrahydrofuran monosolvate, [W(C₂₄H₂₅N₄O)ClO₂]·C₄H₈O, was prepared by the simple mixing of solutions of the ligand and WOCl₄ in tetra­hydro­furan. The tungsten complex was isolated after standing for several weeks. The complex exhibits a κ³N,N′,O-coordination of the ligand. This simple synthetic procedure allows access to the cis isomer in high yield without additional purification steps. The Hirshfeld surface analysis shows a change of the inter­molecular contacts due to the coordination of the WO₂Cl unit with the ligand mol­ecule.

Computing details

For both structures, data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2017 (Sheldrick 2015) for (1); SHELXL2014 (Sheldrick 2015) for (2). For both structures, molecular graphics: ORTEP-3 (Farrugia, 2012). Software used to prepare material for publication: SHELXL2017 (Sheldrick, 2015) for (1); SHELXL2014 (Sheldrick, 2015) for (2).

2,2-Bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethanol (1)

Crystal data

C24H26N4O	Dx = 1.220 Mg m^−3
Mr = 386.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 25184 reflections
a = 19.0555 (6) Å	θ = 2.5–28.3°
b = 12.3840 (5) Å	µ = 0.08 mm^−1
c = 17.8388 (7) Å	T = 193 K
V = 4209.7 (3) Å^3	Prism, colourless
Z = 8	0.45 × 0.25 × 0.10 mm
F(000) = 1648

Data collection

Stoe IPDS 2T diffractometer	4826 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	3611 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.038
Detector resolution: 6.67 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
rotation method scans	h = −24→24
Absorption correction: integration (X-RED; Stoe & Cie, 2009)	k = −16→14
Tmin = 0.789, Tmax = 0.958	l = −23→21
35928 measured 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)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0332P)^2 + 1.8904P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
4826 reflections	Δρmax = 0.17 e Å^−3
281 parameters	Δρmin = −0.21 e Å^−3
0 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.

Refinement. The structures were solved by direct methods with SHELXS-97 and refined by full-matrix least-squares methods on F² for all unique reflections with SHELXL-2014 (Sheldrick, 2008). Crystal data, data collection and structure refinement details are summarized in Table 1.

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

	x	y	z	Uiso*/Ueq
N1	0.71727 (6)	0.50955 (11)	0.88355 (7)	0.0350 (3)
N2	0.67600 (7)	0.41980 (12)	0.87326 (8)	0.0422 (3)
C1	0.75933 (13)	0.67620 (18)	0.81894 (12)	0.0570 (5)
H1A	0.7414 (14)	0.732 (2)	0.8544 (14)	0.088 (8)*
H1B	0.7562 (13)	0.704 (2)	0.7666 (14)	0.086 (8)*
H1C	0.8100 (13)	0.6619 (19)	0.8291 (13)	0.076 (7)*
C2	0.71683 (9)	0.57615 (15)	0.82281 (9)	0.0435 (4)
C3	0.67211 (11)	0.52885 (18)	0.77236 (10)	0.0540 (5)
H3	0.659603	0.555883	0.724349	0.065*
C4	0.64862 (9)	0.43359 (17)	0.80515 (10)	0.0486 (5)
C5	0.60017 (11)	0.3506 (2)	0.77200 (12)	0.0691 (7)
H5A	0.593914	0.291176	0.807622	0.104*
H5B	0.620409	0.322745	0.725362	0.104*
H5C	0.554574	0.383922	0.761400	0.104*
N3	0.83274 (6)	0.48078 (10)	0.93218 (7)	0.0327 (3)
N4	0.84198 (7)	0.38179 (11)	0.89939 (7)	0.0367 (3)
C6	0.90057 (9)	0.64422 (15)	0.97612 (12)	0.0501 (4)
H6A	0.874254	0.696254	0.945738	0.075*
H6B	0.950034	0.665703	0.978072	0.075*
H6C	0.881268	0.642656	1.027024	0.075*
C7	0.89471 (8)	0.53454 (13)	0.94184 (9)	0.0371 (3)
C8	0.94578 (9)	0.46741 (15)	0.91445 (9)	0.0425 (4)
H8	0.994835	0.480981	0.913181	0.051*
C9	0.91115 (9)	0.37467 (14)	0.88865 (9)	0.0390 (4)
C10	0.94185 (11)	0.27706 (17)	0.85142 (11)	0.0551 (5)
H10A	0.909468	0.216062	0.856714	0.083*
H10B	0.986767	0.259088	0.875095	0.083*
H10C	0.949407	0.292187	0.798106	0.083*
C11	0.76206 (7)	0.51941 (13)	0.94908 (8)	0.0314 (3)
H11	0.766210	0.598305	0.960180	0.038*
C12	0.72902 (8)	0.46565 (12)	1.02000 (8)	0.0316 (3)
O1	0.72289 (6)	0.35238 (9)	1.00893 (7)	0.0385 (3)
H1D	0.7002 (12)	0.3486 (18)	0.9631 (13)	0.072 (7)*
C13	0.65677 (8)	0.51540 (13)	1.03702 (8)	0.0328 (3)
C14	0.63903 (8)	0.62154 (14)	1.01928 (9)	0.0402 (4)
H14	0.672179	0.666295	0.994452	0.048*
C15	0.57305 (9)	0.66278 (16)	1.03762 (10)	0.0460 (4)
H15	0.561649	0.735230	1.025059	0.055*
C16	0.52431 (9)	0.59915 (17)	1.07384 (10)	0.0484 (4)
H16	0.479290	0.627186	1.085857	0.058*
C17	0.54161 (9)	0.49421 (16)	1.09246 (10)	0.0483 (4)
H17	0.508513	0.450207	1.118006	0.058*
C18	0.60715 (9)	0.45252 (14)	1.07406 (9)	0.0410 (4)
H18	0.618217	0.380070	1.086975	0.049*
C19	0.77987 (8)	0.48281 (13)	1.08573 (8)	0.0334 (3)
C20	0.82916 (9)	0.40392 (14)	1.10228 (10)	0.0435 (4)
H20	0.829948	0.338932	1.074007	0.052*
C21	0.87740 (11)	0.41891 (17)	1.15980 (11)	0.0537 (5)
H21	0.911179	0.364485	1.170137	0.064*
C22	0.87658 (10)	0.5119 (2)	1.20180 (10)	0.0575 (5)
H22	0.909183	0.521588	1.241516	0.069*
C23	0.82806 (11)	0.5907 (2)	1.18574 (12)	0.0659 (6)
H23	0.827410	0.655303	1.214450	0.079*
C24	0.77993 (10)	0.57693 (17)	1.12796 (11)	0.0519 (5)
H24	0.746886	0.632287	1.117310	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0319 (6)	0.0431 (7)	0.0300 (6)	0.0036 (6)	−0.0037 (5)	−0.0028 (5)
N2	0.0341 (7)	0.0538 (9)	0.0386 (7)	−0.0011 (6)	−0.0075 (6)	−0.0103 (6)
C1	0.0682 (14)	0.0561 (12)	0.0467 (11)	0.0052 (11)	0.0001 (10)	0.0144 (9)
C2	0.0451 (9)	0.0534 (10)	0.0320 (8)	0.0140 (8)	0.0000 (7)	0.0006 (7)
C3	0.0588 (11)	0.0700 (13)	0.0331 (8)	0.0190 (10)	−0.0106 (8)	−0.0044 (8)
C4	0.0382 (9)	0.0681 (13)	0.0393 (9)	0.0118 (9)	−0.0098 (7)	−0.0164 (8)
C5	0.0524 (12)	0.0936 (17)	0.0613 (13)	0.0044 (12)	−0.0246 (10)	−0.0285 (12)
N3	0.0294 (6)	0.0350 (7)	0.0337 (6)	0.0016 (5)	−0.0005 (5)	−0.0016 (5)
N4	0.0375 (7)	0.0391 (7)	0.0337 (6)	0.0052 (6)	0.0001 (5)	−0.0032 (5)
C6	0.0369 (9)	0.0447 (10)	0.0687 (12)	−0.0065 (8)	−0.0035 (8)	−0.0032 (9)
C7	0.0318 (8)	0.0391 (8)	0.0405 (8)	−0.0012 (7)	−0.0027 (6)	0.0050 (7)
C8	0.0301 (8)	0.0517 (10)	0.0458 (9)	0.0036 (7)	0.0013 (7)	0.0084 (8)
C9	0.0389 (8)	0.0447 (9)	0.0333 (8)	0.0099 (7)	0.0020 (6)	0.0046 (7)
C10	0.0558 (11)	0.0577 (12)	0.0518 (10)	0.0186 (10)	0.0083 (9)	−0.0031 (9)
C11	0.0289 (7)	0.0336 (8)	0.0316 (7)	0.0016 (6)	−0.0027 (6)	−0.0024 (6)
C12	0.0341 (7)	0.0288 (7)	0.0320 (7)	−0.0032 (6)	−0.0026 (6)	−0.0021 (6)
O1	0.0437 (6)	0.0311 (6)	0.0409 (6)	−0.0054 (5)	−0.0042 (5)	−0.0044 (5)
C13	0.0319 (7)	0.0370 (8)	0.0295 (7)	−0.0052 (6)	−0.0021 (6)	−0.0037 (6)
C14	0.0348 (8)	0.0425 (9)	0.0432 (9)	0.0013 (7)	0.0042 (7)	0.0005 (7)
C15	0.0388 (9)	0.0515 (10)	0.0478 (9)	0.0074 (8)	0.0009 (7)	−0.0038 (8)
C16	0.0314 (8)	0.0664 (12)	0.0473 (10)	0.0007 (8)	0.0023 (7)	−0.0112 (9)
C17	0.0375 (9)	0.0615 (12)	0.0458 (9)	−0.0149 (9)	0.0065 (7)	−0.0061 (8)
C18	0.0412 (9)	0.0446 (9)	0.0374 (8)	−0.0098 (7)	0.0012 (7)	−0.0031 (7)
C19	0.0335 (7)	0.0379 (8)	0.0286 (7)	−0.0036 (6)	−0.0002 (6)	−0.0004 (6)
C20	0.0484 (10)	0.0386 (9)	0.0434 (9)	−0.0008 (8)	−0.0099 (7)	0.0037 (7)
C21	0.0521 (11)	0.0587 (12)	0.0504 (10)	−0.0012 (9)	−0.0165 (8)	0.0118 (9)
C22	0.0499 (10)	0.0865 (15)	0.0360 (9)	−0.0067 (11)	−0.0114 (8)	−0.0065 (9)
C23	0.0517 (11)	0.0870 (16)	0.0589 (12)	0.0048 (11)	−0.0140 (10)	−0.0381 (12)
C24	0.0425 (9)	0.0586 (12)	0.0546 (10)	0.0062 (9)	−0.0113 (8)	−0.0233 (9)

Geometric parameters (Å, º)

N1—C2	1.362 (2)	C10—H10C	0.9800
N1—N2	1.3739 (19)	C11—C12	1.562 (2)
N1—C11	1.4526 (18)	C11—H11	1.0000
N2—C4	1.333 (2)	C12—O1	1.4214 (18)
C1—C2	1.482 (3)	C12—C19	1.5359 (19)
C1—H1A	1.00 (3)	C12—C13	1.539 (2)
C1—H1B	1.00 (3)	O1—H1D	0.93 (2)
C1—H1C	1.00 (3)	C13—C18	1.392 (2)
C2—C3	1.371 (3)	C13—C14	1.394 (2)
C3—C4	1.391 (3)	C14—C15	1.396 (2)
C3—H3	0.9500	C14—H14	0.9500
C4—C5	1.502 (3)	C15—C16	1.379 (3)
C5—H5A	0.9800	C15—H15	0.9500
C5—H5B	0.9800	C16—C17	1.381 (3)
C5—H5C	0.9800	C16—H16	0.9500
N3—C7	1.3665 (19)	C17—C18	1.391 (2)
N3—N4	1.3696 (18)	C17—H17	0.9500
N3—C11	1.4608 (18)	C18—H18	0.9500
N4—C9	1.335 (2)	C19—C20	1.387 (2)
C6—C7	1.494 (2)	C19—C24	1.388 (2)
C6—H6A	0.9800	C20—C21	1.390 (2)
C6—H6B	0.9800	C20—H20	0.9500
C6—H6C	0.9800	C21—C22	1.374 (3)
C7—C8	1.370 (2)	C21—H21	0.9500
C8—C9	1.402 (3)	C22—C23	1.375 (3)
C8—H8	0.9500	C22—H22	0.9500
C9—C10	1.498 (2)	C23—C24	1.390 (3)
C10—H10A	0.9800	C23—H23	0.9500
C10—H10B	0.9800	C24—H24	0.9500
C2—N1—N2	112.34 (13)	N1—C11—N3	110.37 (11)
C2—N1—C11	126.38 (14)	N1—C11—C12	112.28 (12)
N2—N1—C11	120.79 (13)	N3—C11—C12	113.53 (12)
C4—N2—N1	104.01 (15)	N1—C11—H11	106.7
C2—C1—H1A	111.4 (15)	N3—C11—H11	106.7
C2—C1—H1B	107.6 (15)	C12—C11—H11	106.7
H1A—C1—H1B	109 (2)	O1—C12—C19	107.13 (12)
C2—C1—H1C	111.8 (14)	O1—C12—C13	110.43 (12)
H1A—C1—H1C	110 (2)	C19—C12—C13	111.02 (12)
H1B—C1—H1C	107 (2)	O1—C12—C11	109.95 (12)
N1—C2—C3	105.51 (17)	C19—C12—C11	107.76 (11)
N1—C2—C1	122.69 (16)	C13—C12—C11	110.47 (12)
C3—C2—C1	131.79 (18)	C12—O1—H1D	102.2 (14)
C2—C3—C4	106.64 (16)	C18—C13—C14	118.08 (15)
C2—C3—H3	126.7	C18—C13—C12	118.52 (14)
C4—C3—H3	126.7	C14—C13—C12	123.37 (14)
N2—C4—C3	111.46 (16)	C13—C14—C15	120.69 (16)
N2—C4—C5	120.8 (2)	C13—C14—H14	119.7
C3—C4—C5	127.75 (18)	C15—C14—H14	119.7
C4—C5—H5A	109.5	C16—C15—C14	120.49 (18)
C4—C5—H5B	109.5	C16—C15—H15	119.8
H5A—C5—H5B	109.5	C14—C15—H15	119.8
C4—C5—H5C	109.5	C15—C16—C17	119.31 (16)
H5A—C5—H5C	109.5	C15—C16—H16	120.3
H5B—C5—H5C	109.5	C17—C16—H16	120.3
C7—N3—N4	112.26 (12)	C16—C17—C18	120.46 (17)
C7—N3—C11	127.68 (13)	C16—C17—H17	119.8
N4—N3—C11	119.99 (12)	C18—C17—H17	119.8
C9—N4—N3	104.32 (13)	C17—C18—C13	120.96 (17)
C7—C6—H6A	109.5	C17—C18—H18	119.5
C7—C6—H6B	109.5	C13—C18—H18	119.5
H6A—C6—H6B	109.5	C20—C19—C24	118.39 (15)
C7—C6—H6C	109.5	C20—C19—C12	119.49 (14)
H6A—C6—H6C	109.5	C24—C19—C12	122.08 (15)
H6B—C6—H6C	109.5	C19—C20—C21	120.73 (17)
N3—C7—C8	105.86 (14)	C19—C20—H20	119.6
N3—C7—C6	124.00 (14)	C21—C20—H20	119.6
C8—C7—C6	130.14 (15)	C22—C21—C20	120.45 (19)
C7—C8—C9	106.24 (14)	C22—C21—H21	119.8
C7—C8—H8	126.9	C20—C21—H21	119.8
C9—C8—H8	126.9	C21—C22—C23	119.29 (17)
N4—C9—C8	111.31 (15)	C21—C22—H22	120.4
N4—C9—C10	120.17 (17)	C23—C22—H22	120.4
C8—C9—C10	128.50 (16)	C22—C23—C24	120.74 (19)
C9—C10—H10A	109.5	C22—C23—H23	119.6
C9—C10—H10B	109.5	C24—C23—H23	119.6
H10A—C10—H10B	109.5	C19—C24—C23	120.40 (18)
C9—C10—H10C	109.5	C19—C24—H24	119.8
H10A—C10—H10C	109.5	C23—C24—H24	119.8
H10B—C10—H10C	109.5
C2—N1—N2—C4	−1.35 (18)	N3—C11—C12—O1	−61.42 (15)
C11—N1—N2—C4	−173.81 (13)	N1—C11—C12—C19	−178.92 (12)
N2—N1—C2—C3	1.62 (19)	N3—C11—C12—C19	55.02 (16)
C11—N1—C2—C3	173.56 (14)	N1—C11—C12—C13	−57.49 (16)
N2—N1—C2—C1	−177.62 (17)	N3—C11—C12—C13	176.45 (12)
C11—N1—C2—C1	−5.7 (3)	O1—C12—C13—C18	30.60 (18)
N1—C2—C3—C4	−1.2 (2)	C19—C12—C13—C18	−88.06 (16)
C1—C2—C3—C4	177.9 (2)	C11—C12—C13—C18	152.45 (13)
N1—N2—C4—C3	0.55 (19)	O1—C12—C13—C14	−151.43 (14)
N1—N2—C4—C5	179.26 (16)	C19—C12—C13—C14	89.90 (17)
C2—C3—C4—N2	0.4 (2)	C11—C12—C13—C14	−29.59 (19)
C2—C3—C4—C5	−178.19 (18)	C18—C13—C14—C15	−0.6 (2)
C7—N3—N4—C9	−0.04 (17)	C12—C13—C14—C15	−178.61 (15)
C11—N3—N4—C9	177.00 (13)	C13—C14—C15—C16	0.2 (3)
N4—N3—C7—C8	−0.20 (17)	C14—C15—C16—C17	0.6 (3)
C11—N3—C7—C8	−176.97 (14)	C15—C16—C17—C18	−0.8 (3)
N4—N3—C7—C6	179.93 (15)	C16—C17—C18—C13	0.4 (3)
C11—N3—C7—C6	3.2 (2)	C14—C13—C18—C17	0.4 (2)
N3—C7—C8—C9	0.35 (18)	C12—C13—C18—C17	178.45 (14)
C6—C7—C8—C9	−179.80 (17)	O1—C12—C19—C20	24.83 (19)
N3—N4—C9—C8	0.27 (17)	C13—C12—C19—C20	145.47 (15)
N3—N4—C9—C10	−178.40 (14)	C11—C12—C19—C20	−93.43 (17)
C7—C8—C9—N4	−0.40 (19)	O1—C12—C19—C24	−157.47 (16)
C7—C8—C9—C10	178.12 (16)	C13—C12—C19—C24	−36.8 (2)
C2—N1—C11—N3	−77.25 (19)	C11—C12—C19—C24	84.27 (18)
N2—N1—C11—N3	94.07 (15)	C24—C19—C20—C21	0.0 (3)
C2—N1—C11—C12	154.99 (14)	C12—C19—C20—C21	177.78 (16)
N2—N1—C11—C12	−33.69 (18)	C19—C20—C21—C22	0.7 (3)
C7—N3—C11—N1	126.12 (16)	C20—C21—C22—C23	−0.8 (3)
N4—N3—C11—N1	−50.42 (17)	C21—C22—C23—C24	0.3 (3)
C7—N3—C11—C12	−106.81 (17)	C20—C19—C24—C23	−0.5 (3)
N4—N3—C11—C12	76.65 (16)	C12—C19—C24—C23	−178.24 (18)
N1—C11—C12—O1	64.65 (15)	C22—C23—C24—C19	0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N4^i	1.00 (3)	2.57 (3)	3.503 (3)	155 (2)
O1—H1D···N1	0.93 (2)	2.47 (2)	2.9669 (18)	113.9 (17)
O1—H1D···N2	0.93 (2)	1.89 (2)	2.7116 (18)	147 (2)

Symmetry code: (i) −x+3/2, y+1/2, z.

cis-[2,2-Bis(3,5-dimethylpyrazolyl)-1,1-diphenylethanolato]chloridodioxidotungsten(VI) tetrahydrofuran monosolvate (2)

Crystal data

[W(C24H25N4O)ClO2]·C4H8O	F(000) = 704
Mr = 708.88	Dx = 1.724 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 9.3157 (6) Å	Cell parameters from 12354 reflections
b = 8.4063 (3) Å	θ = 2.7–27.8°
c = 17.4678 (10) Å	µ = 4.37 mm^−1
β = 93.222 (5)°	T = 153 K
V = 1365.75 (13) Å^3	Prism, colourless
Z = 2	0.25 × 0.18 × 0.10 mm

Data collection

Stoe IPDS 2T diffractometer	5165 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	4924 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.019
Detector resolution: 6.67 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
rotation method scans	h = −12→12
Absorption correction: numerical (X-RED; Stoe & Cie, 2009)	k = −10→10
Tmin = 0.391, Tmax = 0.639	l = −22→21
12354 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.024	w = 1/[σ^2(Fo^2) + (0.0148P)^2 + 4.1365P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.055	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.94 e Å^−3
5165 reflections	Δρmin = −1.06 e Å^−3
348 parameters	Absolute structure: Refined as an inversion twin
2 restraints	Absolute structure parameter: 0.489 (10)
Primary atom site location: structure-invariant direct methods

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.

Refinement. Refined as a 2-component inversion twin

The structures were solved by direct methods with SHELXS-97 and refined by full-matrix least-squares methods on F² for all unique reflections with SHELXL-2014 (Sheldrick, 2008). Crystal data, data collection and structure refinement details are summarized in Table 1.

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

	x	y	z	Uiso*/Ueq
W1	1.04108 (2)	0.91051 (2)	0.75170 (2)	0.02602 (7)
Cl1	0.9829 (2)	0.6550 (2)	0.70373 (11)	0.0384 (4)
O1	1.0519 (5)	1.0754 (5)	0.8271 (2)	0.0230 (9)
O2	0.9488 (7)	1.0125 (7)	0.6767 (3)	0.0415 (13)
O3	1.2171 (6)	0.9119 (6)	0.7263 (3)	0.0364 (12)
N1	1.0583 (6)	0.7973 (6)	0.9298 (3)	0.0210 (11)
N2	1.1142 (6)	0.7653 (7)	0.8599 (3)	0.0252 (11)
C1	1.0580 (8)	0.6951 (8)	1.0644 (4)	0.0299 (15)
H1A	1.097589	0.790459	1.089940	0.045*
H1B	1.093916	0.600175	1.091828	0.045*
H1C	0.952780	0.697684	1.064274	0.045*
C2	1.1027 (7)	0.6903 (7)	0.9844 (4)	0.0247 (13)
C3	1.1911 (7)	0.5849 (8)	0.9487 (4)	0.0287 (14)
H3	1.239197	0.495853	0.971711	0.034*
C4	1.1965 (7)	0.6339 (8)	0.8722 (4)	0.0297 (15)
C5	1.2790 (9)	0.5623 (10)	0.8109 (5)	0.044 (2)
H5A	1.225357	0.471908	0.788262	0.066*
H5B	1.372457	0.525620	0.832552	0.066*
H5C	1.293579	0.642069	0.771120	0.066*
N3	0.8289 (5)	0.9045 (6)	0.8927 (3)	0.0204 (10)
N4	0.8279 (6)	0.8789 (6)	0.8150 (3)	0.0227 (11)
C6	0.6630 (8)	0.9110 (9)	1.0021 (4)	0.0325 (15)
H6A	0.709143	0.822947	1.030853	0.049*
H6B	0.558954	0.907368	1.007703	0.049*
H6C	0.701219	1.012312	1.022199	0.049*
C7	0.6929 (7)	0.8965 (7)	0.9195 (4)	0.0251 (13)
C8	0.6042 (7)	0.8661 (8)	0.8561 (4)	0.0297 (15)
H8	0.502680	0.854436	0.855246	0.036*
C9	0.6890 (7)	0.8550 (8)	0.7926 (4)	0.0292 (14)
C10	0.6416 (9)	0.8240 (10)	0.7106 (5)	0.0424 (19)
H10A	0.700576	0.886772	0.677059	0.064*
H10B	0.540452	0.854172	0.701891	0.064*
H10C	0.652895	0.710605	0.699322	0.064*
C11	0.9639 (6)	0.9334 (7)	0.9354 (4)	0.0196 (12)
H11	0.943686	0.948290	0.990534	0.023*
C12	1.0347 (6)	1.0887 (7)	0.9066 (3)	0.0194 (11)
C13	1.1824 (6)	1.1213 (7)	0.9481 (4)	0.0205 (12)
C14	1.2010 (7)	1.1228 (8)	1.0278 (4)	0.0247 (14)
H14	1.126007	1.085861	1.057938	0.030*
C15	1.3286 (7)	1.1779 (9)	1.0634 (4)	0.0294 (15)
H15	1.340200	1.180257	1.117811	0.035*
C16	1.4393 (7)	1.2297 (9)	1.0193 (4)	0.0308 (15)
H16	1.525014	1.271422	1.043636	0.037*
C17	1.4254 (7)	1.2209 (8)	0.9408 (4)	0.0301 (15)
H17	1.502847	1.252174	0.911013	0.036*
C18	1.2979 (7)	1.1661 (8)	0.9048 (4)	0.0256 (13)
H18	1.289046	1.158918	0.850413	0.031*
C19	0.9335 (6)	1.2298 (7)	0.9207 (4)	0.0199 (12)
C20	0.8932 (7)	1.3331 (8)	0.8612 (4)	0.0266 (13)
H20	0.926695	1.315324	0.811532	0.032*
C21	0.8047 (8)	1.4616 (8)	0.8736 (4)	0.0318 (15)
H21	0.778288	1.531871	0.832634	0.038*
C22	0.7543 (7)	1.4884 (8)	0.9459 (5)	0.0302 (15)
H22	0.691265	1.574893	0.953942	0.036*
C23	0.7960 (7)	1.3892 (7)	1.0056 (4)	0.0262 (13)
H23	0.764144	1.409418	1.055429	0.031*
C24	0.8843 (7)	1.2601 (8)	0.9937 (4)	0.0237 (13)
H24	0.911690	1.191508	1.035213	0.028*
O4	0.5979 (6)	0.4017 (7)	0.6188 (3)	0.0466 (14)
C25	0.6737 (9)	0.3274 (12)	0.6824 (5)	0.046 (2)
H25A	0.739923	0.403989	0.709070	0.056*
H25B	0.730398	0.236015	0.664967	0.056*
C26	0.5618 (10)	0.2724 (10)	0.7348 (5)	0.045 (2)
H26A	0.539426	0.356030	0.772203	0.054*
H26B	0.592886	0.174829	0.762814	0.054*
C27	0.4333 (9)	0.2396 (10)	0.6792 (5)	0.046 (2)
H27A	0.439564	0.132565	0.655889	0.055*
H27B	0.341570	0.248830	0.704791	0.055*
C28	0.4477 (9)	0.3688 (10)	0.6201 (5)	0.0432 (19)
H28A	0.409240	0.332480	0.569121	0.052*
H28B	0.394489	0.465268	0.634551	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
W1	0.03934 (12)	0.02519 (10)	0.01392 (10)	−0.0007 (2)	0.00483 (7)	−0.0025 (2)
Cl1	0.0601 (12)	0.0297 (8)	0.0256 (9)	−0.0043 (8)	0.0043 (8)	−0.0063 (7)
O1	0.034 (2)	0.023 (2)	0.012 (2)	−0.001 (2)	0.0021 (17)	−0.0003 (17)
O2	0.058 (4)	0.048 (3)	0.019 (3)	−0.006 (3)	0.006 (2)	0.009 (2)
O3	0.047 (3)	0.039 (3)	0.024 (3)	0.001 (2)	0.016 (2)	−0.008 (2)
N1	0.029 (3)	0.022 (2)	0.013 (3)	0.004 (2)	0.005 (2)	−0.0001 (19)
N2	0.033 (3)	0.024 (3)	0.019 (3)	0.007 (2)	0.003 (2)	−0.002 (2)
C1	0.045 (4)	0.027 (3)	0.019 (3)	0.007 (3)	0.004 (3)	0.006 (3)
C2	0.029 (3)	0.021 (3)	0.024 (3)	−0.001 (3)	0.000 (3)	0.001 (2)
C3	0.033 (3)	0.023 (3)	0.029 (4)	0.010 (3)	−0.003 (3)	−0.002 (3)
C4	0.029 (3)	0.028 (3)	0.032 (4)	0.005 (3)	0.002 (3)	−0.003 (3)
C5	0.053 (5)	0.041 (4)	0.039 (5)	0.022 (4)	0.014 (4)	−0.003 (3)
N3	0.028 (3)	0.017 (2)	0.017 (3)	0.004 (2)	0.0017 (19)	−0.001 (2)
N4	0.030 (3)	0.021 (3)	0.017 (3)	0.002 (2)	−0.001 (2)	−0.002 (2)
C6	0.032 (3)	0.033 (3)	0.033 (4)	0.001 (3)	0.010 (3)	0.000 (3)
C7	0.028 (3)	0.018 (3)	0.030 (4)	0.003 (3)	0.008 (3)	0.002 (3)
C8	0.025 (3)	0.028 (3)	0.036 (4)	0.002 (3)	−0.001 (3)	0.002 (3)
C9	0.033 (4)	0.022 (3)	0.031 (4)	0.002 (3)	−0.009 (3)	0.002 (3)
C10	0.045 (5)	0.044 (4)	0.036 (5)	0.004 (4)	−0.017 (3)	−0.006 (3)
C11	0.024 (3)	0.019 (3)	0.017 (3)	0.003 (2)	0.003 (2)	−0.001 (2)
C12	0.029 (3)	0.018 (3)	0.012 (3)	−0.001 (2)	0.004 (2)	0.001 (2)
C13	0.024 (3)	0.020 (3)	0.018 (3)	0.004 (2)	0.004 (2)	0.001 (2)
C14	0.024 (3)	0.035 (4)	0.016 (3)	0.000 (3)	0.003 (2)	0.001 (3)
C15	0.024 (3)	0.042 (4)	0.022 (4)	0.000 (3)	0.004 (3)	−0.001 (3)
C16	0.022 (3)	0.036 (4)	0.034 (4)	0.001 (3)	0.000 (3)	0.001 (3)
C17	0.023 (3)	0.037 (4)	0.031 (4)	−0.001 (3)	0.008 (3)	0.004 (3)
C18	0.034 (3)	0.027 (3)	0.016 (3)	0.004 (3)	0.007 (3)	0.000 (2)
C19	0.024 (3)	0.017 (3)	0.019 (3)	−0.001 (2)	0.001 (2)	−0.003 (2)
C20	0.036 (4)	0.023 (3)	0.020 (3)	0.002 (3)	−0.001 (3)	0.004 (2)
C21	0.037 (4)	0.023 (3)	0.035 (4)	0.005 (3)	−0.005 (3)	0.005 (3)
C22	0.029 (3)	0.018 (3)	0.043 (4)	0.004 (3)	0.004 (3)	−0.004 (3)
C23	0.027 (3)	0.021 (3)	0.031 (4)	0.000 (2)	0.005 (3)	−0.005 (3)
C24	0.030 (3)	0.020 (3)	0.022 (3)	0.002 (3)	0.004 (3)	0.000 (2)
O4	0.048 (3)	0.055 (3)	0.037 (3)	−0.016 (3)	0.001 (2)	0.017 (3)
C25	0.047 (5)	0.058 (5)	0.035 (5)	−0.001 (4)	−0.001 (4)	0.004 (4)
C26	0.054 (6)	0.046 (4)	0.034 (6)	0.009 (4)	0.002 (4)	0.008 (3)
C27	0.048 (5)	0.043 (4)	0.048 (5)	−0.006 (4)	0.010 (4)	0.003 (4)
C28	0.042 (4)	0.047 (5)	0.040 (5)	0.004 (4)	0.001 (3)	0.008 (4)

Geometric parameters (Å, º)

W1—O3	1.723 (5)	C11—H11	1.0000
W1—O2	1.751 (6)	C12—C13	1.543 (9)
W1—O1	1.911 (4)	C12—C19	1.544 (8)
W1—N2	2.320 (6)	C13—C14	1.393 (9)
W1—N4	2.342 (6)	C13—C18	1.401 (8)
W1—Cl1	2.3572 (18)	C14—C15	1.390 (9)
O1—C12	1.410 (7)	C14—H14	0.9500
N1—C2	1.358 (8)	C15—C16	1.392 (9)
N1—N2	1.380 (7)	C15—H15	0.9500
N1—C11	1.450 (7)	C16—C17	1.372 (10)
N2—C4	1.356 (8)	C16—H16	0.9500
C1—C2	1.481 (9)	C17—C18	1.391 (10)
C1—H1A	0.9800	C17—H17	0.9500
C1—H1B	0.9800	C18—H18	0.9500
C1—H1C	0.9800	C19—C20	1.390 (9)
C2—C3	1.382 (9)	C19—C24	1.402 (8)
C3—C4	1.401 (10)	C20—C21	1.384 (9)
C3—H3	0.9500	C20—H20	0.9500
C4—C5	1.481 (9)	C21—C22	1.389 (10)
C5—H5A	0.9800	C21—H21	0.9500
C5—H5B	0.9800	C22—C23	1.375 (10)
C5—H5C	0.9800	C22—H22	0.9500
N3—N4	1.374 (8)	C23—C24	1.385 (9)
N3—C7	1.376 (8)	C23—H23	0.9500
N3—C11	1.446 (8)	C24—H24	0.9500
N4—C9	1.346 (9)	O4—C25	1.426 (10)
C6—C7	1.491 (10)	O4—C28	1.428 (10)
C6—H6A	0.9800	C25—C26	1.499 (11)
C6—H6B	0.9800	C25—H25A	0.9900
C6—H6C	0.9800	C25—H25B	0.9900
C7—C8	1.369 (10)	C26—C27	1.524 (13)
C8—C9	1.401 (10)	C26—H26A	0.9900
C8—H8	0.9500	C26—H26B	0.9900
C9—C10	1.497 (10)	C27—C28	1.509 (11)
C10—H10A	0.9800	C27—H27A	0.9900
C10—H10B	0.9800	C27—H27B	0.9900
C10—H10C	0.9800	C28—H28A	0.9900
C11—C12	1.559 (8)	C28—H28B	0.9900
O3—W1—O2	103.8 (3)	N1—C11—C12	111.7 (5)
O3—W1—O1	99.1 (2)	N3—C11—H11	108.2
O2—W1—O1	99.5 (3)	N1—C11—H11	108.2
O3—W1—N2	88.5 (2)	C12—C11—H11	108.2
O2—W1—N2	167.7 (2)	O1—C12—C13	109.2 (5)
O1—W1—N2	79.52 (19)	O1—C12—C19	108.8 (5)
O3—W1—N4	165.3 (2)	C13—C12—C19	109.0 (5)
O2—W1—N4	90.9 (2)	O1—C12—C11	108.9 (5)
O1—W1—N4	76.70 (19)	C13—C12—C11	112.3 (5)
N2—W1—N4	76.9 (2)	C19—C12—C11	108.6 (5)
O3—W1—Cl1	96.76 (19)	C14—C13—C18	118.8 (6)
O2—W1—Cl1	95.0 (2)	C14—C13—C12	121.9 (5)
O1—W1—Cl1	155.24 (14)	C18—C13—C12	119.0 (6)
N2—W1—Cl1	82.04 (15)	C15—C14—C13	120.3 (6)
N4—W1—Cl1	83.14 (13)	C15—C14—H14	119.8
C12—O1—W1	137.0 (4)	C13—C14—H14	119.8
C2—N1—N2	112.2 (5)	C14—C15—C16	119.9 (7)
C2—N1—C11	129.6 (5)	C14—C15—H15	120.1
N2—N1—C11	118.3 (5)	C16—C15—H15	120.1
C4—N2—N1	104.9 (5)	C17—C16—C15	120.3 (6)
C4—N2—W1	134.1 (4)	C17—C16—H16	119.8
N1—N2—W1	120.7 (4)	C15—C16—H16	119.8
C2—C1—H1A	109.5	C16—C17—C18	120.0 (6)
C2—C1—H1B	109.5	C16—C17—H17	120.0
H1A—C1—H1B	109.5	C18—C17—H17	120.0
C2—C1—H1C	109.5	C17—C18—C13	120.4 (6)
H1A—C1—H1C	109.5	C17—C18—H18	119.8
H1B—C1—H1C	109.5	C13—C18—H18	119.8
N1—C2—C3	105.9 (6)	C20—C19—C24	118.6 (6)
N1—C2—C1	123.6 (6)	C20—C19—C12	120.1 (5)
C3—C2—C1	130.5 (6)	C24—C19—C12	121.2 (5)
C2—C3—C4	107.2 (6)	C21—C20—C19	120.5 (6)
C2—C3—H3	126.4	C21—C20—H20	119.7
C4—C3—H3	126.4	C19—C20—H20	119.7
N2—C4—C3	109.9 (6)	C20—C21—C22	120.3 (7)
N2—C4—C5	121.9 (7)	C20—C21—H21	119.9
C3—C4—C5	128.2 (6)	C22—C21—H21	119.9
C4—C5—H5A	109.5	C23—C22—C21	119.7 (6)
C4—C5—H5B	109.5	C23—C22—H22	120.1
H5A—C5—H5B	109.5	C21—C22—H22	120.1
C4—C5—H5C	109.5	C22—C23—C24	120.4 (6)
H5A—C5—H5C	109.5	C22—C23—H23	119.8
H5B—C5—H5C	109.5	C24—C23—H23	119.8
N4—N3—C7	111.9 (5)	C23—C24—C19	120.4 (6)
N4—N3—C11	119.5 (5)	C23—C24—H24	119.8
C7—N3—C11	128.6 (5)	C19—C24—H24	119.8
C9—N4—N3	105.3 (6)	C25—O4—C28	110.2 (6)
C9—N4—W1	134.9 (5)	O4—C25—C26	106.2 (7)
N3—N4—W1	119.4 (4)	O4—C25—H25A	110.5
C7—C6—H6A	109.5	C26—C25—H25A	110.5
C7—C6—H6B	109.5	O4—C25—H25B	110.5
H6A—C6—H6B	109.5	C26—C25—H25B	110.5
C7—C6—H6C	109.5	H25A—C25—H25B	108.7
H6A—C6—H6C	109.5	C25—C26—C27	102.4 (7)
H6B—C6—H6C	109.5	C25—C26—H26A	111.3
C8—C7—N3	105.1 (6)	C27—C26—H26A	111.3
C8—C7—C6	131.4 (6)	C25—C26—H26B	111.3
N3—C7—C6	123.4 (6)	C27—C26—H26B	111.3
C7—C8—C9	108.1 (6)	H26A—C26—H26B	109.2
C7—C8—H8	125.9	C28—C27—C26	102.0 (7)
C9—C8—H8	125.9	C28—C27—H27A	111.4
N4—C9—C8	109.6 (6)	C26—C27—H27A	111.4
N4—C9—C10	122.1 (7)	C28—C27—H27B	111.4
C8—C9—C10	128.3 (7)	C26—C27—H27B	111.4
C9—C10—H10A	109.5	H27A—C27—H27B	109.2
C9—C10—H10B	109.5	O4—C28—C27	105.9 (7)
H10A—C10—H10B	109.5	O4—C28—H28A	110.5
C9—C10—H10C	109.5	C27—C28—H28A	110.5
H10A—C10—H10C	109.5	O4—C28—H28B	110.5
H10B—C10—H10C	109.5	C27—C28—H28B	110.5
N3—C11—N1	110.3 (5)	H28A—C28—H28B	108.7
N3—C11—C12	110.3 (5)
C2—N1—N2—C4	−0.2 (7)	W1—O1—C12—C19	−130.9 (5)
C11—N1—N2—C4	−180.0 (5)	W1—O1—C12—C11	−12.7 (8)
C2—N1—N2—W1	173.8 (4)	N3—C11—C12—O1	−56.6 (6)
C11—N1—N2—W1	−5.9 (7)	N1—C11—C12—O1	66.4 (6)
N2—N1—C2—C3	0.1 (8)	N3—C11—C12—C13	−177.7 (5)
C11—N1—C2—C3	179.8 (6)	N1—C11—C12—C13	−54.7 (6)
N2—N1—C2—C1	−179.3 (6)	N3—C11—C12—C19	61.8 (6)
C11—N1—C2—C1	0.4 (11)	N1—C11—C12—C19	−175.3 (5)
N1—C2—C3—C4	0.0 (8)	O1—C12—C13—C14	−172.9 (5)
C1—C2—C3—C4	179.4 (7)	C19—C12—C13—C14	68.4 (7)
N1—N2—C4—C3	0.2 (7)	C11—C12—C13—C14	−51.9 (7)
W1—N2—C4—C3	−172.6 (5)	O1—C12—C13—C18	13.5 (7)
N1—N2—C4—C5	−178.7 (7)	C19—C12—C13—C18	−105.2 (6)
W1—N2—C4—C5	8.5 (11)	C11—C12—C13—C18	134.5 (6)
C2—C3—C4—N2	−0.2 (8)	C18—C13—C14—C15	4.3 (10)
C2—C3—C4—C5	178.6 (8)	C12—C13—C14—C15	−169.3 (6)
C7—N3—N4—C9	0.2 (7)	C13—C14—C15—C16	−1.0 (11)
C11—N3—N4—C9	179.6 (5)	C14—C15—C16—C17	−2.5 (11)
C7—N3—N4—W1	173.9 (4)	C15—C16—C17—C18	2.7 (11)
C11—N3—N4—W1	−6.7 (7)	C16—C17—C18—C13	0.7 (10)
N4—N3—C7—C8	−0.4 (7)	C14—C13—C18—C17	−4.2 (9)
C11—N3—C7—C8	−179.7 (6)	C12—C13—C18—C17	169.6 (6)
N4—N3—C7—C6	176.6 (6)	O1—C12—C19—C20	−9.5 (8)
C11—N3—C7—C6	−2.7 (10)	C13—C12—C19—C20	109.5 (6)
N3—C7—C8—C9	0.5 (7)	C11—C12—C19—C20	−127.9 (6)
C6—C7—C8—C9	−176.2 (7)	O1—C12—C19—C24	172.8 (5)
N3—N4—C9—C8	0.1 (7)	C13—C12—C19—C24	−68.2 (7)
W1—N4—C9—C8	−172.2 (4)	C11—C12—C19—C24	54.4 (8)
N3—N4—C9—C10	179.5 (6)	C24—C19—C20—C21	−0.9 (10)
W1—N4—C9—C10	7.2 (10)	C12—C19—C20—C21	−178.8 (6)
C7—C8—C9—N4	−0.4 (8)	C19—C20—C21—C22	−0.4 (11)
C7—C8—C9—C10	−179.7 (7)	C20—C21—C22—C23	1.9 (11)
N4—N3—C11—N1	−61.5 (7)	C21—C22—C23—C24	−2.0 (10)
C7—N3—C11—N1	117.8 (6)	C22—C23—C24—C19	0.7 (10)
N4—N3—C11—C12	62.4 (6)	C20—C19—C24—C23	0.8 (10)
C7—N3—C11—C12	−118.4 (6)	C12—C19—C24—C23	178.6 (6)
C2—N1—C11—N3	−110.3 (7)	C28—O4—C25—C26	−11.7 (10)
N2—N1—C11—N3	69.3 (7)	O4—C25—C26—C27	29.8 (9)
C2—N1—C11—C12	126.7 (7)	C25—C26—C27—C28	−35.7 (9)
N2—N1—C11—C12	−53.7 (7)	C25—O4—C28—C27	−11.7 (9)
W1—O1—C12—C13	110.3 (6)	C26—C27—C28—O4	29.6 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5C···O3	0.98	2.49	3.325 (10)	143
C10—H10A···O2	0.98	2.54	3.353 (11)	140
C15—H15···O3^i	0.95	2.40	3.174 (9)	139
C6—H6A···O4^ii	0.98	2.68	3.402 (10)	131
C23—H23···O4^i	0.95	2.52	3.289 (8)	138

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