[Bis(3,5-dimethyl­pyrazol-1-yl-κN²)­dithio­acetato-κS](triphenyl­phosphine-κP)copper(I)

In the title compound, [Cu(C₁₂H₁₅N₄S₂)(C₁₈H₁₅P)], the copper(I) center is tetra­hedrally coordinated by one S atom and two N atoms from one bis­(3,5-dimethyl­pyrazol-1-yl)­dithio­acetate ligand and one P atom from a triphenyl­phosphine ligand. In the crystal structure, adjacent pyrazole rings are involved in weak π–π inter­actions, thereby forming a one-dimensional zigzag chain running along the b axis.

S1. Comment

In the past decades, much interest in metal complexes of the tris(pyrazolyl)borate or `scorpionate' ligands (Trofimenko, 1967) has been motivated by their chemistry, their relevance in biological systems (Beck et al., 2001), and their potential applications in advanced materials, such as single-molecule magnets (Li et al., 2006), optoelectronic devices (Enomoto et al., 2001) and catalysts (Noel et al., 2006). Besides these `scorpionate' ligands, several so-called `heteroscopionate' ligands, such as bis(3,5-dimethylpyrazol-1-yl)acetate (bdmpza), 2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide (bdmpze) and bis(3,5-dimethylpyrazol-1-yl)dithioacetate (bdmpzdta), in which one pyrazole group was replaced by a carboxylate, ethoxide group or dithioacetate group, have been reported. A family of transition metal complexes of these `heteroscopionate' ligands have been prepared (Otero et al., 2000, 2002, 2004, 2005; Beck et al., 2001; Hammes et al., 2003; Smith et al., 2002, 2005; Ortiz et al., 2004; Porchia et al., 2006). Among them, only a few examples containing Ti^VI, Zr^IV, Ha^IV, Ru^II, Sc^II and Y^III involve the bdmpzdta ligand. There is no report of a cuprous complex of this ligand.

The title compound, (I), crystallizes in the monoclinic space group P2₁/c and the asymmetric unit contains a discrete [Cu(bdmpzdta)PPh₃] molecule with no crystallographically imposed symmetry. Compound (I) can be viewed as having a scorpionate-shaped structure in which the bdmpzdta ligand is in the tridentate κ³-N,N,S coordination mode (Fig. 1). This coordination resembles that found in [Ti(bdmpzdta)Cl₂{O(CH₂)₄Cl}] (Otero et al., 2002). The Cu center is tetrahedrally coordinated by two N atoms and one S atom from the bdmpzdta ligand and one P atom from the PPh₃ ligand. Tetrahedral Cu^I centers with three different donor atoms are only found in a limited number of complexes, such as [PtCu₂(bpy)₂(tdt)(dppm)₂](ClO₄)₂ [bpy is 2,2'-bipyridine; tdt is 3,4-toluenedithiolate; dppm is bis(diphenylphhosphino); Chen et al., 2004] and [Cu₄(SCN₄Me)₄(PPh₃)₃] [SCN₄Me is 1-methyl-1,2,3,4-tetrazole-5-thilate; Nöth et al., 1998]. The dihedral angle between the two pyrozalate rings in bdmpzdta ligand is 49.83(s.u.?)°. The N—Cu—N and N—Cu—S bond angles range from 88.22 (6) to 94.71 (5)°, and are much smaller than the N—Cu—P and P—Cu—S angles [120.68 (5)–128.91 (2)°]. Such a difference may be due to the steric hindrance between the bdmpzdta and PPh₃ ligands. ##AUTHOR: Is this steric hindrance alone, or the typical bite angles of the bdmpzdta?

As indicated in Table 1, the mean Cu—N bond distance in (I) is longer than those in [Cu(tdmpzb)PPh₃], [Cu(tdphpzb)Cl] and [Cu(tdippzb)Cl]. The Cu—P bond length in (I) is longer than those observed in [Cu(tdmpzb)PPh₃] and [Cu(Tpms)PPh₃] but shorter than that in [Cu(PPh₃)₂PhCOS], while the Cu—S bond length in (I) is comparable to that found in [Cu(C₆H₁₁CN)₂(dmpzdtc)]. The average C—S bond length of (I) is comparable to that observed in [Li(THF)₄][ScCl₃(bdmpzdta)] but much shorter than that in [Ti(bdmpzdta)₂Cl₂], which may be ascribed to the different coordination mode of the CS₂ group in the latter complex.

In the crystal structure of (I), two pyrazolyl rings of neighbouring molecules are stacked in a face-to-face fashion with a separation of 3.744 (s.u.?) Å between the centroids of the two pyrazolate rings A and A^{i [}symmetry code: (i) −x + 1, y − 1/2, −z + 1/2], indicating a weak intermolecular π–π interaction (Janiak, 2000; Tong et al., 1999). These π–π interactions result in the formation of a one-dimensional zigzag chain running along the b axis (Fig. 2).

Related literature

For related literature, see: Beck et al. (2001); Chen et al. (2004); Enomoto et al. (2001); Hammes et al. (2003); Janiak (2000); Li et al. (2006); Nöth et al. (1998); Noel et al. (2006); Ortiz et al. (2004); Otero et al. (2000, 2002, 2004, 2005); Porchia et al. (2006); Smith et al. (2002, 2005); Tong et al. (1999); Trofimenko (1967).

S2. Experimental

To a solution of Cu(PPh₃)Cl (0.181 g, 0.5 mmol) in CH₂Cl₂ (5 ml) was added a solution of [Li(bdmpzdta)(H₂O)]₄ (0.606 g, 0.5 mmol) in MeCN (10 ml) (Otero et al., 2002). The resulting red solution was stirred at room temperature for ten hours and then filtered. Diethyl ether was allowed to diffuse into the filtrate over a period of several days, forming red plates of (I), which were collected by filtration, washed with Et₂O and dried in vacuo (yield 0.527 g, 87% based on Cu). The crystal used for the crystal structure determination was obtained directly from the above preparation. Analysis found: C 59.39, H 5.08, N 9.11%; calculated for C₃₀H₃₀CuN₄PS₂: C 59.53, H 5.00, N 9.26%.

S3. Refinement

Methyl H atoms were constrained to an ideal geometry [C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C)] but were allowed to rotate freely about the parent C—C bonds. All other H atoms were placed in geometrically idealized positions (C—H = 1.0 Å for methine groups and C—H = 0.95 Å for aromatic groups) and constrained to ride on their parent atoms [U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ##AUTHOR - please supply a valid reference; software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. A view of the molecule of complex (I), with displacement ellipsoids drawn at the 30% probability level. H atoms are drawn as spheres of arbitrary radii.
	Fig. 2. The packing of (I), viewed approximately down the a axis, showing the one-dimensional chain generated by π–π interactions. H atoms have been omitted for clarity.

[Bis(3,5-dimethylpyrazol-1-yl-κN²)dithioacetato-κS](triphenylphosphine- κP)copper(I)

Crystal data

[Cu(C12H15N4S2)(C18H15P)]	F(000) = 1256
Mr = 605.24	Dx = 1.365 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 26898 reflections
a = 13.051 (3) Å	θ = 3.0–25.3°
b = 14.256 (3) Å	µ = 0.96 mm^−1
c = 17.100 (3) Å	T = 193 K
β = 112.19 (3)°	Block, red
V = 2945.9 (12) Å^3	0.46 × 0.45 × 0.20 mm
Z = 4

Data collection

Rigaku Mercury diffractometer	6583 independent reflections
Radiation source: fine-focus sealed tube	5364 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (Jacobson, 1998)	h = −16→16
Tmin = 0.666, Tmax = 0.831	k = −18→15
26346 measured reflections	l = −22→21

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0478P)^2 + 0.3127P] where P = (Fo^2 + 2Fc^2)/3
6583 reflections	(Δ/σ)max = 0.001
347 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.34 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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.661659 (18)	0.332640 (14)	0.228606 (12)	0.04044 (8)
P1	0.81652 (4)	0.30604 (3)	0.21163 (3)	0.03676 (11)
S1	0.48239 (4)	0.33890 (4)	0.12713 (3)	0.05269 (13)
S2	0.27265 (4)	0.34758 (4)	0.15807 (4)	0.06221 (15)
N1	0.52769 (12)	0.28636 (12)	0.32650 (9)	0.0490 (4)
N2	0.61854 (13)	0.25412 (10)	0.31415 (9)	0.0452 (3)
N3	0.63721 (12)	0.45354 (10)	0.28825 (9)	0.0438 (3)
N4	0.54426 (12)	0.45162 (11)	0.30576 (9)	0.0458 (3)
C1	0.3956 (2)	0.2420 (3)	0.39433 (19)	0.1152 (13)
H1A	0.4040	0.3023	0.4235	0.173*
H1B	0.3890	0.1917	0.4313	0.173*
H1C	0.3289	0.2433	0.3425	0.173*
C2	0.49394 (18)	0.22453 (19)	0.37266 (12)	0.0681 (6)
C3	0.5680 (2)	0.15238 (17)	0.39168 (14)	0.0720 (7)
H3	0.5676	0.0982	0.4239	0.086*
C4	0.64410 (18)	0.17290 (13)	0.35516 (12)	0.0536 (5)
C5	0.7444 (2)	0.11962 (15)	0.36042 (16)	0.0747 (7)
H5A	0.7666	0.1385	0.3140	0.112*
H5B	0.7281	0.0523	0.3563	0.112*
H5C	0.8047	0.1329	0.4145	0.112*
C6	0.47091 (15)	0.37105 (14)	0.28411 (11)	0.0469 (4)
H6	0.4126	0.3842	0.3073	0.056*
C7	0.40933 (15)	0.35394 (12)	0.18899 (11)	0.0456 (4)
C8	0.4349 (2)	0.5525 (2)	0.36694 (18)	0.0877 (8)
H8A	0.4362	0.6182	0.3842	0.132*
H8B	0.4409	0.5115	0.4145	0.132*
H8C	0.3654	0.5396	0.3195	0.132*
C9	0.52949 (17)	0.53462 (15)	0.34075 (11)	0.0545 (5)
C10	0.61681 (19)	0.58988 (14)	0.34580 (12)	0.0586 (5)
H10	0.6306	0.6520	0.3674	0.070*
C11	0.68200 (17)	0.53806 (12)	0.31335 (11)	0.0505 (4)
C12	0.7879 (2)	0.56582 (16)	0.30592 (16)	0.0715 (6)
H12A	0.8497	0.5514	0.3588	0.107*
H12B	0.7868	0.6333	0.2946	0.107*
H12C	0.7968	0.5311	0.2594	0.107*
C13	0.82232 (14)	0.19913 (12)	0.15376 (10)	0.0401 (4)
C14	0.87552 (18)	0.11736 (13)	0.19136 (12)	0.0567 (5)
H14	0.9181	0.1161	0.2503	0.068*
C15	0.8669 (2)	0.03714 (15)	0.14313 (15)	0.0729 (7)
H15	0.9036	−0.0187	0.1694	0.088*
C16	0.8060 (2)	0.03781 (16)	0.05811 (14)	0.0699 (6)
H16	0.8010	−0.0171	0.0255	0.084*
C17	0.75217 (19)	0.11817 (15)	0.02023 (13)	0.0622 (5)
H17	0.7089	0.1187	−0.0386	0.075*
C18	0.76095 (17)	0.19816 (14)	0.06760 (11)	0.0507 (4)
H18	0.7242	0.2537	0.0407	0.061*
C19	0.93461 (15)	0.30006 (12)	0.31230 (10)	0.0434 (4)
C20	0.91477 (19)	0.32976 (14)	0.38303 (12)	0.0562 (5)
H20	0.8428	0.3504	0.3767	0.067*
C21	0.9985 (2)	0.32953 (17)	0.46235 (14)	0.0739 (7)
H21	0.9836	0.3500	0.5099	0.089*
C22	1.1014 (2)	0.30030 (17)	0.47265 (15)	0.0716 (6)
H22	1.1587	0.3006	0.5272	0.086*
C23	1.12298 (18)	0.27049 (16)	0.40497 (16)	0.0712 (6)
H23	1.1953	0.2496	0.4128	0.085*
C24	1.03961 (17)	0.27017 (15)	0.32342 (13)	0.0575 (5)
H24	1.0556	0.2495	0.2764	0.069*
C25	0.85227 (15)	0.39664 (11)	0.15047 (10)	0.0417 (4)
C26	0.76887 (18)	0.45745 (13)	0.10272 (12)	0.0527 (5)
H26	0.6966	0.4516	0.1033	0.063*
C27	0.7912 (2)	0.52715 (14)	0.05394 (13)	0.0654 (6)
H27	0.7335	0.5673	0.0199	0.078*
C28	0.8956 (2)	0.53775 (14)	0.05492 (13)	0.0647 (6)
H28	0.9107	0.5866	0.0230	0.078*
C29	0.9793 (2)	0.47781 (16)	0.10200 (13)	0.0646 (6)
H29	1.0518	0.4849	0.1022	0.077*
C30	0.95669 (17)	0.40740 (14)	0.14883 (12)	0.0553 (5)
H30	1.0141	0.3656	0.1805	0.066*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03961 (14)	0.03856 (13)	0.04503 (13)	0.00176 (8)	0.01813 (9)	−0.00005 (7)
P1	0.0385 (3)	0.0343 (2)	0.0382 (2)	0.00305 (16)	0.01534 (17)	0.00310 (15)
S1	0.0493 (3)	0.0625 (3)	0.0388 (2)	−0.0003 (2)	0.00820 (19)	−0.00403 (18)
S2	0.0357 (3)	0.0627 (3)	0.0721 (3)	−0.0006 (2)	0.0022 (2)	−0.0002 (2)
N1	0.0390 (9)	0.0641 (10)	0.0430 (8)	−0.0052 (7)	0.0145 (6)	0.0069 (7)
N2	0.0461 (9)	0.0439 (8)	0.0473 (8)	0.0008 (6)	0.0194 (6)	0.0070 (6)
N3	0.0405 (9)	0.0406 (8)	0.0486 (8)	0.0000 (6)	0.0150 (6)	−0.0074 (6)
N4	0.0382 (9)	0.0494 (9)	0.0463 (8)	0.0036 (6)	0.0120 (6)	−0.0108 (6)
C1	0.0675 (19)	0.195 (4)	0.095 (2)	0.004 (2)	0.0449 (16)	0.063 (2)
C2	0.0463 (13)	0.1050 (18)	0.0494 (11)	−0.0135 (12)	0.0141 (9)	0.0246 (11)
C3	0.0643 (16)	0.0822 (16)	0.0613 (13)	−0.0154 (12)	0.0142 (11)	0.0308 (11)
C4	0.0600 (13)	0.0457 (11)	0.0471 (10)	−0.0072 (8)	0.0112 (9)	0.0094 (7)
C5	0.0940 (19)	0.0472 (12)	0.0828 (15)	0.0155 (12)	0.0333 (13)	0.0210 (10)
C6	0.0342 (10)	0.0594 (11)	0.0456 (9)	0.0007 (8)	0.0135 (7)	−0.0033 (7)
C7	0.0408 (11)	0.0382 (9)	0.0492 (10)	0.0007 (7)	0.0074 (7)	0.0005 (7)
C8	0.0695 (18)	0.101 (2)	0.0952 (18)	0.0248 (15)	0.0340 (14)	−0.0268 (15)
C9	0.0508 (12)	0.0585 (12)	0.0483 (10)	0.0194 (9)	0.0121 (8)	−0.0089 (8)
C10	0.0661 (14)	0.0413 (10)	0.0594 (11)	0.0087 (9)	0.0135 (9)	−0.0113 (8)
C11	0.0591 (13)	0.0355 (9)	0.0513 (10)	−0.0003 (8)	0.0143 (8)	−0.0052 (7)
C12	0.0749 (17)	0.0516 (13)	0.0925 (16)	−0.0210 (11)	0.0370 (13)	−0.0172 (11)
C13	0.0424 (10)	0.0376 (9)	0.0432 (9)	0.0016 (7)	0.0194 (7)	0.0009 (6)
C14	0.0690 (14)	0.0448 (11)	0.0505 (10)	0.0119 (9)	0.0160 (9)	0.0023 (8)
C15	0.0938 (19)	0.0438 (12)	0.0741 (14)	0.0193 (11)	0.0238 (13)	−0.0007 (9)
C16	0.0880 (18)	0.0523 (13)	0.0695 (14)	0.0054 (11)	0.0297 (12)	−0.0177 (10)
C17	0.0740 (16)	0.0618 (13)	0.0484 (11)	−0.0014 (11)	0.0203 (10)	−0.0085 (9)
C18	0.0572 (13)	0.0463 (10)	0.0455 (9)	0.0055 (8)	0.0160 (8)	0.0023 (7)
C19	0.0404 (10)	0.0395 (9)	0.0448 (9)	−0.0003 (7)	0.0100 (7)	0.0056 (6)
C20	0.0532 (13)	0.0640 (13)	0.0448 (10)	0.0041 (9)	0.0110 (8)	−0.0026 (8)
C21	0.0747 (18)	0.0831 (17)	0.0488 (12)	0.0025 (12)	0.0062 (11)	−0.0046 (10)
C22	0.0680 (17)	0.0644 (14)	0.0601 (13)	−0.0057 (11)	−0.0012 (11)	0.0083 (10)
C23	0.0401 (12)	0.0593 (13)	0.0997 (17)	0.0062 (10)	0.0098 (11)	0.0250 (12)
C24	0.0481 (12)	0.0570 (12)	0.0665 (12)	0.0051 (9)	0.0206 (9)	0.0125 (9)
C25	0.0514 (11)	0.0347 (8)	0.0402 (8)	0.0000 (7)	0.0186 (7)	0.0013 (6)
C26	0.0628 (13)	0.0438 (10)	0.0552 (10)	0.0092 (9)	0.0266 (9)	0.0078 (8)
C27	0.0974 (19)	0.0427 (11)	0.0611 (12)	0.0152 (11)	0.0357 (12)	0.0135 (8)
C28	0.103 (2)	0.0435 (11)	0.0615 (12)	−0.0091 (11)	0.0466 (12)	0.0019 (9)
C29	0.0714 (16)	0.0680 (14)	0.0639 (12)	−0.0153 (11)	0.0364 (11)	0.0026 (10)
C30	0.0546 (13)	0.0581 (12)	0.0563 (11)	−0.0017 (9)	0.0242 (9)	0.0095 (8)

Geometric parameters (Å, º)

Cu1—N2	2.0812 (14)	C11—C12	1.488 (3)
Cu1—N3	2.0877 (14)	C12—H12A	0.9800
Cu1—P1	2.1809 (7)	C12—H12B	0.9800
Cu1—S1	2.3295 (11)	C12—H12C	0.9800
P1—C19	1.8281 (18)	C13—C14	1.385 (3)
P1—C25	1.8297 (17)	C13—C18	1.386 (2)
P1—C13	1.8343 (17)	C14—C15	1.389 (3)
S1—C7	1.684 (2)	C14—H14	0.9500
S2—C7	1.661 (2)	C15—C16	1.369 (3)
N1—N2	1.360 (2)	C15—H15	0.9500
N1—C2	1.363 (2)	C16—C17	1.372 (3)
N1—C6	1.458 (2)	C16—H16	0.9500
N2—C4	1.329 (2)	C17—C18	1.378 (3)
N3—C11	1.337 (2)	C17—H17	0.9500
N3—N4	1.355 (2)	C18—H18	0.9500
N4—C9	1.372 (2)	C19—C24	1.378 (3)
N4—C6	1.451 (2)	C19—C20	1.395 (3)
C1—C2	1.485 (3)	C20—C21	1.384 (3)
C1—H1A	0.9800	C20—H20	0.9500
C1—H1B	0.9800	C21—C22	1.353 (4)
C1—H1C	0.9800	C21—H21	0.9500
C2—C3	1.364 (3)	C22—C23	1.358 (4)
C3—C4	1.390 (3)	C22—H22	0.9500
C3—H3	0.9500	C23—C24	1.408 (3)
C4—C5	1.487 (3)	C23—H23	0.9500
C5—H5A	0.9800	C24—H24	0.9500
C5—H5B	0.9800	C25—C30	1.382 (3)
C5—H5C	0.9800	C25—C26	1.390 (3)
C6—C7	1.537 (2)	C26—C27	1.397 (3)
C6—H6	1.0000	C26—H26	0.9500
C8—C9	1.485 (3)	C27—C28	1.364 (3)
C8—H8A	0.9800	C27—H27	0.9500
C8—H8B	0.9800	C28—C29	1.382 (3)
C8—H8C	0.9800	C28—H28	0.9500
C9—C10	1.361 (3)	C29—C30	1.384 (3)
C10—C11	1.391 (3)	C29—H29	0.9500
C10—H10	0.9500	C30—H30	0.9500
N2—Cu1—N3	88.22 (6)	C9—C10—H10	126.5
N2—Cu1—P1	120.68 (5)	C11—C10—H10	126.5
N3—Cu1—P1	121.93 (5)	N3—C11—C10	110.34 (19)
N2—Cu1—S1	94.71 (5)	N3—C11—C12	121.31 (18)
N3—Cu1—S1	92.09 (4)	C10—C11—C12	128.34 (18)
P1—Cu1—S1	128.91 (2)	C11—C12—H12A	109.5
C19—P1—C25	105.36 (8)	C11—C12—H12B	109.5
C19—P1—C13	106.10 (8)	H12A—C12—H12B	109.5
C25—P1—C13	101.93 (7)	C11—C12—H12C	109.5
C19—P1—Cu1	112.14 (6)	H12A—C12—H12C	109.5
C25—P1—Cu1	113.74 (6)	H12B—C12—H12C	109.5
C13—P1—Cu1	116.45 (6)	C14—C13—C18	118.19 (16)
C7—S1—Cu1	100.64 (7)	C14—C13—P1	124.38 (14)
N2—N1—C2	111.27 (17)	C18—C13—P1	117.17 (13)
N2—N1—C6	120.77 (14)	C13—C14—C15	120.22 (18)
C2—N1—C6	127.50 (17)	C13—C14—H14	119.9
C4—N2—N1	105.80 (15)	C15—C14—H14	119.9
C4—N2—Cu1	139.34 (14)	C16—C15—C14	120.6 (2)
N1—N2—Cu1	114.22 (11)	C16—C15—H15	119.7
C11—N3—N4	105.46 (15)	C14—C15—H15	119.7
C11—N3—Cu1	140.52 (14)	C15—C16—C17	119.73 (19)
N4—N3—Cu1	113.95 (10)	C15—C16—H16	120.1
N3—N4—C9	111.34 (16)	C17—C16—H16	120.1
N3—N4—C6	121.27 (14)	C16—C17—C18	119.96 (19)
C9—N4—C6	127.31 (17)	C16—C17—H17	120.0
C2—C1—H1A	109.5	C18—C17—H17	120.0
C2—C1—H1B	109.5	C17—C18—C13	121.29 (18)
H1A—C1—H1B	109.5	C17—C18—H18	119.4
C2—C1—H1C	109.5	C13—C18—H18	119.4
H1A—C1—H1C	109.5	C24—C19—C20	118.34 (17)
H1B—C1—H1C	109.5	C24—C19—P1	125.82 (15)
N1—C2—C3	105.72 (19)	C20—C19—P1	115.84 (14)
N1—C2—C1	122.4 (2)	C21—C20—C19	120.9 (2)
C3—C2—C1	131.9 (2)	C21—C20—H20	119.6
C2—C3—C4	107.25 (18)	C19—C20—H20	119.6
C2—C3—H3	126.4	C22—C21—C20	120.4 (2)
C4—C3—H3	126.4	C22—C21—H21	119.8
N2—C4—C3	109.9 (2)	C20—C21—H21	119.8
N2—C4—C5	121.11 (19)	C21—C22—C23	120.0 (2)
C3—C4—C5	128.91 (19)	C21—C22—H22	120.0
C4—C5—H5A	109.5	C23—C22—H22	120.0
C4—C5—H5B	109.5	C22—C23—C24	120.9 (2)
H5A—C5—H5B	109.5	C22—C23—H23	119.5
C4—C5—H5C	109.5	C24—C23—H23	119.5
H5A—C5—H5C	109.5	C19—C24—C23	119.5 (2)
H5B—C5—H5C	109.5	C19—C24—H24	120.3
N4—C6—N1	111.48 (14)	C23—C24—H24	120.3
N4—C6—C7	115.23 (15)	C30—C25—C26	118.57 (17)
N1—C6—C7	111.04 (15)	C30—C25—P1	123.79 (14)
N4—C6—H6	106.1	C26—C25—P1	117.64 (14)
N1—C6—H6	106.1	C25—C26—C27	120.0 (2)
C7—C6—H6	106.1	C25—C26—H26	120.0
C6—C7—S2	114.52 (14)	C27—C26—H26	120.0
C6—C7—S1	119.41 (14)	C28—C27—C26	120.3 (2)
S2—C7—S1	126.01 (11)	C28—C27—H27	119.9
C9—C8—H8A	109.5	C26—C27—H27	119.9
C9—C8—H8B	109.5	C27—C28—C29	120.35 (19)
H8A—C8—H8B	109.5	C27—C28—H28	119.8
C9—C8—H8C	109.5	C29—C28—H28	119.8
H8A—C8—H8C	109.5	C28—C29—C30	119.4 (2)
H8B—C8—H8C	109.5	C28—C29—H29	120.3
C10—C9—N4	105.94 (17)	C30—C29—H29	120.3
C10—C9—C8	130.7 (2)	C25—C30—C29	121.3 (2)
N4—C9—C8	123.3 (2)	C25—C30—H30	119.3
C9—C10—C11	106.91 (17)	C29—C30—H30	119.3