Phenanthroline complexes of zinc and calcium carbamates

Bis(N,N-di-n-butyl­di­thio­carbamato-κ²S,S′)(1,10-phenanthroline-κ²N,N′)­zinc(II) ethanol hemisolvate, [Zn(C₉H₁₈NS₂)₂(C₁₂H₈N₂)]·0.5C₂H₆O, (I), and bis(N,N-di-n-hexyldithiocarbamato-κ²S,S′)­bis(1,10-phenanthroline-κ²N,N′)calcium(II), [Ca(C₁₃H₂₆NS₂)₂(C₁₂H₈N₂)₂], (II), are mixed-ligand com­plexes. In the first compound, the Zn atom has a distorted octahedral coordination, while in the second compound, the Ca atom is eight-coordinate, with four S and four N atoms forming a highly distorted cube.

S1. Comment

During an investigation of the antioxidant properties of metal dithiocarbamate additives (Becker & Knorr, 1996; Becker et al., 1996) in vegetable oils for technical applications, a series of model compounds has been prepared. The crystal structures of zinc dithiocarbamates designed for improved activity (Reck & Becker, 2003a) and of oxidized derivatives believed to play a role as intermediates in the antioxidant action of zinc dithiocarbamates (Reck et al., 1995; Reck & Becker, 2003b) have already been published. Against this background, we present here the crystal structures of the two title complexes, (I) and (II). \sch

While calcium dithiocarbamates themselves were seen to be unstable, the 1,10-phenanthroline complex of calcium dihexyldithiocarbamate, (II), is stable and displays a rare eight-coordination, with four N atoms of two phenanthroline ligands and four S atoms of two dihexyldithiocarbamate ligands. These eight atoms form a highly distorted cube. The average Ca—N and Ca—S distances are 2.59 (3) and 2.96 (6) Å, respectively. The bite distances of the phenanthroline and dithiocarbamate ligands are N1.·N14 2.723 (5), N15.·N28 2.721 (5), S29.·S30 2.949 (3) and S31.·S32 2.948 (3) Å.

In contrast with (II), the zinc dithiocarbamate forms a complex, (I), with only one 1,10-phenanthroline ligand. Two N atoms of the phenanthroline ligand and four S atoms of two dibutyldithiocarbamate molecules form a distorted octahedron. The coordinative bonds in (I) are significantly shorter than the corresponding bonds in (II). The average Zn—N and Zn—S distances are 2.23 (7) and 2.51 (6) Å, respectively. The bite distances of the ligands in (I) are N1.·N14 2.671 (5), S15.·S16 2.929 (3) and S17.·S18 2.902 (3) Å.

The phenanthroline ligands in (I) and (II) are almost planar; the corresponding r.m.s. deviations are 0.035, 0.039 and 0.029 Å, respectively. The dihedral angle between both symmetry-independent phenanthroline molecules in (II) is 78.84 (4)°.

In (I) as well as in (II) there are π–π interactions between symmetry-related phenanthroline ligands. These interactions are defined by the distances between the ring centroids (DC), the distances between the planes through the rings (DP) and the shifts (SH). For compound (I), the numerical values of these parameters are as follows. For ring C5—C10 and ring C9—C13/N14 at (1 − x, −y, 2 − z), DC = 3.632 (4), DP = 3.270 (16) and SH = 1.580 (35) Å. For ring C9—C13/N14 and ring C9—C13/N14 at (1 − x, −y, 2 − z), DC = 3.682 (3), DP = 3.371 (17) and SH = 1.480 (39) Å. For compound (II), these parameters are as follows. For ring C5—C10 and ring C9—C13/N14 at (2 − x, 1 − y, −z), DC = 3.773 (4), DP = 3.719 (15) and SH = 0.634 (92) Å. For ring C19—C24 and ring C23—C27/N28 at (1 − x, −y, −z), DC = 3.744 (3), DP = 3.668 (5) and SH = 0.746 (29) Å.

The crystal structure of (I) contains half an ethanol molecule per complex molecule. The butyl groups in (I) and the hexyl groups in (II) show high displacement parameters, indicating weak hydrophobic interactions between the complex molecules.

S2. Experimental

For the preparation of (I), a stirred solution of zinc di-n-butyl dithiocarbamate in ethanol was treated with a solution of 1,10-phenanthroline (2.2 mole equivalent) in ethanol at ambient temperature. After addition of water, a yellow precipitate was collected, which was recrystallized from ethanol/water (Ratio?). Yellow crystals of (I) were obtained (m.p. 461–462 K). Spectroscopic analysis: IR (ν, cm⁻¹): 3050, 2970, 2925, 2860, 1625, 1595, 1570, 1515, 1500, 1470, 1465, 1425, 1405, 1370, 1355, 1350, 1305, 1300, 1290, 1255, 1240, 1255, 1210, 1195, 1180, 1140, 1105, 1090, 1045, 990, 955, 865, 850, 775, 740, 730, 720. For the preparation of (II), di-n-hexylamine (1.0 mole equivalent) and carbon disulfide (1.2 mole equivalent) were added to a stirred aqueous solution of sodium hydroxide (1.1 mole equivalent). The mixture was kept at 273 K for 30 min and then allowed to reach ambient temperature. An aqueous solution of calcium chloride (0.7 mole equivalent) was then added, followed by the addition of a solution of 1,10-phenanthroline (2.2 mole equivalent). The yellow precipitate was recrystallized from ethanol/water (Ratio?). Yellow crystals of (II) were obtained (m.p. 441 K). Spectroscopic analysis: IR (ν, cm⁻¹): 3010, 2940, 2910, 2850, 1610, 1580, 1575, 1565, 1505, 1465, 1415, 1405, 1360, 1250, 1240, 1205, 1175, 1130, 1100, 1085, 980, 950, 940, 925, 885, 845, 830, 800, 725, 720, 690.

S3. Refinement

The crystal structure of (I) contains one ethanol molecule per unit cell. Because of the very short distances between the centres of symmetry-related molecules, all ethanol atoms were given the occupation factor 0.5. H atoms of (I) and (II) were positioned corresponding to their geometrical conditions and refined using the riding model. The hydroxyl H atom of the ethanol molecule in (I) could not be located.

Computing details

For both compounds, data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Sheldrick, 1999); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I) (top) and (II) (bottom), showing 30% probability displacement ellipsoids. The ethanol molecule in (I) and all H atoms have been omitted for clarity.

(I) Bis(N,N-di-n-butyldithiocarbamato-κ²S,S')(1,10-phenanthroline- κ²N,N')zinc(II) ethanol hemisolvate

Crystal data

[Zn(C9H18NS2)2(C12H8N2)]·0.5C2H6O	Z = 2
Mr = 677.34	F(000) = 718
Triclinic, P1	Dx = 1.242 Mg m^−3
a = 10.006 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.347 (2) Å	Cell parameters from 25 reflections
c = 15.531 (2) Å	θ = 12–20°
α = 103.71 (1)°	µ = 0.94 mm^−1
β = 102.78 (2)°	T = 293 K
γ = 108.37 (2)°	Prismatic, yellow
V = 1811.2 (8) Å^3	0.32 × 0.29 × 0.28 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 1.7°
Graphite monochromator	h = −11→11
2θ/ω scans	k = −15→15
6383 measured reflections	l = 0→18
6383 independent reflections	3 standard reflections every 120 min
5232 reflections with I > 2σ(I)	intensity decay: 0.4%

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
6383 reflections	(Δ/σ)max = 0.010
379 parameters	Δρmax = 0.79 e Å^−3
2 restraints	Δρmin = −0.28 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)
Zn	0.20315 (3)	0.11471 (2)	0.837087 (19)	0.05226 (15)
S15	0.38292 (8)	0.29624 (6)	0.95480 (5)	0.05837 (19)
S16	0.09494 (8)	0.16306 (6)	0.96457 (5)	0.0637 (2)
S17	0.08974 (10)	0.16938 (9)	0.70791 (7)	0.0863 (3)
S18	−0.03409 (11)	−0.05297 (8)	0.71985 (6)	0.0808 (3)
N1	0.3993 (3)	0.1113 (2)	0.78585 (16)	0.0585 (5)
N14	0.2711 (2)	−0.00980 (17)	0.88136 (15)	0.0518 (5)
C2	0.4662 (4)	0.1763 (3)	0.7416 (2)	0.0722 (7)
H1	0.4252	0.2245	0.7232	0.087*
C3	0.5946 (5)	0.1745 (4)	0.7224 (3)	0.0891 (10)
H2	0.6375	0.2206	0.6912	0.107*
C4	0.6588 (4)	0.1049 (3)	0.7493 (3)	0.0822 (9)
H3	0.7458	0.1042	0.7377	0.099*
C5	0.5893 (3)	0.0349 (3)	0.7946 (2)	0.0675 (7)
C6	0.4622 (3)	0.0439 (2)	0.81222 (18)	0.0578 (6)
C7	0.6419 (4)	−0.0443 (3)	0.8229 (2)	0.0765 (8)
H4	0.7265	−0.0503	0.8109	0.092*
C8	0.5733 (4)	−0.1094 (3)	0.8659 (2)	0.0684 (7)
H5	0.6098	−0.1604	0.8828	0.082*
C9	0.4449 (3)	−0.1012 (2)	0.88596 (19)	0.0564 (6)
C10	0.3895 (3)	−0.0254 (2)	0.85984 (16)	0.0506 (5)
C11	0.3687 (3)	−0.1662 (2)	0.9326 (2)	0.0648 (7)
H6	0.3995	−0.2200	0.9488	0.078*
C12	0.2489 (3)	−0.1507 (2)	0.9544 (2)	0.0657 (7)
H7	0.1989	−0.1922	0.9862	0.079*
C13	0.2051 (3)	−0.0696 (2)	0.9268 (2)	0.0587 (6)
H8	0.1249	−0.0580	0.9417	0.070*
C19	0.2559 (3)	0.2825 (2)	1.0139 (2)	0.0574 (6)
C21	−0.0386 (3)	0.0370 (3)	0.6598 (2)	0.0666 (7)
N20	0.2809 (3)	0.3577 (2)	1.09434 (19)	0.0794 (8)
C23	0.4155 (5)	0.4587 (4)	1.1339 (3)	0.0903 (10)
H9	0.3953	0.5201	1.1681	0.108*
H10	0.4499	0.4784	1.0842	0.108*
C24	0.5349 (6)	0.4389 (4)	1.1997 (4)	0.1066 (14)
H11	0.4935	0.4041	1.2411	0.128*
H12	0.5702	0.3890	1.1636	0.128*
C25	0.6632 (7)	0.5497 (5)	1.2567 (4)	0.1314 (19)
H13	0.6267	0.6020	1.2885	0.158*
H14	0.7106	0.5814	1.2158	0.158*
C26	0.7719 (6)	0.5309 (5)	1.3261 (4)	0.1173 (15)
H15	0.8096	0.4807	1.2941	0.141*
H16	0.7241	0.4989	1.3659	0.141*
H17	0.8526	0.6010	1.3632	0.141*
C27	0.1589 (6)	0.3612 (4)	1.1349 (3)	0.1045 (13)
H18	0.1547	0.4347	1.1464	0.125*
H19	0.0640	0.3064	1.0910	0.125*
C28	0.1886 (7)	0.3363 (5)	1.2247 (5)	0.1249 (17)
H20	0.2846	0.3900	1.2680	0.150*
H21	0.1903	0.2621	1.2129	0.150*
C29	0.0689 (8)	0.3427 (6)	1.2664 (4)	0.148 (2)
H22	−0.0124	0.3463	1.2214	0.177*
H23	0.0305	0.2772	1.2843	0.177*
C30	0.1373 (6)	0.4466 (5)	1.3509 (4)	0.1218 (17)
H24	0.1905	0.5089	1.3345	0.146*
H25	0.2047	0.4365	1.3994	0.146*
H26	0.0604	0.4609	1.3728	0.146*
N22	−0.1441 (3)	0.0058 (3)	0.5771 (2)	0.0932 (10)
C31	−0.1295 (6)	0.0702 (5)	0.5153 (4)	0.1185 (16)
H27	−0.1764	0.0211	0.4508	0.142*
H28	−0.0253	0.1105	0.5247	0.142*
C32	−0.2035 (7)	0.1515 (5)	0.5360 (5)	0.1236 (17)
H29	−0.1695	0.1917	0.6026	0.148*
H30	−0.3106	0.1121	0.5154	0.148*
C33	−0.1598 (7)	0.2338 (5)	0.4817 (4)	0.1269 (18)
H31	−0.1810	0.2993	0.5052	0.152*
H32	−0.0543	0.2581	0.4899	0.152*
C34	−0.2471 (8)	0.1752 (5)	0.3810 (4)	0.1304 (18)
H33	−0.1817	0.1637	0.3463	0.156*
H34	−0.2955	0.2199	0.3582	0.156*
H35	−0.3204	0.1042	0.3734	0.156*
C35	−0.2319 (8)	−0.1154 (6)	0.5254 (5)	0.144 (2)
H36	−0.2435	−0.1316	0.4593	0.173*
H37	−0.1824	−0.1598	0.5493	0.173*
C36	−0.3760 (11)	−0.1407 (8)	0.5397 (7)	0.177 (3)
H38	−0.4268	−0.0979	0.5145	0.212*
H39	−0.3647	−0.1234	0.6059	0.212*
C37	−0.4652 (9)	−0.2696 (9)	0.4863 (6)	0.186 (4)
H40	−0.5697	−0.2848	0.4595	0.224*
H41	−0.4281	−0.2942	0.4359	0.224*
C38	−0.4469 (10)	−0.3297 (7)	0.5528 (7)	0.183 (3)
H42	−0.3662	−0.3533	0.5502	0.219*
H43	−0.5369	−0.3941	0.5368	0.219*
H44	−0.4257	−0.2812	0.6149	0.219*
O1E	−0.0939 (10)	0.4038 (5)	0.9465 (5)	0.121 (3)	0.50
C1E	0.0417 (15)	0.4221 (13)	0.9234 (10)	0.201 (8)	0.50
H45	0.0141	0.4052	0.8561	0.241*	0.50
H46	0.0763	0.3655	0.9368	0.241*	0.50
C2E	0.1751 (14)	0.5317 (11)	0.9656 (11)	0.149 (5)	0.50
H47	0.2201	0.5455	0.9188	0.179*	0.50
H48	0.2459	0.5279	1.0164	0.179*	0.50
H49	0.1443	0.5912	0.9884	0.179*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.0483 (2)	0.0620 (2)	0.0543 (2)	0.02772 (15)	0.01953 (14)	0.02128 (15)
S15	0.0489 (4)	0.0642 (4)	0.0628 (4)	0.0212 (3)	0.0216 (3)	0.0200 (3)
S16	0.0527 (4)	0.0670 (4)	0.0699 (4)	0.0196 (3)	0.0293 (3)	0.0161 (3)
S17	0.0621 (5)	0.1042 (7)	0.0738 (5)	0.0125 (4)	0.0069 (4)	0.0378 (5)
S18	0.0778 (5)	0.0815 (5)	0.0731 (5)	0.0397 (4)	0.0006 (4)	0.0183 (4)
N1	0.0643 (13)	0.0688 (12)	0.0545 (12)	0.0328 (11)	0.0251 (10)	0.0265 (10)
N14	0.0406 (10)	0.0582 (11)	0.0550 (11)	0.0206 (8)	0.0129 (8)	0.0163 (9)
C2	0.0770 (19)	0.0779 (18)	0.0691 (17)	0.0324 (16)	0.0289 (15)	0.0293 (14)
C3	0.094 (3)	0.098 (2)	0.086 (2)	0.037 (2)	0.042 (2)	0.037 (2)
C4	0.078 (2)	0.096 (2)	0.086 (2)	0.0365 (18)	0.0429 (18)	0.0331 (19)
C5	0.0600 (17)	0.0841 (18)	0.0604 (15)	0.0341 (15)	0.0230 (13)	0.0156 (14)
C6	0.0568 (15)	0.0697 (15)	0.0514 (13)	0.0312 (13)	0.0192 (11)	0.0172 (11)
C7	0.0708 (19)	0.086 (2)	0.0776 (19)	0.0431 (17)	0.0235 (16)	0.0192 (16)
C8	0.0648 (17)	0.0753 (18)	0.0726 (18)	0.0390 (15)	0.0194 (14)	0.0236 (15)
C9	0.0518 (14)	0.0559 (13)	0.0580 (14)	0.0236 (11)	0.0122 (11)	0.0140 (11)
C10	0.0453 (12)	0.0563 (13)	0.0492 (12)	0.0227 (10)	0.0110 (10)	0.0157 (10)
C11	0.0614 (16)	0.0635 (15)	0.0694 (16)	0.0271 (13)	0.0137 (13)	0.0244 (13)
C12	0.0620 (17)	0.0665 (15)	0.0670 (17)	0.0213 (13)	0.0166 (13)	0.0279 (13)
C13	0.0508 (13)	0.0604 (13)	0.0637 (15)	0.0186 (11)	0.0175 (11)	0.0234 (12)
C19	0.0545 (14)	0.0579 (14)	0.0604 (14)	0.0230 (11)	0.0191 (11)	0.0184 (11)
C21	0.0548 (15)	0.0828 (18)	0.0632 (16)	0.0337 (14)	0.0187 (13)	0.0166 (14)
N20	0.0755 (17)	0.0807 (17)	0.0646 (15)	0.0183 (14)	0.0287 (13)	0.0040 (13)
C23	0.080 (2)	0.095 (2)	0.079 (2)	0.0287 (19)	0.0207 (18)	0.0132 (19)
C24	0.109 (3)	0.095 (3)	0.107 (3)	0.030 (2)	0.035 (3)	0.031 (2)
C25	0.111 (4)	0.130 (4)	0.125 (4)	0.027 (3)	0.019 (3)	0.038 (3)
C26	0.107 (3)	0.123 (4)	0.110 (3)	0.047 (3)	0.018 (3)	0.030 (3)
C27	0.104 (3)	0.107 (3)	0.093 (3)	0.037 (3)	0.030 (2)	0.022 (2)
C28	0.106 (4)	0.139 (4)	0.130 (4)	0.055 (3)	0.023 (3)	0.048 (4)
C29	0.132 (5)	0.183 (6)	0.113 (4)	0.035 (4)	0.064 (4)	0.035 (4)
C30	0.107 (4)	0.137 (4)	0.113 (4)	0.060 (3)	0.028 (3)	0.015 (3)
N22	0.0658 (17)	0.108 (2)	0.0743 (18)	0.0231 (16)	−0.0159 (14)	0.0265 (16)
C31	0.102 (3)	0.147 (4)	0.099 (3)	0.060 (3)	0.018 (3)	0.025 (3)
C32	0.114 (4)	0.150 (5)	0.145 (5)	0.077 (4)	0.059 (4)	0.064 (4)
C33	0.130 (4)	0.131 (4)	0.123 (4)	0.056 (4)	0.031 (3)	0.050 (3)
C34	0.137 (5)	0.127 (4)	0.123 (4)	0.054 (4)	0.040 (4)	0.031 (3)
C35	0.135 (5)	0.165 (6)	0.130 (5)	0.058 (5)	0.033 (4)	0.052 (4)
C36	0.208 (9)	0.196 (8)	0.185 (8)	0.113 (8)	0.114 (7)	0.070 (7)
C37	0.130 (5)	0.227 (9)	0.136 (6)	0.021 (6)	0.029 (5)	0.021 (6)
C38	0.182 (8)	0.190 (8)	0.168 (7)	0.063 (7)	0.037 (6)	0.076 (6)
O1E	0.164 (7)	0.087 (4)	0.100 (4)	0.046 (4)	0.012 (4)	0.044 (3)
C1E	0.26 (2)	0.27 (2)	0.155 (13)	0.15 (2)	0.071 (15)	0.141 (16)
C2E	0.112 (8)	0.167 (11)	0.209 (14)	0.056 (8)	0.048 (9)	0.136 (12)

Geometric parameters (Å, º)

Zn—N14	2.178 (2)	C26—H16	0.9600
Zn—N1	2.284 (2)	C26—H17	0.9600
Zn—S17	2.4605 (10)	C27—C28	1.498 (7)
Zn—S15	2.4793 (11)	C27—H18	0.9700
Zn—S16	2.5083 (9)	C27—H19	0.9700
Zn—S18	2.6012 (14)	C28—C29	1.497 (8)
S15—C19	1.714 (3)	C28—H20	0.9700
S16—C19	1.726 (3)	C28—H21	0.9700
S17—C21	1.688 (3)	C29—C30	1.502 (8)
S18—C21	1.691 (4)	C29—H22	0.9700
N1—C6	1.338 (4)	C29—H23	0.9700
N1—C2	1.338 (4)	C30—H24	0.9600
N14—C13	1.309 (3)	C30—H25	0.9600
N14—C10	1.363 (3)	C30—H26	0.9600
C2—C3	1.388 (5)	N22—C31	1.433 (6)
C2—H1	0.9300	N22—C35	1.486 (8)
C3—C4	1.374 (6)	C31—C32	1.509 (7)
C3—H2	0.9300	C31—H27	0.9700
C4—C5	1.403 (5)	C31—H28	0.9700
C4—H3	0.9300	C32—C33	1.553 (7)
C5—C6	1.393 (4)	C32—H29	0.9700
C5—C7	1.434 (5)	C32—H30	0.9700
C6—C10	1.438 (4)	C33—C34	1.485 (8)
C7—C8	1.332 (5)	C33—H31	0.9700
C7—H4	0.9300	C33—H32	0.9700
C8—C9	1.417 (4)	C34—H33	0.9600
C8—H5	0.9300	C34—H34	0.9600
C9—C10	1.395 (4)	C34—H35	0.9600
C9—C11	1.409 (4)	C35—C36	1.454 (10)
C11—C12	1.377 (5)	C35—H36	0.9700
C11—H6	0.9300	C35—H37	0.9700
C12—C13	1.408 (4)	C36—C37	1.572 (11)
C12—H7	0.9300	C36—H38	0.9700
C13—H8	0.9300	C36—H39	0.9700
C19—N20	1.320 (4)	C37—C38	1.465 (11)
C21—N22	1.344 (4)	C37—H40	0.9700
N20—C23	1.451 (5)	C37—H41	0.9700
N20—C27	1.500 (6)	C38—H42	0.9600
C23—C24	1.526 (7)	C38—H43	0.9600
C23—H9	0.9700	C38—H44	0.9600
C23—H10	0.9700	O1E—C1E	1.441 (9)
C24—C25	1.516 (7)	C1E—C2E	1.509 (9)
C24—H11	0.9700	C1E—H45	0.9700
C24—H12	0.9700	C1E—H46	0.9700
C25—C26	1.480 (7)	C2E—H47	0.9600
C25—H13	0.9700	C2E—H48	0.9600
C25—H14	0.9700	C2E—H49	0.9600
C26—H15	0.9600
N14—Zn—N1	73.48 (8)	C25—C26—H17	109.5
N14—Zn—S17	148.09 (6)	H15—C26—H17	109.5
N1—Zn—S17	93.51 (7)	H16—C26—H17	109.5
N14—Zn—S15	104.44 (6)	C28—C27—N20	109.2 (4)
N1—Zn—S15	85.01 (7)	C28—C27—H18	109.8
S17—Zn—S15	103.22 (4)	N20—C27—H18	109.8
N14—Zn—S16	96.42 (6)	C28—C27—H19	109.8
N1—Zn—S16	151.84 (6)	N20—C27—H19	109.8
S17—Zn—S16	107.07 (4)	H18—C27—H19	108.3
S15—Zn—S16	71.92 (3)	C27—C28—C29	109.2 (5)
N14—Zn—S18	86.24 (6)	C27—C28—H20	109.8
N1—Zn—S18	107.91 (7)	C29—C28—H20	109.9
S17—Zn—S18	69.90 (4)	C27—C28—H21	109.8
S15—Zn—S18	165.37 (3)	C29—C28—H21	109.8
S16—Zn—S18	97.29 (4)	H20—C28—H21	108.3
C19—S15—Zn	86.25 (10)	C30—C29—C28	107.2 (5)
C19—S16—Zn	85.09 (10)	C30—C29—H22	110.3
C21—S17—Zn	88.08 (12)	C28—C29—H22	110.3
C21—S18—Zn	83.48 (11)	C30—C29—H23	110.3
C6—N1—C2	117.2 (3)	C28—C29—H23	110.3
C6—N1—Zn	114.81 (18)	H22—C29—H23	108.5
C2—N1—Zn	127.6 (2)	C29—C30—H24	109.5
C13—N14—C10	118.8 (2)	C29—C30—H25	109.5
C13—N14—Zn	123.92 (19)	H24—C30—H25	109.5
C10—N14—Zn	117.23 (17)	C29—C30—H26	109.5
N1—C2—C3	122.3 (3)	H24—C30—H26	109.5
N1—C2—H1	118.8	H25—C30—H26	109.5
C3—C2—H1	118.8	C21—N22—C31	121.7 (4)
C4—C3—C2	120.4 (3)	C21—N22—C35	119.1 (4)
C4—C3—H2	119.8	C31—N22—C35	112.1 (4)
C2—C3—H2	119.8	N22—C31—C32	108.4 (5)
C3—C4—C5	118.2 (3)	N22—C31—H27	110.0
C3—C4—H3	120.9	C32—C31—H27	110.0
C5—C4—H3	120.9	N22—C31—H28	110.0
C6—C5—C4	117.4 (3)	C32—C31—H28	110.0
C6—C5—C7	119.0 (3)	H27—C31—H28	108.4
C4—C5—C7	123.6 (3)	C31—C32—C33	106.6 (5)
N1—C6—C5	124.5 (3)	C31—C32—H29	110.4
N1—C6—C10	116.7 (2)	C33—C32—H29	110.4
C5—C6—C10	118.8 (3)	C31—C32—H30	110.4
C8—C7—C5	122.1 (3)	C33—C32—H30	110.4
C8—C7—H4	119.0	H29—C32—H30	108.6
C5—C7—H4	119.0	C34—C33—C32	108.4 (5)
C7—C8—C9	120.2 (3)	C34—C33—H31	110.0
C7—C8—H5	119.9	C32—C33—H31	110.0
C9—C8—H5	119.9	C34—C33—H32	110.0
C10—C9—C11	117.1 (3)	C32—C33—H32	110.0
C10—C9—C8	119.8 (3)	H31—C33—H32	108.4
C11—C9—C8	123.1 (3)	C33—C34—H33	109.5
N14—C10—C9	122.5 (2)	C33—C34—H34	109.5
N14—C10—C6	117.5 (2)	H33—C34—H34	109.5
C9—C10—C6	120.0 (2)	C33—C34—H35	109.5
C12—C11—C9	120.5 (3)	H33—C34—H35	109.5
C12—C11—H6	119.7	H34—C34—H35	109.5
C9—C11—H6	119.7	C36—C35—N22	106.6 (7)
C11—C12—C13	117.5 (3)	C36—C35—H36	110.4
C11—C12—H7	121.3	N22—C35—H36	110.4
C13—C12—H7	121.3	C36—C35—H37	110.4
N14—C13—C12	123.5 (3)	N22—C35—H37	110.4
N14—C13—H8	118.2	H36—C35—H37	108.6
C12—C13—H8	118.2	C35—C36—C37	105.5 (6)
N20—C19—S15	122.0 (2)	C35—C36—H38	110.6
N20—C19—S16	121.3 (2)	C37—C36—H38	110.6
S15—C19—S16	116.73 (16)	C35—C36—H39	110.6
N22—C21—S18	121.3 (3)	C37—C36—H39	110.6
N22—C21—S17	120.2 (3)	H38—C36—H39	108.8
S18—C21—S17	118.38 (18)	C38—C37—C36	108.6 (7)
C19—N20—C23	120.6 (3)	C38—C37—H40	110.0
C19—N20—C27	122.0 (3)	C36—C37—H40	110.0
C23—N20—C27	115.1 (3)	C38—C37—H41	110.0
N20—C23—C24	109.3 (4)	C36—C37—H41	110.0
N20—C23—H9	109.8	H40—C37—H41	108.4
C24—C23—H9	109.8	C37—C38—H42	109.5
N20—C23—H10	109.8	C37—C38—H43	109.5
C24—C23—H10	109.8	H42—C38—H43	109.5
H9—C23—H10	108.3	C37—C38—H44	109.5
C25—C24—C23	109.4 (4)	H42—C38—H44	109.5
C25—C24—H11	109.8	H43—C38—H44	109.5
C23—C24—H11	109.8	O1E—C1E—C2E	123.5 (13)
C25—C24—H12	109.8	O1E—C1E—H45	106.4
C23—C24—H12	109.8	C2E—C1E—H45	106.5
H11—C24—H12	108.2	O1E—C1E—H46	106.4
C24—C25—C26	109.0 (5)	C2E—C1E—H46	106.4
C24—C25—H13	109.9	H45—C1E—H46	106.5
C26—C25—H13	109.9	C1E—C2E—H47	109.4
C24—C25—H14	109.9	C1E—C2E—H48	109.5
C26—C25—H14	109.9	H47—C2E—H48	109.5
H13—C25—H14	108.3	C1E—C2E—H49	109.5
C25—C26—H15	109.5	H47—C2E—H49	109.5
C25—C26—H16	109.5	H48—C2E—H49	109.5
H15—C26—H16	109.5

(II) bis(N,N-di-n-hexyldithiocarbamato-κ²S,S')bis(1,10-phenanthroline- κ²N,N')calcium(II)

Crystal data

[Ca(C13H26NS2)2(C12H8N2)2]	Z = 2
Mr = 921.42	F(000) = 988
Triclinic, P1	Dx = 1.191 Mg m^−3
a = 11.875 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.129 (2) Å	Cell parameters from 25 reflections
c = 17.547 (4) Å	θ = 12–20°
α = 72.29 (1)°	µ = 0.32 mm^−1
β = 80.91 (2)°	T = 293 K
γ = 84.20 (2)°	Prismatic, yellow
V = 2569.2 (11) Å^3	0.30 × 0.28 × 0.25 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 1.6°
Graphite monochromator	h = −13→14
2θ/ω scans	k = −14→15
9086 measured reflections	l = 0→20
9086 independent reflections	3 standard reflections every 120 min
7339 reflections with I > 2σ(I)	intensity decay: 0.4%

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) = 0.155	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.1184P)^2] where P = (Fo^2 + 2Fc^2)/3
9086 reflections	(Δ/σ)max = 0.010
550 parameters	Δρmax = 0.82 e Å^−3
316 restraints	Δρmin = −0.24 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
Ca	0.73286 (3)	0.23019 (3)	0.05432 (2)	0.04401 (13)
S29	0.50466 (4)	0.29536 (5)	0.11549 (3)	0.05741 (16)
S30	0.69420 (4)	0.31815 (4)	0.19825 (3)	0.05478 (15)
S31	0.93539 (5)	0.12354 (5)	0.12471 (4)	0.06423 (17)
S32	0.71069 (5)	0.04059 (4)	0.20207 (4)	0.06023 (16)
N1	0.90333 (15)	0.26229 (13)	−0.06464 (10)	0.0517 (4)
N14	0.78812 (14)	0.42403 (11)	−0.01259 (9)	0.0461 (3)
N15	0.60723 (14)	0.27956 (12)	−0.06285 (9)	0.0462 (3)
N28	0.70927 (15)	0.08110 (12)	−0.00674 (10)	0.0512 (4)
N34	0.47861 (15)	0.29887 (16)	0.26815 (11)	0.0591 (4)
N36	0.88987 (17)	0.01289 (15)	0.27953 (12)	0.0637 (5)
C2	0.9597 (2)	0.18568 (18)	−0.09347 (14)	0.0633 (5)
H1	0.9298	0.1184	−0.0769	0.082*
C3	1.0607 (2)	0.2009 (2)	−0.14696 (14)	0.0696 (6)
H2	1.0968	0.1449	−0.1653	0.090*
C4	1.1063 (2)	0.2998 (2)	−0.17234 (16)	0.0717 (6)
H3	1.1739	0.3109	−0.2079	0.093*
C5	1.05085 (17)	0.38374 (18)	−0.14463 (12)	0.0564 (5)
C6	0.94879 (15)	0.36132 (14)	−0.09126 (10)	0.0442 (4)
C7	1.0919 (2)	0.4865 (2)	−0.16690 (18)	0.0744 (7)
H4	1.1607	0.5003	−0.2008	0.097*
C8	1.0356 (2)	0.56406 (19)	−0.14105 (17)	0.0683 (6)
H5	1.0663	0.6309	−0.1568	0.089*
C9	0.92998 (17)	0.54865 (15)	−0.09009 (12)	0.0509 (4)
C10	0.88602 (15)	0.44651 (14)	−0.06285 (10)	0.0422 (4)
C11	0.8643 (2)	0.62967 (15)	−0.06317 (15)	0.0608 (5)
H6	0.8905	0.6983	−0.0783	0.079*
C12	0.7637 (2)	0.60804 (16)	−0.01562 (15)	0.0608 (5)
H7	0.7185	0.6621	0.0002	0.079*
C13	0.72849 (19)	0.50404 (15)	0.00937 (13)	0.0535 (4)
H8	0.6597	0.4897	0.0432	0.070*
C16	0.55512 (19)	0.37433 (16)	−0.09103 (13)	0.0555 (5)
H9	0.5697	0.4289	−0.0710	0.072*
C17	0.4804 (2)	0.39904 (18)	−0.14813 (14)	0.0627 (5)
H10	0.4495	0.4685	−0.1676	0.081*
C18	0.4536 (2)	0.3185 (2)	−0.17478 (15)	0.0665 (6)
H11	0.4015	0.3319	−0.2115	0.087*
C19	0.50478 (17)	0.21478 (17)	−0.14679 (13)	0.0552 (5)
C20	0.58112 (15)	0.19931 (15)	−0.09177 (11)	0.0444 (4)
C21	0.4806 (2)	0.1273 (2)	−0.17275 (18)	0.0761 (7)
H12	0.4281	0.1376	−0.2088	0.099*
C22	0.5332 (2)	0.0302 (2)	−0.14550 (18)	0.0744 (7)
H13	0.5169	−0.0259	−0.1633	0.097*
C23	0.61351 (17)	0.01208 (17)	−0.08983 (14)	0.0558 (5)
C24	0.63692 (15)	0.09372 (14)	−0.06111 (12)	0.0470 (4)
C25	0.6731 (2)	−0.08884 (16)	−0.06137 (15)	0.0657 (6)
H14	0.6601	−0.1462	−0.0789	0.085*
C26	0.7472 (2)	−0.10075 (17)	−0.00991 (17)	0.0695 (6)
H15	0.7889	−0.1655	0.0071	0.090*
C27	0.7623 (2)	−0.01502 (16)	0.01875 (15)	0.0648 (6)
H16	0.8115	−0.0257	0.0572	0.084*
C33	0.55384 (16)	0.30300 (14)	0.20069 (11)	0.0466 (4)
C35	0.84855 (17)	0.05518 (14)	0.20921 (13)	0.0503 (4)
C37	0.3559 (2)	0.2883 (2)	0.27189 (14)	0.0731 (7)
H17	0.3256	0.2515	0.3271	0.095*
H18	0.3457	0.2437	0.2386	0.095*
C38	0.2882 (2)	0.3911 (3)	0.24500 (17)	0.0814 (8)
H19	0.3185	0.4275	0.1897	0.106*
H20	0.2102	0.3753	0.2450	0.106*
C39	0.2863 (3)	0.4654 (3)	0.29387 (18)	0.0880 (8)
H21	0.3642	0.4824	0.2928	0.114*
H22	0.2577	0.4284	0.3494	0.114*
C40	0.2170 (3)	0.5669 (3)	0.2685 (2)	0.1050 (11)
H23	0.2427	0.6026	0.2122	0.136*
H24	0.1380	0.5505	0.2725	0.136*
C41	0.2223 (5)	0.6395 (4)	0.3152 (3)	0.151 (2)
H25	0.3017	0.6535	0.3124	0.196*
H26	0.1949	0.6037	0.3712	0.196*
C42	0.1576 (6)	0.7420 (5)	0.2908 (4)	0.168 (2)
H27	0.1092	0.7400	0.2524	0.219*
H28	0.2095	0.7981	0.2666	0.219*
H29	0.1115	0.7552	0.3373	0.219*
C43	0.5179 (2)	0.2982 (2)	0.34229 (14)	0.0729 (6)
H30	0.4565	0.3281	0.3739	0.095*
H31	0.5809	0.3449	0.3288	0.095*
C44	0.5556 (3)	0.1922 (3)	0.39282 (16)	0.0920 (9)
H32	0.4908	0.1473	0.4095	0.120*
H	0.6126	0.1601	0.3597	0.120*
C45	0.6036 (4)	0.1906 (4)	0.4653 (2)	0.1132 (12)
H33	0.6753	0.2257	0.4477	0.147*
H34	0.5522	0.2341	0.4930	0.147*
C46	0.6252 (5)	0.0883 (4)	0.5237 (2)	0.1293 (15)
H35	0.6820	0.0464	0.4980	0.168*
H36	0.5554	0.0503	0.5393	0.168*
C47	0.6663 (6)	0.0956 (5)	0.5991 (3)	0.156 (2)
H37	0.7418	0.1235	0.5843	0.203*
H38	0.6159	0.1469	0.6197	0.203*
C48	0.6718 (6)	−0.0061 (6)	0.6647 (4)	0.183 (3)
H39	0.6302	−0.0582	0.6540	0.238*
H40	0.6387	0.0056	0.7151	0.238*
H41	0.7501	−0.0318	0.6675	0.238*
C49	1.0085 (3)	0.0226 (3)	0.2883 (2)	0.0908 (9)
H42	1.0571	0.0115	0.2413	0.118*
H43	1.0285	−0.0345	0.3350	0.118*
C50	1.0347 (4)	0.1262 (4)	0.2977 (3)	0.1369 (17)
H44	1.1162	0.1251	0.2990	0.178*
H45	1.0168	0.1830	0.2502	0.178*
C51	0.9753 (4)	0.1525 (5)	0.3685 (4)	0.150 (2)
H46	0.9863	0.0926	0.4158	0.194*
H47	0.8942	0.1621	0.3644	0.194*
C52	1.0129 (5)	0.2498 (5)	0.3800 (4)	0.167 (2)
H48	1.0088	0.3077	0.3304	0.217*
H49	1.0924	0.2373	0.3887	0.217*
C53	0.9476 (7)	0.2855 (6)	0.4475 (5)	0.200 (3)
H50	0.8672	0.2908	0.4417	0.260*
H51	0.9579	0.2301	0.4975	0.260*
C54	0.9764 (6)	0.3873 (6)	0.4555 (5)	0.182 (3)
H52	0.9285	0.4445	0.4262	0.237*
H53	1.0550	0.3996	0.4341	0.237*
H54	0.9644	0.3846	0.5115	0.237*
C55	0.8190 (2)	−0.0495 (2)	0.35136 (16)	0.0744 (6)
H55	0.7422	−0.0163	0.3520	0.097*
H56	0.8484	−0.0448	0.3987	0.097*
C56	0.8118 (3)	−0.1653 (2)	0.35882 (19)	0.0838 (8)
H57	0.7851	−0.1710	0.3109	0.109*
H58	0.8877	−0.2002	0.3613	0.109*
C57	0.7348 (4)	−0.2221 (3)	0.4307 (3)	0.1170 (13)
H59	0.6589	−0.1873	0.4277	0.152*
H60	0.7611	−0.2154	0.4784	0.152*
C58	0.7267 (6)	−0.3398 (4)	0.4403 (4)	0.169 (2)
H61	0.8028	−0.3703	0.4279	0.220*
H62	0.6996	−0.3756	0.4963	0.220*
C59	0.6518 (7)	−0.3626 (5)	0.3896 (4)	0.175 (2)
H63	0.5769	−0.3287	0.3999	0.228*
H64	0.6813	−0.3296	0.3335	0.228*
C60	0.6385 (8)	−0.4751 (6)	0.4007 (6)	0.225 (4)
H65	0.5784	−0.4818	0.3720	0.292*
H66	0.6195	−0.5112	0.4571	0.292*
H67	0.7086	−0.5067	0.3802	0.292*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca	0.0501 (2)	0.0284 (2)	0.0577 (2)	−0.00478 (15)	−0.00767 (16)	−0.01777 (15)
S29	0.0526 (3)	0.0636 (3)	0.0642 (3)	−0.0032 (2)	−0.0098 (2)	−0.0299 (2)
S30	0.0498 (3)	0.0533 (3)	0.0684 (3)	−0.0107 (2)	−0.0058 (2)	−0.0269 (2)
S31	0.0555 (3)	0.0541 (3)	0.0803 (4)	−0.0085 (2)	−0.0103 (3)	−0.0134 (3)
S32	0.0577 (3)	0.0474 (3)	0.0761 (3)	−0.0151 (2)	−0.0166 (2)	−0.0112 (2)
N1	0.0564 (9)	0.0393 (8)	0.0612 (9)	0.0033 (7)	−0.0055 (7)	−0.0203 (7)
N14	0.0545 (9)	0.0311 (7)	0.0552 (8)	−0.0074 (6)	−0.0007 (7)	−0.0182 (6)
N15	0.0538 (8)	0.0350 (7)	0.0543 (8)	−0.0019 (6)	−0.0069 (6)	−0.0201 (6)
N28	0.0611 (9)	0.0323 (7)	0.0647 (9)	−0.0047 (7)	−0.0130 (7)	−0.0181 (7)
N34	0.0510 (9)	0.0703 (12)	0.0577 (9)	−0.0130 (8)	−0.0026 (7)	−0.0207 (8)
N36	0.0679 (11)	0.0513 (10)	0.0752 (11)	−0.0031 (8)	−0.0245 (9)	−0.0157 (8)
C2	0.0767 (14)	0.0467 (11)	0.0687 (12)	0.0046 (10)	−0.0060 (10)	−0.0246 (9)
C3	0.0694 (14)	0.0686 (15)	0.0670 (13)	0.0199 (12)	0.0028 (11)	−0.0279 (11)
C4	0.0542 (12)	0.0785 (16)	0.0750 (14)	0.0066 (11)	0.0060 (10)	−0.0225 (12)
C5	0.0446 (10)	0.0638 (13)	0.0589 (10)	−0.0006 (9)	−0.0074 (8)	−0.0155 (9)
C6	0.0451 (9)	0.0400 (9)	0.0468 (8)	−0.0019 (7)	−0.0104 (7)	−0.0097 (7)
C7	0.0468 (11)	0.0845 (17)	0.0903 (16)	−0.0200 (11)	0.0052 (11)	−0.0253 (13)
C8	0.0608 (13)	0.0535 (12)	0.0901 (16)	−0.0185 (10)	−0.0130 (11)	−0.0141 (11)
C9	0.0514 (10)	0.0411 (9)	0.0645 (11)	−0.0157 (8)	−0.0170 (8)	−0.0128 (8)
C10	0.0440 (9)	0.0368 (9)	0.0480 (8)	−0.0074 (7)	−0.0124 (7)	−0.0110 (7)
C11	0.0704 (13)	0.0313 (9)	0.0853 (14)	−0.0126 (9)	−0.0204 (11)	−0.0160 (9)
C12	0.0703 (13)	0.0363 (9)	0.0823 (13)	−0.0029 (9)	−0.0114 (11)	−0.0266 (9)
C13	0.0629 (11)	0.0364 (9)	0.0656 (11)	−0.0053 (8)	−0.0062 (9)	−0.0218 (8)
C16	0.0662 (12)	0.0387 (9)	0.0640 (11)	0.0022 (8)	−0.0094 (9)	−0.0196 (8)
C17	0.0628 (12)	0.0544 (12)	0.0657 (12)	0.0110 (10)	−0.0040 (10)	−0.0170 (10)
C18	0.0612 (13)	0.0705 (14)	0.0723 (13)	0.0057 (10)	−0.0234 (10)	−0.0231 (11)
C19	0.0535 (11)	0.0533 (11)	0.0666 (11)	−0.0068 (9)	−0.0114 (9)	−0.0260 (9)
C20	0.0393 (8)	0.0437 (9)	0.0506 (9)	−0.0075 (7)	0.0037 (7)	−0.0177 (7)
C21	0.0808 (16)	0.0733 (16)	0.0925 (17)	−0.0134 (13)	−0.0347 (14)	−0.0370 (14)
C22	0.0783 (15)	0.0587 (13)	0.1031 (18)	−0.0159 (11)	−0.0243 (13)	−0.0389 (13)
C23	0.0544 (11)	0.0472 (10)	0.0764 (12)	−0.0145 (8)	−0.0045 (9)	−0.0321 (10)
C24	0.0430 (9)	0.0372 (9)	0.0655 (10)	−0.0080 (7)	−0.0021 (8)	−0.0228 (8)
C25	0.0887 (16)	0.0363 (9)	0.0799 (14)	−0.0147 (10)	−0.0061 (12)	−0.0275 (9)
C26	0.0818 (15)	0.0375 (10)	0.0989 (17)	0.0010 (10)	−0.0224 (13)	−0.0308 (11)
C27	0.0881 (16)	0.0311 (10)	0.0802 (14)	0.0010 (9)	−0.0246 (12)	−0.0184 (9)
C33	0.0515 (10)	0.0366 (8)	0.0536 (9)	−0.0089 (7)	−0.0001 (8)	−0.0177 (7)
C35	0.0552 (10)	0.0335 (9)	0.0654 (10)	−0.0056 (7)	−0.0134 (8)	−0.0157 (8)
C37	0.0613 (13)	0.0969 (18)	0.0602 (12)	−0.0284 (13)	0.0090 (10)	−0.0225 (12)
C38	0.0491 (12)	0.120 (2)	0.0741 (14)	−0.0007 (13)	−0.0038 (10)	−0.0305 (15)
C39	0.0709 (16)	0.113 (2)	0.0771 (16)	0.0104 (16)	−0.0047 (13)	−0.0311 (16)
C40	0.083 (2)	0.140 (3)	0.095 (2)	0.020 (2)	−0.0008 (16)	−0.054 (2)
C41	0.145 (4)	0.159 (5)	0.146 (4)	0.064 (4)	−0.038 (3)	−0.057 (4)
C42	0.164 (5)	0.189 (6)	0.161 (5)	0.021 (4)	−0.025 (4)	−0.073 (5)
C43	0.0758 (15)	0.0874 (18)	0.0594 (12)	−0.0077 (13)	0.0002 (11)	−0.0308 (12)
C44	0.102 (2)	0.100 (2)	0.0656 (15)	−0.0196 (17)	−0.0130 (14)	−0.0080 (14)
C45	0.105 (3)	0.153 (4)	0.0779 (19)	−0.017 (2)	−0.0263 (17)	−0.019 (2)
C46	0.156 (4)	0.127 (3)	0.100 (3)	−0.007 (3)	−0.042 (3)	−0.012 (2)
C47	0.157 (5)	0.163 (5)	0.147 (4)	−0.007 (4)	−0.040 (4)	−0.036 (4)
C48	0.187 (6)	0.200 (7)	0.143 (5)	−0.026 (5)	−0.028 (4)	−0.016 (5)
C49	0.0774 (17)	0.0821 (19)	0.118 (2)	−0.0008 (14)	−0.0488 (17)	−0.0203 (17)
C50	0.107 (3)	0.154 (4)	0.170 (4)	−0.030 (3)	−0.049 (3)	−0.055 (3)
C51	0.126 (4)	0.156 (5)	0.198 (6)	−0.044 (3)	−0.010 (4)	−0.092 (4)
C52	0.151 (5)	0.186 (6)	0.185 (6)	−0.045 (4)	−0.023 (4)	−0.075 (5)
C53	0.194 (7)	0.189 (7)	0.228 (8)	−0.066 (6)	0.007 (6)	−0.078 (6)
C54	0.180 (6)	0.191 (7)	0.204 (7)	−0.046 (5)	0.002 (5)	−0.103 (6)
C55	0.0829 (17)	0.0654 (14)	0.0743 (14)	0.0057 (12)	−0.0202 (12)	−0.0177 (11)
C56	0.0934 (19)	0.0608 (14)	0.0871 (17)	−0.0021 (13)	−0.0027 (14)	−0.0125 (13)
C57	0.134 (3)	0.092 (2)	0.112 (3)	−0.033 (2)	0.005 (2)	−0.012 (2)
C58	0.175 (6)	0.122 (4)	0.184 (6)	−0.047 (4)	−0.008 (5)	−0.001 (4)
C59	0.212 (7)	0.159 (6)	0.169 (5)	−0.020 (5)	−0.017 (5)	−0.069 (5)
C60	0.258 (9)	0.196 (8)	0.254 (10)	−0.057 (7)	−0.019 (8)	−0.110 (7)

Geometric parameters (Å, º)

Ca—N28	2.5571 (15)	C38—C39	1.478 (4)
Ca—N14	2.5616 (15)	C38—H19	0.9700
Ca—N15	2.6145 (18)	C38—H20	0.9700
Ca—N1	2.6333 (19)	C39—C40	1.478 (4)
Ca—S29	2.8981 (11)	C39—H21	0.9700
Ca—S31	2.9114 (11)	C39—H22	0.9700
Ca—S32	2.9963 (8)	C40—C41	1.445 (6)
Ca—S30	3.0371 (8)	C40—H23	0.9700
S29—C33	1.722 (2)	C40—H24	0.9700
S30—C33	1.691 (2)	C41—C42	1.459 (6)
S31—C35	1.721 (2)	C41—H25	0.9700
S32—C35	1.696 (2)	C41—H26	0.9700
N1—C2	1.335 (3)	C42—H27	0.9600
N1—C6	1.376 (2)	C42—H28	0.9600
N14—C13	1.328 (2)	C42—H29	0.9600
N14—C10	1.343 (2)	C43—C44	1.473 (4)
N15—C16	1.320 (3)	C43—H30	0.9700
N15—C20	1.380 (2)	C43—H31	0.9700
N28—C27	1.332 (3)	C44—C45	1.467 (4)
N28—C24	1.345 (3)	C44—H32	0.9700
N34—C33	1.356 (3)	C44—H	0.9700
N34—C43	1.447 (3)	C45—C46	1.448 (5)
N34—C37	1.467 (3)	C45—H33	0.9700
N36—C35	1.338 (3)	C45—H34	0.9700
N36—C49	1.463 (3)	C46—C47	1.512 (6)
N36—C55	1.464 (3)	C46—H35	0.9700
C2—C3	1.392 (3)	C46—H36	0.9700
C2—H1	0.9300	C47—C48	1.477 (7)
C3—C4	1.376 (4)	C47—H37	0.9700
C3—H2	0.9300	C47—H38	0.9700
C4—C5	1.401 (3)	C48—H39	0.9600
C4—H3	0.9300	C48—H40	0.9600
C5—C7	1.400 (4)	C48—H41	0.9600
C5—C6	1.407 (3)	C49—C50	1.488 (5)
C6—C10	1.452 (3)	C49—H42	0.9700
C7—C8	1.319 (4)	C49—H43	0.9700
C7—H4	0.9300	C50—C51	1.448 (6)
C8—C9	1.414 (3)	C50—H44	0.9700
C8—H5	0.9300	C50—H45	0.9700
C9—C10	1.404 (2)	C51—C52	1.474 (6)
C9—C11	1.409 (3)	C51—H46	0.9700
C11—C12	1.347 (3)	C51—H47	0.9700
C11—H6	0.9300	C52—C53	1.483 (7)
C12—C13	1.387 (3)	C52—H48	0.9700
C12—H7	0.9300	C52—H49	0.9700
C13—H8	0.9300	C53—C54	1.464 (7)
C16—C17	1.386 (3)	C53—H50	0.9700
C16—H9	0.9300	C53—H51	0.9700
C17—C18	1.362 (4)	C54—H52	0.9600
C17—H10	0.9300	C54—H53	0.9600
C18—C19	1.409 (3)	C54—H54	0.9600
C18—H11	0.9300	C55—C56	1.497 (4)
C19—C20	1.384 (3)	C55—H55	0.9700
C19—C21	1.426 (3)	C55—H56	0.9700
C20—C24	1.457 (3)	C56—C57	1.478 (4)
C21—C22	1.344 (4)	C56—H57	0.9700
C21—H12	0.9300	C56—H58	0.9700
C22—C23	1.424 (4)	C57—C58	1.514 (6)
C22—H13	0.9300	C57—H59	0.9700
C23—C24	1.383 (3)	C57—H60	0.9700
C23—C25	1.423 (3)	C58—C59	1.462 (8)
C25—C26	1.323 (4)	C58—H61	0.9700
C25—H14	0.9300	C58—H62	0.9700
C26—C27	1.402 (3)	C59—C60	1.452 (8)
C26—H15	0.9300	C59—H63	0.9700
C27—H16	0.9300	C59—H64	0.9700
C37—C38	1.485 (4)	C60—H65	0.9600
C37—H17	0.9700	C60—H66	0.9600
C37—H18	0.9700	C60—H67	0.9600
N28—Ca—N14	131.02 (5)	C37—C38—H19	108.3
N28—Ca—N15	63.48 (5)	C39—C38—H20	108.3
N14—Ca—N15	81.55 (5)	C37—C38—H20	108.3
N28—Ca—N1	78.98 (6)	H19—C38—H20	107.4
N14—Ca—N1	63.20 (5)	C38—C39—C40	116.0 (3)
N15—Ca—N1	83.56 (6)	C38—C39—H21	108.3
N28—Ca—S29	106.14 (5)	C40—C39—H21	108.3
N14—Ca—S29	92.79 (4)	C38—C39—H22	108.3
N15—Ca—S29	71.63 (4)	C40—C39—H22	108.3
N1—Ca—S29	148.04 (4)	H21—C39—H22	107.4
N28—Ca—S31	93.34 (4)	C41—C40—C39	114.2 (3)
N14—Ca—S31	103.74 (5)	C41—C40—H23	108.7
N15—Ca—S31	150.42 (4)	C39—C40—H23	108.7
N1—Ca—S31	73.59 (5)	C41—C40—H24	108.7
S29—Ca—S31	135.86 (3)	C39—C40—H24	108.7
N28—Ca—S32	78.80 (4)	H23—C40—H24	107.6
N14—Ca—S32	148.88 (4)	C40—C41—C42	116.1 (5)
N15—Ca—S32	126.42 (4)	C40—C41—H25	108.3
N1—Ca—S32	126.43 (4)	C42—C41—H25	108.3
S29—Ca—S32	85.16 (3)	C40—C41—H26	108.3
S31—Ca—S32	59.85 (3)	C42—C41—H26	108.3
N28—Ca—S30	149.53 (4)	H25—C41—H26	107.4
N14—Ca—S30	78.73 (4)	C41—C42—H27	109.5
N15—Ca—S30	125.70 (4)	C41—C42—H28	109.5
N1—Ca—S30	128.22 (4)	H27—C42—H28	109.5
S29—Ca—S30	59.54 (2)	C41—C42—H29	109.5
S31—Ca—S30	83.69 (3)	H27—C42—H29	109.5
S32—Ca—S30	73.50 (2)	H28—C42—H29	109.5
C33—S29—Ca	90.14 (7)	N34—C43—C44	115.4 (2)
C33—S30—Ca	86.12 (7)	N34—C43—H30	108.4
C35—S31—Ca	89.19 (7)	C44—C43—H30	108.4
C35—S32—Ca	86.86 (7)	N34—C43—H31	108.4
C2—N1—C6	116.77 (18)	C44—C43—H31	108.4
C2—N1—Ca	124.69 (14)	H30—C43—H31	107.5
C6—N1—Ca	117.84 (11)	C45—C44—C43	116.3 (3)
C13—N14—C10	117.68 (15)	C45—C44—H32	108.2
C13—N14—Ca	120.74 (12)	C43—C44—H32	108.2
C10—N14—Ca	121.02 (11)	C45—C44—H	108.2
C16—N15—C20	116.09 (17)	C43—C44—H	108.2
C16—N15—Ca	124.61 (13)	H32—C44—H	107.4
C20—N15—Ca	118.84 (12)	C46—C45—C44	118.6 (4)
C27—N28—C24	117.37 (17)	C46—C45—H33	107.7
C27—N28—Ca	120.79 (14)	C44—C45—H33	107.7
C24—N28—Ca	121.66 (12)	C46—C45—H34	107.7
C33—N34—C43	120.68 (18)	C44—C45—H34	107.7
C33—N34—C37	122.68 (18)	H33—C45—H34	107.1
C43—N34—C37	116.53 (18)	C45—C46—C47	114.6 (4)
C35—N36—C49	122.3 (2)	C45—C46—H35	108.6
C35—N36—C55	121.3 (2)	C47—C46—H35	108.6
C49—N36—C55	116.4 (2)	C45—C46—H36	108.6
N1—C2—C3	123.6 (2)	C47—C46—H36	108.6
N1—C2—H1	118.2	H35—C46—H36	107.6
C3—C2—H1	118.2	C48—C47—C46	115.5 (5)
C4—C3—C2	119.2 (2)	C48—C47—H37	108.4
C4—C3—H2	120.4	C46—C47—H37	108.4
C2—C3—H2	120.4	C48—C47—H38	108.4
C3—C4—C5	119.9 (2)	C46—C47—H38	108.4
C3—C4—H3	120.0	H37—C47—H38	107.5
C5—C4—H3	120.0	C47—C48—H39	109.5
C4—C5—C7	123.6 (2)	C47—C48—H40	109.5
C4—C5—C6	117.0 (2)	H39—C48—H40	109.5
C7—C5—C6	119.4 (2)	C47—C48—H41	109.5
N1—C6—C5	123.51 (17)	H39—C48—H41	109.5
N1—C6—C10	117.35 (15)	H40—C48—H41	109.5
C5—C6—C10	119.14 (17)	N36—C49—C50	115.8 (3)
C8—C7—C5	121.7 (2)	N36—C49—H42	108.3
C8—C7—H4	119.1	C50—C49—H42	108.3
C5—C7—H4	119.1	N36—C49—H43	108.3
C7—C8—C9	122.0 (2)	C50—C49—H43	108.3
C7—C8—H5	119.0	H42—C49—H43	107.4
C9—C8—H5	119.0	C51—C50—C49	116.0 (4)
C10—C9—C11	116.41 (18)	C51—C50—H44	108.3
C10—C9—C8	119.29 (19)	C49—C50—H44	108.3
C11—C9—C8	124.30 (18)	C51—C50—H45	108.3
N14—C10—C9	123.26 (17)	C49—C50—H45	108.3
N14—C10—C6	118.38 (15)	H44—C50—H45	107.4
C9—C10—C6	118.36 (17)	C50—C51—C52	114.1 (5)
C12—C11—C9	120.22 (17)	C50—C51—H46	108.7
C12—C11—H6	119.9	C52—C51—H46	108.7
C9—C11—H6	119.9	C50—C51—H47	108.7
C11—C12—C13	119.07 (19)	C52—C51—H47	108.7
C11—C12—H7	120.5	H46—C51—H47	107.6
C13—C12—H7	120.5	C51—C52—C53	116.1 (5)
N14—C13—C12	123.26 (19)	C51—C52—H48	108.3
N14—C13—H8	118.4	C53—C52—H48	108.3
C12—C13—H8	118.4	C51—C52—H49	108.3
N15—C16—C17	125.23 (19)	C53—C52—H49	108.3
N15—C16—H9	117.4	H48—C52—H49	107.4
C17—C16—H9	117.4	C54—C53—C52	117.1 (6)
C18—C17—C16	117.9 (2)	C54—C53—H50	108.0
C18—C17—H10	121.0	C52—C53—H50	108.0
C16—C17—H10	121.0	C54—C53—H51	108.0
C17—C18—C19	120.1 (2)	C52—C53—H51	108.0
C17—C18—H11	120.0	H50—C53—H51	107.3
C19—C18—H11	120.0	C53—C54—H52	109.5
C20—C19—C18	117.41 (19)	C53—C54—H53	109.5
C20—C19—C21	119.9 (2)	H52—C54—H53	109.5
C18—C19—C21	122.7 (2)	C53—C54—H54	109.5
N15—C20—C19	123.17 (17)	H52—C54—H54	109.5
N15—C20—C24	117.13 (17)	H53—C54—H54	109.5
C19—C20—C24	119.69 (17)	N36—C55—C56	116.2 (2)
C22—C21—C19	120.6 (2)	N36—C55—H55	108.2
C22—C21—H12	119.7	C56—C55—H55	108.2
C19—C21—H12	119.7	N36—C55—H56	108.2
C21—C22—C23	120.9 (2)	C56—C55—H56	108.2
C21—C22—H13	119.6	H55—C55—H56	107.4
C23—C22—H13	119.6	C57—C56—C55	113.3 (3)
C24—C23—C25	117.0 (2)	C57—C56—H57	108.9
C24—C23—C22	120.5 (2)	C55—C56—H57	108.9
C25—C23—C22	122.47 (19)	C57—C56—H58	108.9
N28—C24—C23	123.48 (18)	C55—C56—H58	108.9
N28—C24—C20	118.13 (16)	H57—C56—H58	107.7
C23—C24—C20	118.40 (19)	C56—C57—C58	114.5 (4)
C26—C25—C23	119.76 (18)	C56—C57—H59	108.6
C26—C25—H14	120.1	C58—C57—H59	108.6
C23—C25—H14	120.1	C56—C57—H60	108.6
C25—C26—C27	119.5 (2)	C58—C57—H60	108.6
C25—C26—H15	120.2	H59—C57—H60	107.6
C27—C26—H15	120.2	C59—C58—C57	114.9 (5)
N28—C27—C26	122.8 (2)	C59—C58—H61	108.5
N28—C27—H16	118.6	C57—C58—H61	108.5
C26—C27—H16	118.6	C59—C58—H62	108.5
N34—C33—S30	121.19 (15)	C57—C58—H62	108.5
N34—C33—S29	119.23 (15)	H61—C58—H62	107.5
S30—C33—S29	119.57 (11)	C60—C59—C58	115.8 (7)
N36—C35—S32	120.41 (16)	C60—C59—H63	108.3
N36—C35—S31	120.30 (16)	C58—C59—H63	108.3
S32—C35—S31	119.29 (12)	C60—C59—H64	108.3
N34—C37—C38	114.7 (2)	C58—C59—H64	108.3
N34—C37—H17	108.6	H63—C59—H64	107.4
C38—C37—H17	108.6	C59—C60—H65	109.5
N34—C37—H18	108.6	C59—C60—H66	109.5
C38—C37—H18	108.6	H65—C60—H66	109.5
H17—C37—H18	107.6	C59—C60—H67	109.5
C39—C38—C37	115.8 (2)	H65—C60—H67	109.5
C39—C38—H19	108.3	H66—C60—H67	109.5