Bis(O,O'-diiso­propyl di­thio­phosphato-S,S')(1,10-phenanthroline-N,N')metal(II) complexes with cadmium(II) and iron(II)

The two title compounds, [M(C₆H₁₄O₂PS₂)₂(C₁₂H₈N₂)], where M = Cd^II and Fe^II, are isomorphous. Each compound has a crystallographic twofold axis of symmetry through the metal atom and the 1,10-phenanthroline mol­ecule. The central metal atom is coordinated to four S atoms from the two dithiophos­phate groups and two N atoms from the 1,10-phenanthroline ligand. The environment of the metal atom is a distorted octahedron.

S1. Comment

Metal dialkyl dithiophosphates and their derivatives have been widely employed both as antioxidant and antiwear additives in rubber and as lubricating oils (Harrison & Kikabhai, 1987; Kovtun et al., 1992). Adducts and their formation reactions have also been found useful in a wide variety of ways, such as with biological systems (Livingstone & Mihkelson, 1970). Metal complex ions of the type [M(LL)₃], where LL is either 1,10-phenanthroline (phen) or a modified phen ligand, are particularly attractive species for developing new diagnostic and therapeutic agents which can recognize and cleave DNA (Barton, 1986; Naing et al., 1995). Furthermore, cadmium is often substituted in the proteins and used to aid in the determination of the coordination environment of the native metal, primarily because of the usefulness of Cd NMR. Also a series of potential models, [M(SR)_x(N-donor)_{(4 - x)}] (M = Zn, Co, Cd) have been reported for cysteine containing zinc metalloproteins (Santos et al., 1990). The original Co^II(dtp)₂ is easily oxidized. However, similar complexes are very stable in air. Fe(II)(dtp)₂ and its adducts are also expected to have this property. The title adducts, (I) and (II), were prepared and the structures were determined so that the determination of the equilibrium constants can be done to confirm the property. \sch

In complex (I), the Cd—N bond length is comparable with the complexes of [Cd{(n-BuS₂CS)₂}(bipy)] [2.368 (3) Å] (Black et al., 1986). It is however shorter than those of [Cd{(Et)₂NCS₂}(bipy) [2.434 (6) Å] (Glinskaya et al., 1992) but longer than those of [Cd(C₂₄H₁₈O₄)(bipy)] [2.342 (5), 2.355 (5) Å; Annan et al., 1990). The Fe—N bond length in complex (II) is comparable to those of the complex [Fe(phen)₂PhCOO]₂OCl₂·7H₂O [2.221 (4), 2.168 (3), 2.139 (3) and 2.270 (3) Å] (Li et al., 1995).

The Cd—S distances in (I) are in good agreement with [Cd(II){(Et-dtp)₂}(hex)₂] [2.682 (1), 2.704 (1) Å] (Shimoi et al., 1982). However, the Cd—S bond lengths are longer than those found in tetrahedral configuration, [Cd(II)(iPr-dtp)₂] [2.486 (7), 2.590 (8) Å] (Lawton & Kokotailo, 1969) but shorter than those in [Cd{(iPr-dtp)₂}(NMe₄)] [2.659 (1), 2.777 (2) Å] (McCleverty et al., 1982). Fe—S bond distances in (II), the Fe^II—S distances are are longer than Fe^III—S reported by Drew et al., 1986 [2.461 (2), 2.492 (2), 2.473 (2) Å].

The P—S distances in the dtp groups in (I) and (II) are nearly identical, and are intermediate between the single bond (2.09 Å) and the double bond (1.87 Å) values.

In (I), the S1—Cd1—S2 bond angle is larger than those found in [Cd{(iPr-dtp)₂}(NMe₄)] [74.9 (5)°] and [Cd{(Et)₂NCS₂}(bipy)] [67.3 (1), 68.5 (2)°]. The N1—Cd1—N1A bond angle is in good agreement with those of [Cd(phen)₃](ClO₄)₂ [71.7 (1)°; Xiong et al., 1997]. In (II), the S1—Fe1—S2 bond angle is 79.8 (7)°. The N1—Fe1—N1a bond angle [75.1 (2)°] is similar to that of the six-coordiate compound [Fe(phen)₂ph]₂OCl·7H₂O [75.1 (1)°; Li et al., 1995].

The coordination around Cd1 in (I) and Fe1 in (II) is a distorted octahedron with bond angles ranging from 70.7 (2) to 164.2 (1)° and 75.1 (2) to 168.2 (1)°, respectively. The central metal atom is coordinated to four S atoms from the two dtp groups and two N atoms from the 1,10-phenanthroline ligand. In both complexes, the four-membered ring formed by M1, S1, S2, and P1 atoms is almost planar. This plane and the plane through M1, N1, C7, N1A and C7A atoms make a dihedral angle of 86.5 (1) and 86.9° for (I) and (II), respectively.

S2. Experimental

Complex (I): This compound was prepared by mixing EtOH solution (50 ml) of cadmium(II) bis(O,O'-diisopropyl dithiophosphate) (0.1 mmol) and phen (0.1 mmol) with heating. After cooling to room temperature and filtration, colorless single crystals suitable for X-ray analysis were obtained on slow evaporation of the solvent. Complex (II): this complex was prepared by using iron(II) bis(O,O'-diisopropyldithiophosphate) and phen in acetone solvent using the method as in complex (I). The dark red single crystals suitable for X-ray analysis were obtained on slow evaporation of the solvent.

S3. Refinement

After checking their presence in the difference map, all H-atom positions were placed at idealized positions and were allowed to ride on their parent carbon atoms. Due to the large fraction of weak data at higher angles in (II), the 2θ maximum for (II) is limited to 50°.

Computing details

For both compounds, data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 1990).

Figures

	Fig. 1. The structure of compound (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. The structure of compound (II) showing 50% probability displacement ellipsoids and the atom-numbering scheme.

(I)

Crystal data

[Cd(C6H14O2PS2)2(C12H8N2)]	F(000) = 1472
Mr = 719.13	Dx = 1.459 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 6966 reflections
a = 11.7493 (1) Å	θ = 2.0–28.3°
b = 19.0809 (3) Å	µ = 1.05 mm^−1
c = 14.6006 (2) Å	T = 293 K
V = 3273.27 (7) Å^3	Block, colourless
Z = 4	0.46 × 0.42 × 0.36 mm

Data collection

Siemens SMART CCD area detector diffractometer	4054 independent reflections
Radiation source: fine-focus sealed tube	2965 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.078
Detector resolution: 8.33 pixels mm^-1	θmax = 28.4°, θmin = 2.0°
ω scans	h = −15→12
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −16→25
Tmin = 0.644, Tmax = 0.704	l = −19→18
21589 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.168	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0962P)^2 + 1.5469P] where P = (Fo^2 + 2Fc^2)/3
4054 reflections	(Δ/σ)max < 0.001
168 parameters	Δρmax = 1.03 e Å^−3
0 restraints	Δρmin = −1.02 e Å^−3

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

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
Cd1	0.0000	0.190082 (18)	0.2500	0.04888 (17)
P1	−0.21444 (9)	0.11766 (6)	0.16000 (9)	0.0589 (3)
S1	−0.10398 (11)	0.17045 (8)	0.08559 (8)	0.0776 (4)
S2	−0.16992 (10)	0.10456 (6)	0.28886 (9)	0.0665 (3)
O2	−0.2503 (3)	0.0454 (2)	0.1180 (3)	0.0931 (12)
O1	−0.3345 (3)	0.15485 (19)	0.1671 (3)	0.0848 (10)
N1	−0.1055 (3)	0.29127 (15)	0.2900 (2)	0.0477 (7)
C4	−0.1800 (7)	−0.0036 (3)	0.0699 (5)	0.109 (2)
H4A	−0.1471	0.0213	0.0175	0.131*
C6	−0.0854 (8)	−0.0346 (4)	0.1205 (6)	0.135 (3)
H6A	−0.0359	0.0019	0.1421	0.202*
H6B	−0.0437	−0.0655	0.0809	0.202*
H6C	−0.1144	−0.0606	0.1717	0.202*
C5	−0.2648 (7)	−0.0557 (4)	0.0320 (6)	0.139 (3)
H5A	−0.3238	−0.0310	−0.0001	0.209*
H5B	−0.2975	−0.0821	0.0814	0.209*
H5C	−0.2268	−0.0870	−0.0094	0.209*
C1	−0.3908 (5)	0.1841 (3)	0.0882 (5)	0.0900 (17)
H1A	−0.3414	0.1772	0.0348	0.108*
C2	−0.4007 (11)	0.2593 (5)	0.1046 (9)	0.221 (7)
H2A	−0.3265	0.2786	0.1156	0.331*
H2B	−0.4481	0.2672	0.1572	0.331*
H2C	−0.4340	0.2814	0.0520	0.331*
C3	−0.4998 (6)	0.1483 (6)	0.0704 (8)	0.177 (6)
H3A	−0.4861	0.0993	0.0603	0.266*
H3B	−0.5350	0.1682	0.0171	0.266*
H3C	−0.5492	0.1540	0.1222	0.266*
C7	−0.0552 (3)	0.35357 (18)	0.2706 (2)	0.0448 (8)
C8	−0.2070 (4)	0.2914 (2)	0.3273 (3)	0.0637 (10)
H8A	−0.2410	0.2487	0.3412	0.076*
C9	−0.2664 (4)	0.3533 (3)	0.3468 (4)	0.0751 (13)
H9A	−0.3387	0.3514	0.3726	0.090*
C10	−0.2178 (4)	0.4154 (2)	0.3281 (3)	0.0730 (13)
H10A	−0.2563	0.4567	0.3412	0.088*
C11	−0.1098 (4)	0.41773 (19)	0.2890 (3)	0.0577 (10)
C12	−0.0520 (5)	0.4815 (2)	0.2681 (4)	0.0785 (15)
H12A	−0.0876	0.5240	0.2802	0.118*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0405 (2)	0.0336 (2)	0.0726 (3)	0.000	−0.00371 (16)	0.000
P1	0.0474 (6)	0.0508 (6)	0.0786 (7)	−0.0086 (4)	−0.0097 (5)	−0.0022 (5)
S1	0.0656 (8)	0.1065 (10)	0.0607 (6)	−0.0285 (7)	−0.0048 (5)	0.0086 (6)
S2	0.0655 (7)	0.0562 (6)	0.0778 (7)	−0.0186 (5)	0.0021 (6)	0.0104 (5)
O2	0.085 (3)	0.080 (2)	0.114 (3)	−0.0264 (19)	−0.002 (2)	−0.023 (2)
O1	0.059 (2)	0.101 (3)	0.094 (2)	0.0079 (17)	−0.0029 (17)	0.024 (2)
N1	0.0436 (16)	0.0386 (14)	0.0610 (18)	0.0038 (12)	0.0008 (14)	0.0027 (14)
C4	0.119 (6)	0.087 (4)	0.122 (5)	−0.011 (4)	0.004 (4)	−0.046 (4)
C6	0.123 (7)	0.101 (5)	0.181 (8)	0.007 (5)	0.020 (6)	−0.016 (5)
C5	0.187 (9)	0.107 (5)	0.125 (6)	−0.055 (5)	−0.012 (6)	−0.043 (4)
C1	0.064 (3)	0.105 (4)	0.101 (4)	0.000 (3)	−0.021 (3)	0.017 (3)
C2	0.255 (14)	0.119 (7)	0.289 (15)	0.055 (8)	−0.163 (12)	−0.006 (8)
C3	0.106 (7)	0.176 (10)	0.249 (13)	−0.048 (6)	−0.099 (7)	0.074 (9)
C7	0.047 (2)	0.0382 (17)	0.0490 (18)	0.0078 (14)	−0.0104 (15)	−0.0021 (13)
C8	0.053 (2)	0.057 (2)	0.081 (3)	0.0061 (18)	0.008 (2)	0.006 (2)
C9	0.055 (3)	0.084 (3)	0.086 (3)	0.023 (2)	0.012 (2)	−0.008 (3)
C10	0.076 (3)	0.057 (3)	0.086 (3)	0.025 (2)	−0.008 (2)	−0.014 (2)
C11	0.061 (2)	0.0409 (19)	0.071 (2)	0.0124 (16)	−0.018 (2)	−0.0053 (17)
C12	0.087 (3)	0.037 (2)	0.112 (4)	0.012 (2)	−0.031 (3)	−0.007 (2)

Geometric parameters (Å, º)

Cd1—N1	2.368 (3)	N1—C7	1.358 (5)
Cd1—N1^i	2.368 (3)	C4—C6	1.459 (11)
Cd1—S2	2.6402 (10)	C4—C5	1.512 (8)
Cd1—S2^i	2.6402 (10)	C1—C2	1.458 (10)
Cd1—S1^i	2.7194 (12)	C1—C3	1.474 (8)
Cd1—S1	2.7194 (12)	C7—C11	1.408 (5)
P1—O2	1.566 (4)	C7—C7^i	1.429 (8)
P1—O1	1.582 (4)	C8—C9	1.402 (6)
P1—S2	1.9688 (18)	C9—C10	1.342 (7)
P1—S1	1.9695 (16)	C10—C11	1.391 (7)
O2—C4	1.432 (7)	C11—C12	1.427 (6)
O1—C1	1.442 (6)	C12—C12^i	1.331 (12)
N1—C8	1.311 (5)
N1—Cd1—N1^i	70.73 (15)	P1—S2—Cd1	85.24 (5)
N1—Cd1—S2	93.16 (8)	C4—O2—P1	127.7 (4)
N1^i—Cd1—S2	162.35 (8)	C1—O1—P1	122.0 (4)
N1—Cd1—S2^i	162.35 (8)	C8—N1—C7	118.8 (3)
N1^i—Cd1—S2^i	93.16 (8)	C8—N1—Cd1	125.4 (3)
S2—Cd1—S2^i	103.65 (6)	C7—N1—Cd1	115.8 (2)
N1—Cd1—S1^i	97.44 (8)	O2—C4—C6	117.2 (6)
N1^i—Cd1—S1^i	95.46 (9)	O2—C4—C5	103.2 (6)
S2—Cd1—S1^i	93.72 (4)	C6—C4—C5	114.9 (6)
S2^i—Cd1—S1^i	76.40 (4)	O1—C1—C2	106.6 (6)
N1—Cd1—S1	95.46 (9)	O1—C1—C3	111.1 (6)
N1^i—Cd1—S1	97.44 (8)	C2—C1—C3	114.6 (8)
S2—Cd1—S1	76.40 (4)	N1—C7—C11	121.5 (4)
S2^i—Cd1—S1	93.72 (4)	N1—C7—C7^i	118.9 (2)
S1^i—Cd1—S1	164.16 (7)	C11—C7—C7^i	119.6 (3)
O2—P1—O1	100.4 (2)	N1—C8—C9	122.6 (4)
O2—P1—S2	109.50 (18)	C10—C9—C8	119.4 (4)
O1—P1—S2	103.35 (15)	C9—C10—C11	120.0 (4)
O2—P1—S1	114.28 (17)	C10—C11—C7	117.7 (4)
O1—P1—S1	113.22 (15)	C10—C11—C12	123.4 (4)
S2—P1—S1	114.65 (7)	C7—C11—C12	118.9 (4)
P1—S1—Cd1	83.08 (5)	C12^i—C12—C11	121.5 (3)
O2—P1—S1—Cd1	−134.76 (19)	S1—Cd1—N1—C8	83.1 (3)
O1—P1—S1—Cd1	111.07 (17)	N1^i—Cd1—N1—C7	0.23 (17)
S2—P1—S1—Cd1	−7.17 (8)	S2—Cd1—N1—C7	−172.4 (2)
N1—Cd1—S1—P1	−86.94 (9)	S2^i—Cd1—N1—C7	25.3 (5)
N1^i—Cd1—S1—P1	−158.17 (9)	S1^i—Cd1—N1—C7	93.4 (2)
S2—Cd1—S1—P1	5.00 (6)	S1—Cd1—N1—C7	−95.8 (2)
S2^i—Cd1—S1—P1	108.15 (6)	P1—O2—C4—C6	62.5 (9)
S1^i—Cd1—S1—P1	57.52 (5)	P1—O2—C4—C5	−170.2 (5)
O2—P1—S2—Cd1	137.34 (17)	P1—O1—C1—C2	−117.2 (8)
O1—P1—S2—Cd1	−116.33 (15)	P1—O1—C1—C3	117.4 (7)
S1—P1—S2—Cd1	7.36 (8)	C8—N1—C7—C11	−0.3 (5)
N1—Cd1—S2—P1	89.88 (9)	Cd1—N1—C7—C11	178.6 (3)
N1^i—Cd1—S2—P1	66.3 (3)	C8—N1—C7—C7^i	−179.6 (4)
S2^i—Cd1—S2—P1	−95.55 (6)	Cd1—N1—C7—C7^i	−0.7 (5)
S1^i—Cd1—S2—P1	−172.44 (6)	C7—N1—C8—C9	0.7 (7)
S1—Cd1—S2—P1	−4.98 (6)	Cd1—N1—C8—C9	−178.1 (4)
O1—P1—O2—C4	159.5 (6)	N1—C8—C9—C10	−0.8 (8)
S2—P1—O2—C4	−92.1 (6)	C8—C9—C10—C11	0.4 (8)
S1—P1—O2—C4	38.0 (6)	C9—C10—C11—C7	0.0 (7)
O2—P1—O1—C1	−76.7 (4)	C9—C10—C11—C12	−179.2 (5)
S2—P1—O1—C1	170.2 (4)	N1—C7—C11—C10	0.0 (6)
S1—P1—O1—C1	45.6 (4)	C7^i—C7—C11—C10	179.2 (4)
N1^i—Cd1—N1—C8	179.0 (4)	N1—C7—C11—C12	179.2 (4)
S2—Cd1—N1—C8	6.4 (3)	C7^i—C7—C11—C12	−1.6 (7)
S2^i—Cd1—N1—C8	−155.9 (3)	C10—C11—C12—C12^i	179.1 (6)
S1^i—Cd1—N1—C8	−87.7 (3)	C7—C11—C12—C12^i	0.0 (9)

Symmetry code: (i) −x, y, −z+1/2.

(II) Bis(O,O'- diisopropyldithiophosphato-S,S')(1,10-phenanthroline)Iron(II) complex: [Fe{(iPr-dtp)₂}(phen)]

Crystal data

[Fe(C12H8N2)(C6H14O2PS2)2]	F(000) = 1384
Mr = 662.58	Dx = 1.375 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 6556 reflections
a = 11.5761 (2) Å	θ = 2.1–28.4°
b = 18.8015 (1) Å	µ = 0.86 mm^−1
c = 14.7098 (2) Å	T = 293 K
V = 3201.56 (7) Å^3	Block, dark red
Z = 4	0.32 × 0.28 × 0.20 mm

Data collection

Siemens SMART CCD area detector diffractometer	2834 independent reflections
Radiation source: fine-focus sealed tube	1686 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.089
Detector resolution: 8.33 pixels mm^-1	θmax = 25.0°, θmin = 2.1°
ω scans	h = −7→13
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	k = −22→13
Tmin = 0.770, Tmax = 0.846	l = −12→17
8551 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.1222P)^2] where P = (Fo^2 + 2Fc^2)/3
2834 reflections	(Δ/σ)max < 0.001
168 parameters	Δρmax = 1.02 e Å^−3
0 restraints	Δρmin = −0.61 e Å^−3

Special details

Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 4 cm and the detector swing angle was -35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the duplicate reflections, and was found to be negligible.

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
Fe1	0.0000	0.31194 (5)	0.2500	0.0409 (4)
P1	−0.20786 (13)	0.38234 (8)	0.33768 (12)	0.0525 (5)
S1	−0.09554 (14)	0.32606 (10)	0.40749 (11)	0.0665 (6)
S2	−0.15747 (14)	0.39888 (8)	0.21160 (11)	0.0565 (5)
O1	−0.3302 (4)	0.3447 (2)	0.3283 (3)	0.0734 (13)
O2	−0.2469 (5)	0.4532 (3)	0.3844 (4)	0.0915 (16)
N1	−0.1036 (4)	0.2188 (2)	0.2085 (3)	0.0421 (11)
C1	−0.3890 (6)	0.3155 (4)	0.4078 (5)	0.073 (2)
H1A	−0.3406	0.3229	0.4616	0.088*
C2	−0.3979 (11)	0.2369 (5)	0.3890 (9)	0.172 (6)
H2A	−0.3219	0.2175	0.3810	0.258*
H2B	−0.4424	0.2294	0.3348	0.258*
H2C	−0.4351	0.2138	0.4394	0.258*
C3	−0.5002 (8)	0.3518 (6)	0.4210 (9)	0.170 (6)
H3A	−0.4869	0.4016	0.4316	0.254*
H3B	−0.5393	0.3316	0.4725	0.254*
H3C	−0.5470	0.3461	0.3677	0.254*
C4	−0.1777 (9)	0.5052 (5)	0.4270 (7)	0.111 (3)
H4A	−0.1413	0.4809	0.4785	0.133*
C5	−0.2635 (9)	0.5568 (5)	0.4693 (7)	0.133 (4)
H5A	−0.3233	0.5305	0.4997	0.199*
H5B	−0.2971	0.5858	0.4225	0.199*
H5C	−0.2243	0.5866	0.5123	0.199*
C6	−0.0844 (9)	0.5382 (5)	0.3782 (7)	0.122 (3)
H6A	−0.0346	0.5022	0.3538	0.183*
H6B	−0.0412	0.5681	0.4188	0.183*
H6C	−0.1151	0.5665	0.3295	0.183*
C7	−0.0553 (5)	0.1550 (3)	0.2279 (3)	0.0401 (13)
C8	−0.2059 (5)	0.2191 (3)	0.1679 (4)	0.0551 (16)
H8A	−0.2396	0.2626	0.1538	0.066*
C9	−0.2650 (6)	0.1570 (4)	0.1455 (5)	0.0695 (19)
H9A	−0.3362	0.1594	0.1163	0.083*
C10	−0.2184 (6)	0.0932 (4)	0.1662 (5)	0.069 (2)
H10A	−0.2580	0.0516	0.1524	0.083*
C11	−0.1104 (5)	0.0901 (3)	0.2085 (4)	0.0553 (17)
C12	−0.0522 (6)	0.0249 (3)	0.2310 (6)	0.079 (2)
H12A	−0.0882	−0.0183	0.2187	0.095*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0367 (6)	0.0294 (6)	0.0565 (8)	0.000	−0.0014 (5)	0.000
P1	0.0440 (9)	0.0387 (8)	0.0749 (12)	0.0048 (7)	0.0108 (8)	−0.0026 (7)
S1	0.0557 (10)	0.0902 (14)	0.0537 (10)	0.0231 (9)	0.0040 (8)	0.0049 (9)
S2	0.0543 (9)	0.0430 (9)	0.0723 (12)	0.0107 (8)	−0.0042 (8)	0.0077 (7)
O1	0.050 (2)	0.078 (3)	0.093 (3)	−0.009 (2)	0.003 (3)	0.019 (3)
O2	0.092 (4)	0.059 (3)	0.124 (4)	0.010 (3)	0.023 (3)	−0.019 (3)
N1	0.038 (2)	0.033 (2)	0.055 (3)	−0.001 (2)	−0.002 (2)	0.001 (2)
C1	0.054 (4)	0.085 (5)	0.080 (5)	−0.002 (4)	0.012 (4)	0.016 (4)
C2	0.189 (12)	0.091 (7)	0.236 (14)	−0.060 (8)	0.110 (10)	−0.003 (8)
C3	0.109 (8)	0.152 (10)	0.248 (15)	0.051 (8)	0.101 (9)	0.081 (10)
C4	0.104 (7)	0.089 (6)	0.140 (8)	−0.004 (6)	0.005 (7)	−0.059 (6)
C5	0.182 (10)	0.081 (6)	0.135 (8)	0.021 (7)	0.046 (7)	−0.046 (6)
C6	0.108 (8)	0.083 (6)	0.174 (10)	0.007 (6)	−0.004 (7)	−0.032 (7)
C7	0.046 (3)	0.029 (3)	0.046 (3)	−0.005 (3)	0.011 (3)	−0.003 (2)
C8	0.050 (4)	0.055 (4)	0.061 (4)	−0.008 (3)	−0.009 (3)	0.000 (3)
C9	0.049 (4)	0.080 (5)	0.080 (5)	−0.021 (4)	−0.009 (4)	−0.012 (4)
C10	0.069 (5)	0.052 (4)	0.086 (5)	−0.026 (4)	0.007 (4)	−0.014 (3)
C11	0.059 (4)	0.035 (3)	0.072 (4)	−0.011 (3)	0.021 (3)	−0.009 (3)
C12	0.090 (5)	0.025 (3)	0.123 (7)	−0.009 (3)	0.036 (5)	−0.004 (3)

Geometric parameters (Å, º)

Fe1—N1	2.209 (4)	N1—C7	1.354 (6)
Fe1—N1^i	2.209 (4)	C1—C3	1.470 (10)
Fe1—S2	2.513 (2)	C1—C2	1.506 (11)
Fe1—S2^i	2.5127 (16)	C4—C6	1.438 (11)
Fe1—S1	2.581 (2)	C4—C5	1.520 (11)
Fe1—S1^i	2.5808 (17)	C7—C11	1.406 (7)
P1—O2	1.566 (5)	C7—C7^i	1.435 (11)
P1—O1	1.589 (4)	C8—C9	1.393 (8)
P1—S1	1.966 (2)	C9—C10	1.349 (9)
P1—S2	1.969 (2)	C10—C11	1.398 (9)
O1—C1	1.460 (8)	C11—C12	1.438 (8)
O2—C4	1.412 (9)	C12—C12^i	1.331 (15)
N1—C8	1.327 (7)
N1—Fe1—N1^i	75.1 (2)	P1—S2—Fe1	84.29 (7)
N1—Fe1—S2	93.44 (11)	C1—O1—P1	120.9 (4)
N1^i—Fe1—S2	166.38 (12)	C4—O2—P1	128.4 (5)
N1—Fe1—S2^i	166.38 (12)	C8—N1—C7	117.9 (5)
N1^i—Fe1—S2^i	93.44 (11)	C8—N1—Fe1	127.2 (4)
S2—Fe1—S2^i	98.84 (8)	C7—N1—Fe1	114.8 (3)
N1—Fe1—S1	95.56 (12)	O1—C1—C3	109.9 (7)
N1^i—Fe1—S1	93.80 (12)	O1—C1—C2	104.7 (6)
S2—Fe1—S1	79.86 (6)	C3—C1—C2	114.9 (9)
S2^i—Fe1—S1	92.42 (6)	O2—C4—C6	120.2 (8)
N1—Fe1—S1^i	93.80 (12)	O2—C4—C5	104.6 (8)
N1^i—Fe1—S1^i	95.56 (12)	C6—C4—C5	114.8 (8)
S2—Fe1—S1^i	92.42 (6)	N1—C7—C11	122.6 (5)
S2^i—Fe1—S1^i	79.86 (6)	N1—C7—C7^i	117.6 (3)
S1—Fe1—S1^i	168.19 (10)	C11—C7—C7^i	119.8 (4)
O2—P1—O1	99.2 (3)	N1—C8—C9	122.7 (6)
O2—P1—S1	114.8 (2)	C10—C9—C8	119.7 (6)
O1—P1—S1	113.27 (19)	C9—C10—C11	119.7 (6)
O2—P1—S2	111.4 (2)	C10—C11—C7	117.4 (6)
O1—P1—S2	104.6 (2)	C10—C11—C12	123.9 (6)
S1—P1—S2	112.40 (10)	C7—C11—C12	118.7 (6)
P1—S1—Fe1	82.53 (7)	C12^i—C12—C11	121.5 (4)
O2—P1—S1—Fe1	−137.2 (2)	S1^i—Fe1—N1—C8	−85.5 (5)
O1—P1—S1—Fe1	109.9 (2)	N1^i—Fe1—N1—C7	0.0 (3)
S2—P1—S1—Fe1	−8.47 (10)	S2—Fe1—N1—C7	−172.5 (3)
N1—Fe1—S1—P1	−86.29 (13)	S2^i—Fe1—N1—C7	33.1 (8)
N1^i—Fe1—S1—P1	−161.62 (13)	S1—Fe1—N1—C7	−92.4 (4)
S2—Fe1—S1—P1	6.22 (7)	S1^i—Fe1—N1—C7	94.8 (4)
S2^i—Fe1—S1—P1	104.77 (8)	P1—O1—C1—C3	118.6 (7)
S1^i—Fe1—S1—P1	55.99 (7)	P1—O1—C1—C2	−117.5 (8)
O2—P1—S2—Fe1	139.1 (2)	P1—O2—C4—C6	55.7 (12)
O1—P1—S2—Fe1	−114.64 (19)	P1—O2—C4—C5	−173.4 (6)
S1—P1—S2—Fe1	8.67 (10)	C8—N1—C7—C11	−1.4 (8)
N1—Fe1—S2—P1	88.85 (13)	Fe1—N1—C7—C11	178.3 (4)
N1^i—Fe1—S2—P1	57.0 (5)	C8—N1—C7—C7^i	−179.9 (6)
S2^i—Fe1—S2—P1	−97.08 (7)	Fe1—N1—C7—C7^i	−0.1 (7)
S1—Fe1—S2—P1	−6.19 (7)	C7—N1—C8—C9	0.5 (9)
S1^i—Fe1—S2—P1	−177.19 (7)	Fe1—N1—C8—C9	−179.2 (5)
O2—P1—O1—C1	−73.0 (5)	N1—C8—C9—C10	0.8 (10)
S1—P1—O1—C1	49.2 (5)	C8—C9—C10—C11	−1.2 (10)
S2—P1—O1—C1	171.9 (4)	C9—C10—C11—C7	0.3 (9)
O1—P1—O2—C4	167.0 (7)	C9—C10—C11—C12	−178.2 (7)
S1—P1—O2—C4	45.9 (8)	N1—C7—C11—C10	1.0 (9)
S2—P1—O2—C4	−83.3 (8)	C7^i—C7—C11—C10	179.5 (6)
N1^i—Fe1—N1—C8	179.7 (6)	N1—C7—C11—C12	179.6 (6)
S2—Fe1—N1—C8	7.1 (5)	C7^i—C7—C11—C12	−2.0 (10)
S2^i—Fe1—N1—C8	−147.2 (4)	C10—C11—C12—C12^i	178.1 (9)
S1—Fe1—N1—C8	87.3 (5)	C7—C11—C12—C12^i	−0.4 (13)

Symmetry code: (i) −x, y, −z+1/2.