An unexpected product: di-μ-iodo-bis{[2-(N-di­phenyl­phosphino­methyl-N-cyclo­hexyl­amino)­pyridine]­iodo­mercury(II)}

Cui, D.-J.; Zeng, X.-S.; Leng, X.-B.; Xu, F.-B.; Zhang, Z.-Z.

doi:10.1107/S1600536803008754

An unexpected product: di-μ-iodo-bis{[2-(N-diphenylphosphinomethyl-N-cyclohexylamino)pyridine]iodomercury(II)}

D.-J. Cui, X.-S. Zeng, X.-B. Leng, F.-B. Xu and Z.-Z. Zhang

The title compound, [Hg₂I₄(C₂₄H₂₇N₂P)₂], is found to be a symmetric doubly iodide-bridged dimer, with the phosphine ligands attached trans to the two Hg atoms [Hg—P = 2.4726 (12) Å]. The molecule has a centre of symmetry at the centre of the four-membered ring formed by the two Hg and two bridging I atoms.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008754/wn6148sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008754/wn6148Isup2.hkl Contains datablock I

CCDC reference: 214851

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.008 Å
R factor = 0.030
wR factor = 0.076
Data-to-parameter ratio = 19.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



ABSTM_02  Alert A Crystal and compound unsuitable for non-numerical
          corrections. Product of mu and tmid > 3.0
           Value of mu given =     8.576 tmid =     0.350


 1 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 0 Alert Level C = Please check

Comment top

Pyridylphosphines continue to generate much interest as excellent ligands for stabilizing many transition-metal coordination and organometallic complexes (Espinet & Soulantica, 1999). One important property of these ligands is that they can stabilize metal ions in a variety of valence states and geometries. Hence, a metal–metal bond between an electron-rich metal (soft base) and a high-oxidation-state metal (Lewis acid) is easily formed (Zhang & Cheng, 1996). Recently, we designed and synthesized a new pyridylphosphine ligand, namely 2-(N-diphenylphosphinomethyl-N-cyclohexylamino)pyridine, L, and obtained a hetero-binuclear complex containing an Fe—Cu bond (Cui et al., 2001). However, when trans-Fe(CO)₃L₂ is reacted with HgI₂, instead of the desired compound containing an Fe—Hg bond, the title compound, (I), was unexpectedly formed.

In (I), each Hg atom is four-coordinated by two bridging I atoms (Fig. 1), [Hg1—I1 2.8035 (4) Å and Hg1—I1A 2.9665 (4) Å], one terminal I atom [Hg1—I2 2.7698 (4) Å] and one P atom from the ligand L [Hg1—P4 2.4726 (12) Å]. There is significant distortion from tetrahedral geometry, the angles about the metal ranging from 94.044 (10) to 127.87 (3)° (Table 1).

The title compound may be compared with the series (PPh₃)₂Hg₂X₄ which have the same molecular structure as (I) (X = Cl, Br, I), but with replacement of ligand L by triphenylphosphine (Bell et al., 1980, 1989b; Bowmaker et al., 1993). As in (I), the complex with X = Cl is centrosymmetric, whereas the bromo and iodo complexes are non-centrosymmetric. While the larger X_br—Hg—X_br angles (X_br is bridging halogen) and Hg—X distances in the iodide complex may be readily attributed to the increasing size of the halogen, no ready explanation is available for the substantial asymmetry of the Hg—X_br distances found in the iodide complex. In contrast to (R₃P)₂HgX₂ complexes, in which the P—Hg—P angle is an effective indicator of the σ-donating ability of both the phosphine and also of the halogen (Allen et al., 1985; Bell et al., 1989a), the P—Hg—X_t angles (X_t is terminal halogen) in the present complex, which might, on the basis of the stronger σ-donor properties of iodide compared to chloride and bromide, have been anticipated to be larger than in the chloride and bromide, are, in fact, very similar. The relative σ-donating ability of the halides is, however, reflected in the Hg—P distance. Thus the significantly larger distance found in the iodide complex may be attributed to the greater σ-donor ability of iodide compared to chloride and bromide.

Experimental top

The synthesis was carried out under an Ar atmosphere. To a solution of trans-Fe(CO)₃L₂ (0.23 g, 0.25 mmol) was added solid HgI₂ (0.11 g, 0.25 mmol). After stirring for 5 min, the solid disappeared. The mixture was filtered and the solvent was removed. The residue was recrystallized from CH₂Cl₂/CH₃OH and gave 0.17 g (85%) of a dark yellow solid.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998) and SHELXTL (Bruker, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. A view of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

(I) top

Crystal data top

[Hg₂I₄(C₂₄H₂₇N₂P)₂]	F(000) = 1544
M_r = 1657.67	D_x = 2.170 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.5386 (7) Å	Cell parameters from 634 reflections
b = 16.1113 (9) Å	θ = 2.8–25.3°
c = 12.6488 (7) Å	µ = 8.58 mm⁻¹
β = 96.773 (1)°	T = 298 K
V = 2537.4 (2) Å³	Plate, dark yellow
Z = 2	0.40 × 0.35 × 0.05 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	5142 independent reflections
Radiation source: fine-focus sealed tube	4365 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.52, T_max = 0.96	k = −18→20
11685 measured reflections	l = −11→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0458P)² + 0.249P] where P = (F_o² + 2F_c²)/3
5142 reflections	(Δ/σ)_max = 0.002
271 parameters	Δρ_max = 1.49 e Å⁻³
0 restraints	Δρ_min = −1.15 e Å⁻³

Crystal data top

[Hg₂I₄(C₂₄H₂₇N₂P)₂]	V = 2537.4 (2) Å³
M_r = 1657.67	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.5386 (7) Å	µ = 8.58 mm⁻¹
b = 16.1113 (9) Å	T = 298 K
c = 12.6488 (7) Å	0.40 × 0.35 × 0.05 mm
β = 96.773 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5142 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4365 reflections with I > 2σ(I)
T_min = 0.52, T_max = 0.96	R_int = 0.041
11685 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 0.98	Δρ_max = 1.49 e Å⁻³
5142 reflections	Δρ_min = −1.15 e Å⁻³
271 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Hg1	0.880430 (15)	1.041510 (12)	0.399125 (15)	0.04192 (8)
I1	1.09502 (2)	1.09284 (2)	0.43945 (3)	0.04204 (9)
I2	0.76220 (3)	1.16437 (2)	0.48490 (3)	0.05642 (11)
P4	0.79110 (9)	0.97287 (7)	0.23759 (9)	0.0307 (2)
C1	0.6745 (4)	0.9145 (3)	0.2708 (4)	0.0355 (10)
C2	0.6396 (4)	0.8408 (3)	0.2220 (4)	0.0459 (12)
H2A	0.6788	0.8172	0.1717	0.055*
C3	0.5470 (4)	0.8016 (3)	0.2469 (5)	0.0543 (14)
H3A	0.5258	0.7513	0.2150	0.065*
C4	0.4868 (5)	0.8372 (4)	0.3187 (5)	0.0582 (15)
H4A	0.4238	0.8119	0.3339	0.070*
C5	0.5203 (5)	0.9110 (4)	0.3684 (5)	0.0667 (17)
H5A	0.4802	0.9347	0.4180	0.080*
C6	0.6130 (4)	0.9495 (3)	0.3445 (5)	0.0518 (14)
H6A	0.6347	0.9992	0.3778	0.062*
C7	0.7313 (4)	1.0463 (3)	0.1387 (4)	0.0342 (10)
C8	0.7580 (4)	1.1301 (3)	0.1491 (4)	0.0426 (11)
H8A	0.8028	1.1487	0.2081	0.051*
C9	0.7170 (4)	1.1857 (3)	0.0706 (4)	0.0513 (13)
H9A	0.7354	1.2416	0.0765	0.062*
C10	0.6491 (5)	1.1579 (4)	−0.0159 (5)	0.0544 (14)
H10A	0.6223	1.1953	−0.0685	0.065*
C11	0.6209 (4)	1.0764 (4)	−0.0250 (4)	0.0542 (14)
H11A	0.5739	1.0586	−0.0829	0.065*
C12	0.6624 (4)	1.0195 (3)	0.0523 (4)	0.0429 (11)
H12A	0.6436	0.9638	0.0456	0.051*
C13	0.8712 (4)	0.8974 (3)	0.1687 (4)	0.0385 (10)
H13A	0.8431	0.8421	0.1776	0.046*
H13B	0.8624	0.9098	0.0931	0.046*
N1	0.9852 (3)	0.8978 (2)	0.2071 (3)	0.0414 (9)
C14	1.0405 (4)	0.9670 (3)	0.1804 (4)	0.0395 (11)
C15	1.1522 (4)	0.9720 (3)	0.1824 (5)	0.0505 (13)
H15A	1.1951	0.9260	0.2012	0.061*
C16	1.1970 (5)	1.0451 (4)	0.1562 (5)	0.0587 (15)
H16A	1.2711	1.0493	0.1571	0.070*
C17	1.1324 (5)	1.1134 (4)	0.1283 (5)	0.0572 (15)
H17A	1.1617	1.1636	0.1099	0.069*
C18	1.0246 (5)	1.1041 (3)	0.1287 (4)	0.0510 (13)
H18A	0.9808	1.1499	0.1115	0.061*
N2	0.9777 (4)	1.0327 (3)	0.1526 (4)	0.0447 (10)
C19	1.0409 (4)	0.8168 (3)	0.2200 (4)	0.0369 (10)
H19A	1.1114	0.8275	0.2600	0.044*
C20	1.0618 (4)	0.7806 (4)	0.1130 (4)	0.0500 (13)
H20A	0.9940	0.7702	0.0697	0.060*
H20B	1.1021	0.8202	0.0756	0.060*
C21	1.1247 (5)	0.7001 (4)	0.1290 (5)	0.0641 (16)
H21A	1.1341	0.6766	0.0601	0.077*
H21B	1.1954	0.7117	0.1660	0.077*
C22	1.0687 (5)	0.6387 (4)	0.1916 (6)	0.073 (2)
H22A	1.1125	0.5891	0.2032	0.088*
H22B	1.0010	0.6229	0.1514	0.088*
C23	1.0476 (5)	0.6746 (4)	0.2985 (5)	0.0632 (16)
H23A	1.0076	0.6347	0.3356	0.076*
H23B	1.1156	0.6847	0.3417	0.076*
C24	0.9849 (4)	0.7550 (3)	0.2847 (5)	0.0532 (13)
H24A	0.9135	0.7438	0.2491	0.064*
H24B	0.9774	0.7784	0.3541	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.04240 (12)	0.04233 (12)	0.03901 (12)	0.00316 (7)	−0.00362 (8)	−0.00396 (8)
I1	0.04130 (18)	0.04217 (18)	0.04169 (18)	−0.00951 (13)	0.00087 (13)	0.00790 (13)
I2	0.0576 (2)	0.0521 (2)	0.0595 (2)	0.01379 (16)	0.00647 (17)	−0.01155 (17)
P4	0.0294 (6)	0.0300 (6)	0.0323 (6)	0.0023 (4)	0.0020 (4)	0.0003 (4)
C1	0.034 (2)	0.031 (2)	0.041 (3)	0.0013 (17)	0.0018 (19)	0.0058 (19)
C2	0.047 (3)	0.043 (3)	0.047 (3)	−0.003 (2)	0.003 (2)	−0.006 (2)
C3	0.050 (3)	0.036 (3)	0.074 (4)	−0.010 (2)	−0.002 (3)	0.004 (3)
C4	0.047 (3)	0.054 (3)	0.076 (4)	−0.010 (3)	0.013 (3)	0.011 (3)
C5	0.062 (4)	0.072 (4)	0.071 (4)	−0.011 (3)	0.032 (3)	−0.002 (3)
C6	0.052 (3)	0.045 (3)	0.063 (4)	−0.011 (2)	0.026 (3)	−0.010 (3)
C7	0.029 (2)	0.037 (2)	0.036 (2)	0.0026 (17)	0.0052 (18)	0.0019 (18)
C8	0.047 (3)	0.036 (3)	0.044 (3)	0.003 (2)	0.001 (2)	0.001 (2)
C9	0.056 (3)	0.041 (3)	0.057 (3)	0.011 (2)	0.006 (3)	0.011 (3)
C10	0.066 (4)	0.051 (3)	0.045 (3)	0.016 (3)	0.000 (3)	0.015 (2)
C11	0.047 (3)	0.068 (4)	0.044 (3)	0.008 (3)	−0.009 (2)	0.004 (3)
C12	0.043 (3)	0.045 (3)	0.039 (3)	0.002 (2)	0.001 (2)	0.002 (2)
C13	0.031 (2)	0.035 (2)	0.048 (3)	0.0012 (18)	0.003 (2)	−0.011 (2)
N1	0.031 (2)	0.038 (2)	0.056 (3)	0.0032 (16)	0.0064 (18)	−0.0015 (18)
C14	0.042 (3)	0.037 (3)	0.040 (3)	0.0002 (19)	0.007 (2)	−0.006 (2)
C15	0.044 (3)	0.045 (3)	0.061 (4)	−0.002 (2)	0.005 (3)	−0.005 (2)
C16	0.049 (3)	0.063 (4)	0.069 (4)	−0.016 (3)	0.024 (3)	−0.013 (3)
C17	0.073 (4)	0.046 (3)	0.055 (3)	−0.017 (3)	0.022 (3)	−0.002 (3)
C18	0.069 (4)	0.043 (3)	0.043 (3)	−0.001 (2)	0.016 (3)	0.001 (2)
N2	0.052 (3)	0.041 (2)	0.042 (2)	0.0023 (18)	0.0090 (19)	0.0026 (18)
C19	0.033 (2)	0.037 (2)	0.040 (3)	0.0083 (18)	0.0047 (19)	−0.002 (2)
C20	0.048 (3)	0.058 (3)	0.043 (3)	0.008 (2)	0.004 (2)	−0.009 (2)
C21	0.069 (4)	0.057 (4)	0.066 (4)	0.017 (3)	0.009 (3)	−0.020 (3)
C22	0.073 (4)	0.041 (3)	0.098 (5)	0.016 (3)	−0.024 (4)	−0.017 (3)
C23	0.062 (4)	0.047 (3)	0.080 (4)	0.003 (3)	0.004 (3)	0.019 (3)
C24	0.048 (3)	0.049 (3)	0.065 (4)	0.004 (2)	0.014 (3)	0.008 (3)

Geometric parameters (Å, º) top

Hg1—P4	2.4723 (11)	C13—H13A	0.9700
Hg1—I2	2.7699 (4)	C13—H13B	0.9700
Hg1—I1	2.8036 (4)	N1—C14	1.376 (6)
Hg1—I1ⁱ	2.9667 (4)	N1—C19	1.480 (6)
I1—Hg1ⁱ	2.9667 (4)	C14—N2	1.340 (6)
P4—C7	1.818 (5)	C14—C15	1.400 (7)
P4—C1	1.829 (5)	C15—C16	1.364 (8)
P4—C13	1.858 (5)	C15—H15A	0.9300
C1—C2	1.384 (7)	C16—C17	1.387 (9)
C1—C6	1.397 (7)	C16—H16A	0.9300
C2—C3	1.390 (7)	C17—C18	1.361 (8)
C2—H2A	0.9300	C17—H17A	0.9300
C3—C4	1.373 (9)	C18—N2	1.343 (7)
C3—H3A	0.9300	C18—H18A	0.9300
C4—C5	1.387 (9)	C19—C24	1.513 (7)
C4—H4A	0.9300	C19—C20	1.525 (7)
C5—C6	1.383 (8)	C19—H19A	0.9800
C5—H5A	0.9300	C20—C21	1.519 (8)
C6—H6A	0.9300	C20—H20A	0.9700
C7—C12	1.381 (7)	C20—H20B	0.9700
C7—C8	1.393 (7)	C21—C22	1.495 (10)
C8—C9	1.389 (7)	C21—H21A	0.9700
C8—H8A	0.9300	C21—H21B	0.9700
C9—C10	1.379 (8)	C22—C23	1.522 (10)
C9—H9A	0.9300	C22—H22A	0.9700
C10—C11	1.362 (8)	C22—H22B	0.9700
C10—H10A	0.9300	C23—C24	1.515 (8)
C11—C12	1.394 (8)	C23—H23A	0.9700
C11—H11A	0.9300	C23—H23B	0.9700
C12—H12A	0.9300	C24—H24A	0.9700
C13—N1	1.455 (6)	C24—H24B	0.9700

P4—Hg1—I2	115.61 (3)	C14—N1—C13	115.1 (4)
P4—Hg1—I1	127.87 (3)	C14—N1—C19	119.8 (4)
I2—Hg1—I1	105.332 (13)	C13—N1—C19	117.7 (4)
P4—Hg1—I1ⁱ	104.03 (3)	N2—C14—N1	114.0 (4)
I2—Hg1—I1ⁱ	105.587 (13)	N2—C14—C15	121.0 (5)
I1—Hg1—I1ⁱ	94.047 (10)	N1—C14—C15	124.9 (4)
Hg1—I1—Hg1ⁱ	85.953 (10)	C16—C15—C14	119.0 (5)
C7—P4—C1	102.5 (2)	C16—C15—H15A	120.5
C7—P4—C13	107.8 (2)	C14—C15—H15A	120.5
C1—P4—C13	105.2 (2)	C15—C16—C17	120.1 (6)
C7—P4—Hg1	112.77 (15)	C15—C16—H16A	119.9
C1—P4—Hg1	109.69 (16)	C17—C16—H16A	119.9
C13—P4—Hg1	117.58 (15)	C18—C17—C16	117.6 (5)
C2—C1—C6	118.3 (5)	C18—C17—H17A	121.2
C2—C1—P4	123.9 (4)	C16—C17—H17A	121.2
C6—C1—P4	117.7 (4)	N2—C18—C17	123.8 (5)
C1—C2—C3	121.1 (5)	N2—C18—H18A	118.1
C1—C2—H2A	119.4	C17—C18—H18A	118.1
C3—C2—H2A	119.4	C14—N2—C18	118.4 (5)
C4—C3—C2	119.9 (5)	N1—C19—C24	113.4 (4)
C4—C3—H3A	120.0	N1—C19—C20	111.5 (4)
C2—C3—H3A	120.0	C24—C19—C20	111.6 (4)
C3—C4—C5	119.9 (5)	N1—C19—H19A	106.6
C3—C4—H4A	120.1	C24—C19—H19A	106.6
C5—C4—H4A	120.1	C20—C19—H19A	106.6
C6—C5—C4	120.1 (6)	C21—C20—C19	110.4 (5)
C6—C5—H5A	119.9	C21—C20—H20A	109.6
C4—C5—H5A	119.9	C19—C20—H20A	109.6
C5—C6—C1	120.6 (5)	C21—C20—H20B	109.6
C5—C6—H6A	119.7	C19—C20—H20B	109.6
C1—C6—H6A	119.7	H20A—C20—H20B	108.1
C12—C7—C8	119.9 (4)	C22—C21—C20	111.6 (5)
C12—C7—P4	120.7 (4)	C22—C21—H21A	109.3
C8—C7—P4	119.4 (4)	C20—C21—H21A	109.3
C9—C8—C7	119.6 (5)	C22—C21—H21B	109.3
C9—C8—H8A	120.2	C20—C21—H21B	109.3
C7—C8—H8A	120.2	H21A—C21—H21B	108.0
C10—C9—C8	120.0 (5)	C21—C22—C23	111.1 (5)
C10—C9—H9A	120.0	C21—C22—H22A	109.4
C8—C9—H9A	120.0	C23—C22—H22A	109.4
C11—C10—C9	120.6 (5)	C21—C22—H22B	109.4
C11—C10—H10A	119.7	C23—C22—H22B	109.4
C9—C10—H10A	119.7	H22A—C22—H22B	108.0
C10—C11—C12	120.2 (5)	C24—C23—C22	111.4 (5)
C10—C11—H11A	119.9	C24—C23—H23A	109.3
C12—C11—H11A	119.9	C22—C23—H23A	109.3
C7—C12—C11	119.8 (5)	C24—C23—H23B	109.3
C7—C12—H12A	120.1	C22—C23—H23B	109.3
C11—C12—H12A	120.1	H23A—C23—H23B	108.0
N1—C13—P4	113.9 (3)	C19—C24—C23	110.9 (5)
N1—C13—H13A	108.8	C19—C24—H24A	109.5
P4—C13—H13A	108.8	C23—C24—H24A	109.5
N1—C13—H13B	108.8	C19—C24—H24B	109.5
P4—C13—H13B	108.8	C23—C24—H24B	109.5
H13A—C13—H13B	107.7	H24A—C24—H24B	108.0

P4—Hg1—I1—Hg1ⁱ	−111.28 (3)	C8—C9—C10—C11	0.5 (9)
I2—Hg1—I1—Hg1ⁱ	107.381 (14)	C9—C10—C11—C12	−1.4 (9)
I1ⁱ—Hg1—I1—Hg1ⁱ	0.0	C8—C7—C12—C11	0.9 (7)
I2—Hg1—P4—C7	47.74 (16)	P4—C7—C12—C11	−177.3 (4)
I1—Hg1—P4—C7	−90.34 (16)	C10—C11—C12—C7	0.7 (8)
I1ⁱ—Hg1—P4—C7	163.01 (16)	C7—P4—C13—N1	118.3 (4)
I2—Hg1—P4—C1	−65.85 (15)	C1—P4—C13—N1	−132.9 (4)
I1—Hg1—P4—C1	156.07 (15)	Hg1—P4—C13—N1	−10.5 (4)
I1ⁱ—Hg1—P4—C1	49.42 (15)	P4—C13—N1—C14	−70.9 (5)
I2—Hg1—P4—C13	174.06 (19)	P4—C13—N1—C19	139.0 (4)
I1—Hg1—P4—C13	36.0 (2)	C13—N1—C14—N2	19.3 (6)
I1ⁱ—Hg1—P4—C13	−70.67 (19)	C19—N1—C14—N2	168.8 (4)
C7—P4—C1—C2	93.4 (4)	C13—N1—C14—C15	−161.7 (5)
C13—P4—C1—C2	−19.2 (5)	C19—N1—C14—C15	−12.2 (7)
Hg1—P4—C1—C2	−146.6 (4)	N2—C14—C15—C16	0.4 (8)
C7—P4—C1—C6	−82.0 (4)	N1—C14—C15—C16	−178.5 (6)
C13—P4—C1—C6	165.4 (4)	C14—C15—C16—C17	0.1 (9)
Hg1—P4—C1—C6	38.0 (4)	C15—C16—C17—C18	0.3 (9)
C6—C1—C2—C3	−1.2 (8)	C16—C17—C18—N2	−1.3 (9)
P4—C1—C2—C3	−176.6 (4)	N1—C14—N2—C18	177.8 (5)
C1—C2—C3—C4	1.9 (8)	C15—C14—N2—C18	−1.3 (7)
C2—C3—C4—C5	−1.8 (9)	C17—C18—N2—C14	1.8 (8)
C3—C4—C5—C6	1.1 (10)	C14—N1—C19—C24	160.0 (5)
C4—C5—C6—C1	−0.5 (10)	C13—N1—C19—C24	−51.3 (6)
C2—C1—C6—C5	0.5 (9)	C14—N1—C19—C20	−73.1 (6)
P4—C1—C6—C5	176.2 (5)	C13—N1—C19—C20	75.7 (5)
C1—P4—C7—C12	−50.6 (4)	N1—C19—C20—C21	176.7 (4)
C13—P4—C7—C12	60.1 (4)	C24—C19—C20—C21	−55.4 (6)
Hg1—P4—C7—C12	−168.5 (3)	C19—C20—C21—C22	56.1 (7)
C1—P4—C7—C8	131.1 (4)	C20—C21—C22—C23	−56.4 (7)
C13—P4—C7—C8	−118.2 (4)	C21—C22—C23—C24	55.7 (7)
Hg1—P4—C7—C8	13.3 (4)	N1—C19—C24—C23	−178.0 (5)
C12—C7—C8—C9	−1.7 (7)	C20—C19—C24—C23	55.1 (6)
P4—C7—C8—C9	176.5 (4)	C22—C23—C24—C19	−54.9 (7)
C7—C8—C9—C10	1.0 (8)

Symmetry code: (i) −x+2, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Hg₂I₄(C₂₄H₂₇N₂P)₂]
M_r	1657.67
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	12.5386 (7), 16.1113 (9), 12.6488 (7)
β (°)	96.773 (1)
V (Å³)	2537.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	8.58
Crystal size (mm)	0.40 × 0.35 × 0.05

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.52, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	11685, 5142, 4365
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.076, 0.98
No. of reflections	5142
No. of parameters	271
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.49, −1.15

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998) and SHELXTL (Bruker, 1997), SHELXTL.

Selected geometric parameters (Å, º) top

Hg1—P4	2.4723 (11)	Hg1—I1	2.8036 (4)
Hg1—I2	2.7699 (4)	Hg1—I1ⁱ	2.9667 (4)

P4—Hg1—I2	115.61 (3)	I2—Hg1—I1ⁱ	105.587 (13)
P4—Hg1—I1	127.87 (3)	I1—Hg1—I1ⁱ	94.047 (10)
I2—Hg1—I1	105.332 (13)	Hg1—I1—Hg1ⁱ	85.953 (10)
P4—Hg1—I1ⁱ	104.03 (3)