Two isomorphous complexes: di­chloro­[phthalocyaninato(2–)]­tin(IV) and di­chloro­[phthalocyaninato(2–)]­germanium(IV)

Isomorphous triclinic forms of di­chloro­[phthalocyaninato(2−)]­tin(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and di­chloro­[phthalocyaninato(2−)]­ger­manium(IV), [Sn(C₃₂H₁₆N₈)Cl₂], and a monoclinic form of the latter have been obtained from the reaction of pure tin and germanium powder, respectively, with phthalo­nitrile under a stream of ICl vapour. All three crystal structures consist of centrosymmetric [SnPcCl₂] and [GePcCl₂] [Pc is phthalocyaninate(2−)] mol­ecules, which are separated but interacting. In the triclinic forms (Sn and Ge), the Pc macrocycles are not staggered but slipped, and in the monoclinic form (Ge), the mol­ecules are additionally inclined. In both cases, the central Sn or Ge atom is six-coordinated by the four iso­indole N atoms of the Pc macrocyclic ligand and by two Cl atoms (located trans) into a tetragonal–bipyramidal structure. The arrangement of [SnPcCl₂] and [GePcCl₂] mol­ecules in the crystal structure is determined mainly by intermolecular C—H...Cl, π–π and van der Waals interactions.

S1. Comment

Continuing our investigation of the synthesis and characterization of metallophthalocyaninato complexes under a stream of halogen vapour (I₂, IBr and ICl), we have obtained several metallophthalocyaninato complexes. The iodine-doped metallophthalocyaninato complexes have been reported previously (Kubiak & Janczak, 1997; Janczak et al., 1998, 1999a, 2000; Janczak & Kubiak, 1999a,b; Janczak & Idemori, 2001a; Janczak, 2003; Janczak & Kubiak, 1999c; Janczak & Idemori, 2001b; Janczak et al., 1999b; Janczak et al., 1999c; Janczak & Idemori, 2002). Quite recently, we reported two Nb(V) diphthalocyaninato complexes stapled by two interring σ C—C bonds obtained under IBr vapour (Janczak & Kubiak, 2003a) and the SbPcCl complex obtained under ICl vapour (Janczak & Kubiak, 2001).

Isostructural triclinic crystals of the SnPcCl₂, (Ia), and GePcCl₂, (IIa), complexes have been obtained directly from the reactions of powdered Sn and Ge, respectively, with phthalonitrile under a stream of ICl vapour at about 433 K, while at higher temperature (ca 453 K), the monoclinic modifications of these complexes, (Ib) and (IIb), are formed (Kubiak & Janczak, 2003). We report here the crystal structures of the triclinic forms of SnPcCl₂, (Ia), and GePcCl₂,(IIa), and the monoclinic form of GePcCl₂, (IIb).

Crystals of (I) and (II) are built up from separate but interacting SnPcCl₂ and GePcCl₂ molecules (Fig. 1). The central Sn [(Ia)] and Ge [(IIa) and (IIb)] atoms are six-coordinated by four isoindole N atoms of the [phthalocyaninato]²⁻ (Pc) macrocyclic ligand and by two Cl atoms (in a trans geometry) in a slightly distorted square bipyramid. This geometry is in agreement with the interpretation of the spectra of these compounds and related (4 + 2)-coordinated metallophthaloyaninato complexes (O'Rourke & Curran, 1970; Fujiki et al., 1986). In both cases, the slightly buckled Pc macro-ring resides on an crystallographic inversion centre. The largest displacements from the N₄-isoindole plane are observed from the outermost C atoms, C4 and C5, which are displaced by ~0.53, ~0.42 and ~0.21 Å in (Ia), (IIa) and (IIb), respectively. The Sn^IV and Ge^IV atoms are located at the centre of the N₄-isoindole square. The Sn—N and Ge—N distances in (Ia) and (IIa) are comparable to those found in their monoclinic modifications, (Ib)? (Rogers & Osborn, 1971) and (IIb), as well as to the distances observed in other Sn and Ge phthalocyaninato complexes (Ejsmont & Kubiak, 1997; Krämer, 1985; Janczak et al. 1999c; Janczak & Kubiak,1999 d).

In both (Ia) and (IIa), the axially coordinated Cl atoms are at comparable distances from the Sn and Ge atoms [2.470 (2) Å in (Ia) and 2.475 (2) Å in (IIa)]. However, in the monoclinic modifications of these complexes, the axial Sn—Cl and Ge—Cl distances are different, viz. 2.448 (2) Å (Ib)? (Rogers & Osborn, 1971) and 2.299 (1) Å in (IIb). Thus, in the triclinic modification, the Ge—Cl bond is longer than that in the monoclinic modification, which indicates the different character of the Ge—Cl bond in these modifications; the longer Ge—Cl bond in the triclinic form is more ionic than the shorter bond in the monoclinic modification. The Sn—Cl bond lengths in the two modifications of the SnPcCl₂ complex are comparable, which supports the hypothesis that these bonds have the same character?. The differences between the Ge—Cl bonds of the two modifications are consistent with far-IR spectroscopy, which shows the band at a higher frequency for the monoclinic modification (shorter Ge—Cl bond) than the band in the triclinic modification (longer Ge—Cl bond), while the Sn—Cl vibrational bands are observed at almost the same frequency (Kubiak & Janczak, 2003).

The most remarkable feature of (Ia) and (IIa) is that the [phthalocyaninato]²⁻ macrocycles are not staggered but slipped. In the monoclinic form, the molecules are additionally inclined, the angle between the N₄-isoindole planes of two neighbouring [phthalocyaninato]²⁻ macrocycles being equal to 19.2 (2)°. In the unit cell (Figs. 2a and 2 b) there are significant intermolecular C14—H14···Clⁱ [symmetry code: (i) 1 − x,1 + y,1 − z] hydrogen-bonding interactions, with H14···Clⁱ distances of 2.83 and 2.89 Å, C14···Clⁱ distances of 3.679 (2) and 3.747 (2) Å, and C4—H4···Clⁱ angles of 153 and 154° in (Ia) and (IIa), respectively. The corresponding C4—H4···Clⁱⁱ [symmetry code: (ii) 1/2 − x,-1/2 + y,1/2 − z] hydrogen-bonding interactions in (IIb) exhibit H4···Clⁱⁱ distances of 2.87 Å, C4···Clⁱⁱ distances of 3.579 (2) Å and C4—H4···Clⁱⁱ angles of 134°. This interaction causes the slight tilt of the Sn—Cl [1.3 (1)° in (Ia) and 2.5° in (Ib?); Rogers & Osborn, 1971] and Ge—Cl [0.9 (1)° in (IIa) and 1.2 (1)° in (IIb)] axis from the normal to the N2/M/N4 plane (M = Sn and Ge). The C—H···Cl intermolecular interactions that link the SnPcCl₂ and GePcCl₂ molecules into two-dimensional sheets makes the distance between the halves of the phthalocyaninato(2-) rings of neighbouring molecules shorter than ~3.4 Å. This value indicates the π–π interaction between the phenyl rings of the [phthalocyaninato]²⁻ macrocycles, since this distance is shorter than van der Waals distance for an aromatic C atom (Pauling, 1960). This π–π interaction between the phthalocyaninato rings of neighbouring molecules within the sheet (Figs. 2a and 2 b) is significant and, together with the van der Waals and C—H···Cl interactions, is responsible for the molecular arrangement and the crystal packing. The π–π intermolecular interaction is a common feature in the field of phthalocyanine chemistry, since phthalocyanine and its metal complexes tend to aggregate the molecules to each other as a result of the strong π–π intermolecular interaction (Nevin et al., 1987; Terekhov et al., 1996; Insago et al., 1997, 1998). The solubility of the SnPcCl₂ and GePcCl₂ complexes in polar solvents, such as water, methanol and ethanol, is insignificant, but they are slightly soluble in pyridine, DMF, DMSO, THF and high-boiling aromatic solvents, such as chloronaphthalene or quinoline. As can be seen, from the crystal structure architecture of SnPcCl₂ and GePcCl₂, molecules with polar Sn—Cl and Ge—Cl bonds on both sides of the [phthalocyaninato]²⁻ ring are surrounded by the hydrophobic peripheral phenyl rings of neighbouring molecules, which prevent the interactions of polar solvents with the polar Sn—Cl or Ge—Cl bonds, thus leading to the limited solubility of the crystals in polar solvents.

S2. Experimental

The triclinic and monoclinic crystals of SnPcCl₂ and GePcCl₂ were obtained by the direct reaction of the pure powdered tin or germanium with phthalonitrile under a stream of ICl vapours at about 433 and 453 K, respectively (Kubiak & Janczak, 2003). At this temperature, the liquid 1,2-dicyanobenzene undergoes catalytic tetramerization, with simultaneous transfer of two electrons from Sn (Ge) to the Pc ring, the other two electrons are transfered from Sn(Ge) to the ICl to form I⁻ and Cl⁻ ions. Crystals of SnPcCl₂ and GePcCl₂ were grown, as well as their iodine analogues (SnPcI₂ and GePcI₂).

S3. Refinement

The 960 images for six different runs covered over 95% of the Ewald sphere. H atoms were treated as riding, with C—H distances of 0.93 Å.

Computing details

Data collection: KM-4 CCD Software (Kuma, 2000) for (Ia); KM-4 CCD software (Kuma, 2000) for (IIa); KM-4 CCD Software (Kuma, 2000 for (IIb). Cell refinement: KM-4 CCD Software for (Ia), (IIb); KM-4 CCD software for (IIa). Data reduction: KM-4 CCD Software for (Ia), (IIb); KM-4 CCD software for (IIa). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecular structure of (I) and (II), showing displacement ellipsoids at the 50% probability level. H atoms are shown as spheres of arbitrary radii.
	Fig. 2. A view of the molecular packing in the unit cell, showing the intermolecular C—H···Cl interactions between the M^IVPcCl2 molecules [M = Sn (Ia) and Ge (IIa)] in the triclinic form (a) and in the monoclinic form (b).

(Ia) dichloro(phthalocyaninato(2-))tin(IV)

Crystal data

[Sn(C32H16N8)Cl2]	Z = 1
Mr = 702.12	F(000) = 348
Triclinic, P1	Dx = 1.743 Mg m^−3 Dm = 1.74 Mg m^−3 Dm measured by floatation
Hall symbol: -P 1	Melting point: sublimation K
a = 7.363 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.676 (2) Å	Cell parameters from 2604 reflections
c = 11.048 (2) Å	θ = 3.7–27.6°
α = 74.21 (3)°	µ = 1.20 mm^−1
β = 80.33 (3)°	T = 293 K
γ = 85.47 (3)°	Parallelepiped, violet
V = 669.1 (2) Å^3	0.36 × 0.18 × 0.12 mm

Data collection

Kuma KM-4 CCD area-detector diffractometer	2968 independent reflections
Radiation source: fine-focus sealed tube	2604 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 27.6°, θmin = 3.7°
ω scan	h = −9→9
Absorption correction: analytical face-indexed, SHELXTL (Sheldrick, 1990)	k = −10→11
Tmin = 0.673, Tmax = 0.870	l = −12→14
6020 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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0274P)^2 + 0.8816P] where P = (Fo^2 + 2Fc^2)/3
2968 reflections	(Δ/σ)max < 0.001
197 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.54 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
Cl	0.23050 (13)	0.14501 (11)	0.40982 (8)	0.0544 (2)
Sn	0.5000	0.0000	0.5000	0.03902 (12)
N1	0.6095 (3)	0.3194 (3)	0.5933 (2)	0.0342 (5)
N2	0.4291 (3)	0.0797 (3)	0.6619 (2)	0.0353 (6)
N3	0.2387 (4)	−0.1413 (3)	0.7897 (2)	0.0367 (6)
N4	0.3429 (4)	−0.1964 (3)	0.5833 (2)	0.0381 (6)
C1	0.5000 (4)	0.2131 (3)	0.6782 (3)	0.0326 (6)
C2	0.4346 (4)	0.2169 (4)	0.8101 (3)	0.0340 (6)
C3	0.4650 (5)	0.3226 (4)	0.8780 (3)	0.0415 (7)
H3	0.5350	0.4126	0.8400	0.050*
C4	0.3866 (5)	0.2883 (4)	1.0056 (3)	0.0478 (8)
H4	0.4068	0.3561	1.0540	0.057*
C5	0.2789 (5)	0.1557 (4)	1.0628 (3)	0.0469 (8)
H5	0.2278	0.1374	1.1481	0.056*
C6	0.2462 (4)	0.0500 (4)	0.9951 (3)	0.0404 (7)
H6	0.1737	−0.0384	1.0333	0.049*
C7	0.3261 (4)	0.0815 (4)	0.8680 (3)	0.0345 (6)
C8	0.3239 (4)	−0.0047 (4)	0.7712 (3)	0.0339 (6)
C9	0.2452 (4)	−0.2265 (4)	0.7046 (3)	0.0351 (6)
C10	0.1494 (4)	−0.3744 (3)	0.7263 (3)	0.0359 (6)
C11	0.0310 (4)	−0.4577 (4)	0.8306 (3)	0.0414 (7)
H11	−0.0019	−0.4205	0.9030	0.050*
C12	−0.0366 (5)	−0.5991 (4)	0.8226 (3)	0.0477 (8)
H12	−0.1153	−0.6583	0.8915	0.057*
C13	0.0106 (5)	−0.6544 (4)	0.7140 (4)	0.0474 (8)
H13	−0.0382	−0.7491	0.7119	0.057*
C14	0.1289 (4)	−0.5714 (4)	0.6086 (3)	0.0407 (7)
H14	0.1611	−0.6090	0.5364	0.049*
C15	0.1973 (4)	−0.4294 (3)	0.6160 (3)	0.0344 (6)
C16	0.3197 (4)	−0.3130 (3)	0.5245 (3)	0.0345 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.0634 (6)	0.0622 (6)	0.0470 (5)	0.0162 (4)	−0.0195 (4)	−0.0289 (4)
Sn	0.0534 (2)	0.03832 (19)	0.02815 (17)	−0.01040 (13)	0.00157 (12)	−0.01566 (13)
N1	0.0402 (14)	0.0342 (13)	0.0316 (13)	−0.0033 (10)	−0.0044 (10)	−0.0144 (10)
N2	0.0453 (14)	0.0364 (13)	0.0280 (12)	−0.0078 (11)	−0.0008 (10)	−0.0159 (10)
N3	0.0464 (15)	0.0377 (14)	0.0273 (12)	−0.0063 (11)	0.0000 (10)	−0.0127 (11)
N4	0.0502 (15)	0.0374 (14)	0.0294 (13)	−0.0114 (11)	0.0014 (11)	−0.0151 (11)
C1	0.0366 (16)	0.0351 (15)	0.0305 (14)	−0.0006 (12)	−0.0053 (12)	−0.0162 (12)
C2	0.0367 (16)	0.0374 (16)	0.0317 (15)	0.0045 (12)	−0.0059 (12)	−0.0166 (13)
C3	0.0464 (18)	0.0430 (17)	0.0428 (18)	0.0015 (14)	−0.0086 (14)	−0.0238 (15)
C4	0.059 (2)	0.056 (2)	0.0393 (18)	0.0059 (17)	−0.0117 (15)	−0.0304 (16)
C5	0.059 (2)	0.057 (2)	0.0280 (15)	0.0091 (17)	−0.0055 (14)	−0.0202 (15)
C6	0.0469 (18)	0.0454 (18)	0.0297 (15)	0.0044 (14)	−0.0035 (13)	−0.0141 (14)
C7	0.0394 (16)	0.0373 (16)	0.0290 (14)	0.0041 (12)	−0.0054 (12)	−0.0141 (12)
C8	0.0411 (16)	0.0362 (15)	0.0263 (14)	−0.0005 (12)	−0.0024 (11)	−0.0133 (12)
C9	0.0416 (17)	0.0353 (15)	0.0289 (14)	−0.0053 (13)	−0.0007 (12)	−0.0111 (12)
C10	0.0426 (17)	0.0315 (15)	0.0323 (15)	−0.0039 (13)	−0.0042 (12)	−0.0062 (12)
C11	0.0445 (18)	0.0387 (17)	0.0371 (16)	−0.0028 (14)	−0.0033 (13)	−0.0050 (13)
C12	0.0438 (19)	0.0412 (18)	0.050 (2)	−0.0102 (15)	−0.0038 (15)	0.0022 (15)
C13	0.049 (2)	0.0333 (17)	0.060 (2)	−0.0088 (14)	−0.0166 (16)	−0.0053 (15)
C14	0.0458 (18)	0.0349 (16)	0.0449 (18)	−0.0011 (13)	−0.0147 (14)	−0.0121 (14)
C15	0.0375 (16)	0.0341 (15)	0.0329 (15)	−0.0020 (12)	−0.0083 (12)	−0.0090 (12)
C16	0.0411 (17)	0.0331 (15)	0.0327 (15)	−0.0046 (12)	−0.0040 (12)	−0.0143 (12)

Geometric parameters (Å, º)

Sn—Cl	2.4700 (12)	C4—H4	0.9300
Sn—N2	2.063 (2)	C5—C6	1.388 (5)
Sn—N4	2.047 (3)	C5—H5	0.9300
Sn—N4^i	2.047 (3)	C6—C7	1.389 (4)
Sn—N2^i	2.063 (2)	C6—H6	0.9300
Sn—Cl^i	2.4700 (12)	C7—C8	1.465 (4)
N1—C1	1.331 (4)	C9—C10	1.456 (4)
N1—C16^i	1.332 (4)	C10—C11	1.386 (4)
N2—C1	1.372 (4)	C10—C15	1.407 (4)
N2—C8	1.374 (4)	C11—C12	1.390 (5)
N3—C8	1.335 (4)	C11—H11	0.9300
N3—C9	1.338 (4)	C12—C13	1.391 (5)
N4—C16	1.378 (4)	C12—H12	0.9300
N4—C9	1.377 (4)	C13—C14	1.391 (5)
C1—C2	1.464 (4)	C13—H13	0.9300
C2—C3	1.385 (4)	C14—C15	1.395 (4)
C2—C7	1.412 (4)	C14—H14	0.9300
C3—C4	1.390 (5)	C15—C16	1.462 (4)
C3—H3	0.9300	C16—N1^i	1.332 (4)
C4—C5	1.390 (5)
N4—Sn—N4^i	180.00 (19)	C6—C5—H5	119.3
N2—Sn—Cl	91.36 (8)	C4—C5—H5	119.3
N4—Sn—Cl	89.42 (8)	C5—C6—C7	117.4 (3)
N4—Sn—N2^i	89.91 (10)	C5—C6—H6	121.3
N4—Sn—Cl^i	90.58 (8)	C7—C6—H6	121.3
N4^i—Sn—N2^i	90.09 (10)	C6—C7—C2	121.1 (3)
N4—Sn—N2	90.09 (10)	C6—C7—C8	131.8 (3)
N4^i—Sn—N2	89.91 (10)	C2—C7—C8	107.1 (2)
N2^i—Sn—N2	180.00 (6)	N3—C8—N2	127.9 (3)
N4^i—Sn—Cl	90.58 (8)	N3—C8—C7	125.3 (3)
N2^i—Sn—Cl	88.64 (8)	N2—C8—C7	106.8 (2)
N4^i—Sn—Cl^i	89.42 (8)	N3—C9—N4	128.2 (3)
N2^i—Sn—Cl^i	91.36 (8)	N3—C9—C10	125.1 (3)
N2—Sn—Cl^i	88.64 (8)	N4—C9—C10	106.7 (2)
Cl—Sn—Cl^i	180.00 (4)	C11—C10—C15	121.4 (3)
C1—N1—C16^i	126.5 (2)	C11—C10—C9	131.1 (3)
C1—N2—C8	112.1 (2)	C15—C10—C9	107.5 (2)
C1—N2—Sn	123.65 (19)	C10—C11—C12	117.2 (3)
C8—N2—Sn	123.81 (19)	C10—C11—H11	121.4
C8—N3—C9	125.9 (2)	C12—C11—H11	121.4
C16—N4—C9	111.8 (2)	C13—C12—C11	121.7 (3)
C16—N4—Sn	124.26 (19)	C13—C12—H12	119.2
C9—N4—Sn	123.89 (19)	C11—C12—H12	119.2
N1—C1—N2	127.9 (3)	C12—C13—C14	121.6 (3)
N1—C1—C2	125.3 (3)	C12—C13—H13	119.2
N2—C1—C2	106.8 (2)	C14—C13—H13	119.2
C3—C2—C7	121.1 (3)	C13—C14—C15	117.0 (3)
C3—C2—C1	131.6 (3)	C13—C14—H14	121.5
C7—C2—C1	107.3 (2)	C15—C14—H14	121.5
C2—C3—C4	117.2 (3)	C14—C15—C10	121.1 (3)
C2—C3—H3	121.4	C14—C15—C16	131.6 (3)
C4—C3—H3	121.4	C10—C15—C16	107.4 (2)
C5—C4—C3	121.8 (3)	N1^i—C16—N4	127.6 (3)
C5—C4—H4	119.1	N1^i—C16—C15	125.9 (3)
C3—C4—H4	119.1	N4—C16—C15	106.5 (2)
C6—C5—C4	121.3 (3)

Symmetry code: (i) −x+1, −y, −z+1.

(IIa) dichloro(phthalocyaninato(2-))germanium(IV)

Crystal data

[Ge(C32H16N8)Cl2]	Z = 1
Mr = 656.02	F(000) = 330
Triclinic, P1	Dx = 1.635 Mg m^−3 Dm = 1.63 Mg m^−3 Dm measured by floatation
Hall symbol: -P 1	Melting point: sublimation K
a = 7.365 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.704 (2) Å	Cell parameters from 3082 reflections
c = 10.966 (2) Å	θ = 2.8–28°
α = 73.85 (3)°	µ = 1.39 mm^−1
β = 80.61 (3)°	T = 293 K
γ = 86.39 (3)°	Parallelepiped, violet
V = 666.1 (2) Å^3	0.36 × 0.25 × 0.18 mm

Data collection

KUMA KM-4 CCD area-detector diffractometer	3082 independent reflections
Radiation source: fine-focus sealed tube	1936 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 28.0°, θmin = 2.8°
ω scan	h = −9→9
Absorption correction: analytical face-indexed, SHELXTL (Sheldrick, 1990)	k = −11→10
Tmin = 0.634, Tmax = 0.787	l = −14→13
5657 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.151	w = 1/[σ^2(Fo^2) + (0.0686P)^2 + 0.2297P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3082 reflections	Δρmax = 0.35 e Å^−3
197 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.110 (10)

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
Ge	0.5000	0.0000	0.5000	0.0816 (3)
Cl	0.22982 (11)	0.14435 (10)	0.41116 (8)	0.0687 (3)
N1	0.3866 (5)	−0.3169 (4)	0.4072 (3)	0.0841 (9)
N2	0.5651 (4)	−0.0748 (4)	0.3434 (3)	0.0763 (8)
N3	0.7611 (4)	0.1418 (4)	0.2114 (3)	0.0796 (9)
N4	0.6527 (5)	0.1896 (4)	0.4186 (3)	0.0851 (9)
C1	0.4963 (5)	−0.2066 (4)	0.3231 (4)	0.0766 (10)
C2	0.5612 (5)	−0.2122 (5)	0.1943 (4)	0.0825 (10)
C3	0.5343 (6)	−0.3205 (5)	0.1253 (4)	0.0883 (11)
H3	0.4639	−0.4112	0.1641	0.106*
C4	0.6131 (7)	−0.2898 (6)	0.0008 (5)	0.1025 (14)
H4	0.5947	−0.3589	−0.0470	0.123*
C5	0.7237 (6)	−0.1532 (5)	−0.0578 (4)	0.0918 (12)
H5	0.7770	−0.1334	−0.1434	0.110*
C6	0.7514 (6)	−0.0521 (5)	0.0105 (4)	0.0840 (11)
H6	0.8263	0.0359	−0.0272	0.101*
C7	0.6693 (6)	−0.0794 (5)	0.1350 (4)	0.0814 (10)
C8	0.6717 (5)	0.0053 (4)	0.2335 (4)	0.0759 (9)
C9	0.7496 (5)	0.2191 (4)	0.2967 (4)	0.0759 (9)
C10	0.8628 (7)	0.3607 (6)	0.2798 (4)	0.1078 (18)
C11	0.9684 (6)	0.4542 (5)	0.1683 (5)	0.0928 (13)
H11	0.9943	0.4233	0.0926	0.111*
C12	1.0318 (6)	0.5973 (5)	0.1796 (5)	0.0923 (12)
H12	1.1077	0.6610	0.1102	0.111*
C13	0.9866 (6)	0.6470 (5)	0.2889 (5)	0.0979 (14)
H13	1.0386	0.7394	0.2936	0.117*
C14	0.8694 (6)	0.5657 (5)	0.3890 (5)	0.0850 (11)
H14	0.8354	0.6043	0.4606	0.102*
C15	0.7998 (5)	0.4252 (5)	0.3854 (4)	0.0799 (10)
C16	0.6775 (5)	0.3097 (4)	0.4740 (4)	0.0777 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge	0.0903 (4)	0.0753 (4)	0.0770 (4)	−0.0119 (3)	0.0052 (3)	−0.0250 (3)
Cl	0.0738 (5)	0.0686 (5)	0.0657 (5)	0.0019 (4)	−0.0033 (4)	−0.0263 (4)
N1	0.086 (2)	0.0753 (19)	0.096 (2)	−0.0091 (16)	−0.0015 (18)	−0.0380 (17)
N2	0.0773 (18)	0.0684 (17)	0.079 (2)	−0.0123 (14)	−0.0064 (15)	−0.0133 (15)
N3	0.086 (2)	0.0721 (19)	0.079 (2)	−0.0150 (15)	0.0044 (16)	−0.0242 (16)
N4	0.098 (2)	0.078 (2)	0.078 (2)	−0.0108 (17)	0.0009 (17)	−0.0272 (16)
C1	0.078 (2)	0.068 (2)	0.080 (2)	0.0010 (17)	−0.0023 (19)	−0.0213 (18)
C2	0.072 (2)	0.080 (2)	0.096 (3)	0.0054 (18)	−0.010 (2)	−0.029 (2)
C3	0.094 (3)	0.095 (3)	0.086 (3)	−0.007 (2)	−0.001 (2)	−0.046 (2)
C4	0.115 (3)	0.113 (3)	0.094 (3)	0.006 (3)	−0.018 (3)	−0.053 (3)
C5	0.102 (3)	0.100 (3)	0.069 (2)	−0.004 (2)	0.009 (2)	−0.027 (2)
C6	0.093 (3)	0.077 (2)	0.078 (2)	0.0100 (19)	−0.004 (2)	−0.0229 (19)
C7	0.087 (2)	0.072 (2)	0.086 (3)	0.0045 (19)	−0.003 (2)	−0.029 (2)
C8	0.081 (2)	0.071 (2)	0.072 (2)	−0.0040 (17)	−0.0017 (18)	−0.0188 (17)
C9	0.081 (2)	0.066 (2)	0.071 (2)	−0.0045 (17)	0.0017 (18)	−0.0110 (17)
C10	0.142 (4)	0.102 (3)	0.081 (3)	−0.075 (3)	0.036 (3)	−0.040 (2)
C11	0.078 (2)	0.073 (2)	0.107 (3)	−0.0114 (19)	0.005 (2)	0.000 (2)
C12	0.087 (3)	0.084 (3)	0.100 (3)	−0.014 (2)	−0.013 (2)	−0.012 (2)
C13	0.094 (3)	0.062 (2)	0.136 (4)	−0.001 (2)	−0.040 (3)	−0.012 (3)
C14	0.086 (2)	0.068 (2)	0.099 (3)	−0.0039 (19)	−0.023 (2)	−0.014 (2)
C15	0.085 (2)	0.074 (2)	0.079 (2)	−0.0049 (18)	−0.0130 (19)	−0.0173 (19)
C16	0.086 (2)	0.070 (2)	0.076 (2)	−0.0085 (18)	−0.0063 (19)	−0.0206 (18)

Geometric parameters (Å, º)

Ge—Cl	2.4747 (11)	C4—H4	0.9300
Ge—N2	1.979 (3)	C5—C6	1.347 (6)
Ge—N4	1.968 (3)	C5—H5	0.9300
Ge—N2^i	1.979 (3)	C6—C7	1.361 (6)
Ge—Cl^i	2.4747 (11)	C6—H6	0.9300
Ge—N4^i	1.968 (3)	C7—C8	1.470 (6)
N1—C16^i	1.329 (5)	C9—C10	1.484 (5)
N1—C1	1.337 (5)	C10—C11	1.406 (5)
N2—C8	1.360 (5)	C10—C15	1.423 (6)
N2—C1	1.369 (5)	C11—C12	1.401 (6)
N3—C9	1.286 (5)	C11—H11	0.9300
N3—C8	1.337 (5)	C12—C13	1.369 (7)
N4—C9	1.373 (5)	C12—H12	0.9300
N4—C16	1.381 (5)	C13—C14	1.337 (6)
C1—C2	1.428 (6)	C13—H13	0.9300
C2—C7	1.387 (6)	C14—C15	1.368 (5)
C2—C3	1.404 (6)	C14—H14	0.9300
C3—C4	1.353 (6)	C15—C16	1.432 (5)
C3—H3	0.9300	C16—N1^i	1.329 (5)
C4—C5	1.420 (7)
N2—Ge—Cl	89.09 (10)	C6—C5—H5	119.9
N4—Ge—Cl	90.71 (11)	C4—C5—H5	119.9
N4^i—Ge—N2	89.83 (13)	C5—C6—C7	119.7 (4)
N2—Ge—N4	90.17 (13)	C5—C6—H6	120.1
N4^i—Ge—N4	180.00 (13)	C7—C6—H6	120.1
N4^i—Ge—N2^i	90.17 (13)	C6—C7—C2	121.2 (4)
N4—Ge—N2^i	89.83 (13)	C6—C7—C8	133.0 (4)
N2—Ge—N2^i	180.0	C2—C7—C8	105.8 (3)
N4^i—Ge—Cl	89.29 (11)	N3—C8—N2	128.0 (4)
N2^i—Ge—Cl	90.91 (10)	N3—C8—C7	123.3 (3)
N4^i—Ge—Cl^i	90.71 (11)	N2—C8—C7	108.7 (3)
N4—Ge—Cl^i	89.29 (11)	N3—C9—N4	131.4 (3)
N2—Ge—Cl^i	90.91 (10)	N3—C9—C10	122.7 (3)
N2^i—Ge—Cl^i	89.09 (10)	N4—C9—C10	105.7 (3)
Cl—Ge—Cl^i	180.00 (4)	C11—C10—C15	120.2 (4)
C16^i—N1—C1	123.2 (3)	C11—C10—C9	129.6 (4)
C8—N2—C1	108.7 (3)	C15—C10—C9	107.2 (3)
C8—N2—Ge	125.2 (3)	C12—C11—C10	115.2 (5)
C1—N2—Ge	125.8 (3)	C12—C11—H11	122.4
C9—N3—C8	121.8 (3)	C10—C11—H11	122.4
C9—N4—C16	110.9 (3)	C13—C12—C11	122.6 (4)
C9—N4—Ge	123.3 (3)	C13—C12—H12	118.7
C16—N4—Ge	125.7 (3)	C11—C12—H12	118.7
N1—C1—N2	127.4 (3)	C14—C13—C12	121.5 (4)
N1—C1—C2	123.2 (4)	C14—C13—H13	119.3
N2—C1—C2	109.4 (3)	C12—C13—H13	119.3
C7—C2—C3	119.8 (4)	C13—C14—C15	119.6 (5)
C7—C2—C1	107.5 (4)	C13—C14—H14	120.2
C3—C2—C1	132.7 (4)	C15—C14—H14	120.2
C4—C3—C2	118.4 (4)	C14—C15—C10	119.9 (4)
C4—C3—H3	120.8	C14—C15—C16	134.0 (4)
C2—C3—H3	120.8	C10—C15—C16	106.0 (3)
C3—C4—C5	120.8 (4)	N1^i—C16—N4	127.6 (3)
C3—C4—H4	119.6	N1^i—C16—C15	123.2 (4)
C5—C4—H4	119.6	N4—C16—C15	109.0 (3)
C6—C5—C4	120.1 (4)

Symmetry code: (i) −x+1, −y, −z+1.

(IIb) dichloro(phthalocyaninato(2-))germanium(IV)

Crystal data

[Ge(C32H16N8)Cl2]	F(000) = 660
Mr = 656.02	Dx = 1.593 Mg m^−3 Dm = 1.59 Mg m^−3 Dm measured by floatation in CHCl3/CHBr3
Monoclinic, P21/n	Melting point: sublimation K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.124 (2) Å	Cell parameters from 2102 reflections
b = 14.810 (3) Å	θ = 3.4–29°
c = 10.233 (2) Å	µ = 1.36 mm^−1
β = 98.50 (3)°	T = 293 K
V = 1367.6 (5) Å^3	Parallelepiped, violet
Z = 2	0.30 × 0.22 × 0.18 mm

Data collection

Kuma KM-4 CCD area-detector diffractometer	3561 independent reflections
Radiation source: fine-focus sealed tube	2102 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 1024x1024 with blocks 2x2 pixels mm^-1	θmax = 29.0°, θmin = 3.4°
ω–scan	h = −12→10
Absorption correction: analytical face-indexed, SHELXTL (Sheldrick, 1990)	k = −20→20
Tmin = 0.687, Tmax = 0.792	l = −13→13
12868 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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.098	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0407P)^2 + 0.227P] where P = (Fo^2 + 2Fc^2)/3
3561 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 1.04 e Å^−3
0 restraints	Δρmin = −0.33 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
Ge	0.0000	0.0000	0.0000	0.04143 (13)
Cl	−0.05960 (7)	−0.03141 (5)	0.20579 (6)	0.04980 (18)
N1	0.3453 (2)	−0.07923 (15)	0.1058 (2)	0.0459 (5)
N2	0.0966 (2)	−0.11822 (14)	0.00139 (19)	0.0428 (5)
N3	−0.1123 (2)	−0.21143 (14)	−0.0925 (2)	0.0447 (5)
N4	−0.1869 (2)	−0.05404 (13)	−0.0811 (2)	0.0418 (5)
C1	0.2432 (3)	−0.13618 (17)	0.0539 (2)	0.0428 (6)
C2	0.2702 (3)	−0.23225 (17)	0.0407 (2)	0.0434 (6)
C3	0.3958 (3)	−0.28385 (19)	0.0776 (3)	0.0534 (7)
H3	0.4844	−0.2582	0.1171	0.064*
C4	0.3830 (4)	−0.3763 (2)	0.0526 (3)	0.0640 (8)
H4	0.4654	−0.4131	0.0755	0.077*
C5	0.2510 (4)	−0.4147 (2)	−0.0054 (3)	0.0654 (8)
H5	0.2469	−0.4767	−0.0197	0.078*
C6	0.1245 (3)	−0.36329 (19)	−0.0427 (3)	0.0571 (7)
H6	0.0360	−0.3893	−0.0818	0.069*
C7	0.1369 (3)	−0.27045 (18)	−0.0186 (2)	0.0459 (6)
C8	0.0292 (3)	−0.19836 (17)	−0.0418 (2)	0.0433 (6)
C9	−0.2107 (3)	−0.14518 (17)	−0.1103 (2)	0.0431 (6)
C10	−0.3645 (3)	−0.15829 (18)	−0.1654 (2)	0.0434 (6)
C11	−0.4451 (3)	−0.23517 (19)	−0.2081 (2)	0.0484 (6)
H11	−0.4004	−0.2917	−0.2039	0.058*
C12	−0.5941 (3)	−0.2249 (2)	−0.2571 (3)	0.0560 (7)
H12	−0.6502	−0.2753	−0.2870	0.067*
C13	−0.6614 (3)	−0.1396 (2)	−0.2621 (3)	0.0551 (7)
H13	−0.7617	−0.1345	−0.2949	0.066*
C14	−0.5828 (3)	−0.0633 (2)	−0.2197 (3)	0.0503 (7)
H14	−0.6281	−0.0069	−0.2233	0.060*
C15	−0.4328 (3)	−0.07338 (18)	−0.1711 (2)	0.0448 (6)
C16	−0.3194 (3)	−0.00868 (17)	−0.1173 (2)	0.0431 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ge	0.0360 (2)	0.0393 (2)	0.0490 (2)	0.00555 (17)	0.00630 (16)	−0.00128 (17)
Cl	0.0503 (4)	0.0506 (4)	0.0501 (4)	0.0052 (3)	0.0124 (3)	0.0003 (3)
N1	0.0403 (12)	0.0444 (14)	0.0530 (13)	0.0093 (11)	0.0062 (10)	−0.0006 (10)
N2	0.0414 (12)	0.0415 (13)	0.0460 (11)	0.0058 (10)	0.0078 (10)	−0.0024 (10)
N3	0.0444 (12)	0.0432 (12)	0.0468 (12)	0.0047 (10)	0.0072 (10)	−0.0019 (10)
N4	0.0387 (11)	0.0375 (12)	0.0494 (12)	0.0046 (10)	0.0073 (9)	−0.0013 (9)
C1	0.0412 (15)	0.0392 (15)	0.0477 (14)	0.0101 (12)	0.0061 (12)	−0.0005 (11)
C2	0.0484 (15)	0.0405 (14)	0.0424 (13)	0.0093 (12)	0.0105 (12)	0.0020 (11)
C3	0.0539 (17)	0.0537 (17)	0.0508 (15)	0.0181 (14)	0.0019 (13)	−0.0021 (13)
C4	0.070 (2)	0.058 (2)	0.0631 (18)	0.0279 (17)	0.0034 (16)	−0.0025 (15)
C5	0.084 (2)	0.0419 (17)	0.0685 (19)	0.0195 (17)	0.0067 (17)	−0.0090 (14)
C6	0.0631 (19)	0.0443 (17)	0.0622 (17)	0.0089 (14)	0.0036 (14)	−0.0093 (13)
C7	0.0506 (16)	0.0446 (15)	0.0437 (14)	0.0074 (13)	0.0107 (12)	−0.0023 (12)
C8	0.0463 (15)	0.0424 (15)	0.0416 (13)	0.0068 (12)	0.0084 (11)	−0.0013 (11)
C9	0.0425 (15)	0.0418 (15)	0.0454 (14)	0.0003 (12)	0.0076 (11)	−0.0017 (11)
C10	0.0395 (14)	0.0478 (16)	0.0435 (14)	0.0003 (12)	0.0082 (11)	−0.0006 (12)
C11	0.0453 (15)	0.0483 (16)	0.0524 (15)	−0.0018 (13)	0.0100 (13)	−0.0025 (13)
C12	0.0481 (16)	0.0582 (19)	0.0625 (17)	−0.0096 (14)	0.0104 (14)	−0.0050 (14)
C13	0.0364 (14)	0.067 (2)	0.0618 (17)	−0.0019 (14)	0.0054 (13)	0.0032 (15)
C14	0.0432 (15)	0.0524 (17)	0.0551 (16)	0.0094 (13)	0.0065 (13)	0.0046 (13)
C15	0.0411 (14)	0.0486 (16)	0.0452 (14)	0.0021 (12)	0.0080 (12)	0.0025 (11)
C16	0.0383 (13)	0.0490 (17)	0.0422 (13)	0.0075 (12)	0.0063 (11)	0.0032 (12)

Geometric parameters (Å, º)

Ge—Cl	2.2989 (8)	C4—H4	0.9300
Ge—N2	1.959 (2)	C5—C6	1.387 (4)
Ge—N4	1.954 (2)	C5—H5	0.9300
Ge—N2^i	1.959 (2)	C6—C7	1.398 (4)
Ge—N4^i	1.954 (2)	C6—H6	0.9300
Ge—Cl^i	2.2989 (8)	C7—C8	1.446 (3)
N1—C1	1.309 (3)	C9—C10	1.447 (4)
N1—C16^i	1.332 (3)	C10—C11	1.390 (4)
N2—C8	1.379 (3)	C10—C15	1.401 (4)
N2—C1	1.392 (3)	C11—C12	1.386 (4)
N3—C9	1.324 (3)	C11—H11	0.9300
N3—C8	1.333 (3)	C12—C13	1.403 (4)
N4—C16	1.385 (3)	C12—H12	0.9300
N4—C9	1.392 (3)	C13—C14	1.373 (4)
C1—C2	1.454 (3)	C13—H13	0.9300
C2—C3	1.383 (3)	C14—C15	1.393 (3)
C2—C7	1.397 (4)	C14—H14	0.9300
C3—C4	1.394 (4)	C15—C16	1.458 (4)
C3—H3	0.9300	C16—N1^i	1.332 (3)
C4—C5	1.385 (4)
N2—Ge—Cl	88.83 (6)	C4—C5—H5	119.1
N4—Ge—Cl	89.80 (6)	C6—C5—H5	119.1
N2—Ge—N4	90.02 (8)	C5—C6—C7	116.7 (3)
N4—Ge—N2^i	89.98 (8)	C5—C6—H6	121.7
N4^i—Ge—N2	89.98 (8)	C7—C6—H6	121.7
N4^i—Ge—N4	180.00 (15)	C2—C7—C6	121.1 (2)
N4^i—Ge—N2^i	90.02 (8)	C2—C7—C8	107.4 (2)
N2^i—Ge—N2	180.00 (15)	C6—C7—C8	131.5 (3)
N4^i—Ge—Cl	90.20 (6)	N3—C8—N2	127.6 (2)
N2^i—Ge—Cl	91.17 (6)	N3—C8—C7	123.5 (2)
N4^i—Ge—Cl^i	89.80 (6)	N2—C8—C7	108.9 (2)
N4—Ge—Cl^i	90.20 (6)	N3—C9—N4	127.4 (2)
N2^i—Ge—Cl^i	88.83 (6)	N3—C9—C10	123.6 (2)
N2—Ge—Cl^i	91.17 (6)	N4—C9—C10	109.0 (2)
Cl—Ge—Cl^i	180.00 (5)	C11—C10—C15	120.7 (2)
C1—N1—C16^i	122.7 (2)	C11—C10—C9	132.1 (2)
C8—N2—C1	108.5 (2)	C15—C10—C9	107.2 (2)
C8—N2—Ge	126.03 (17)	C12—C11—C10	118.0 (3)
C1—N2—Ge	125.40 (17)	C12—C11—H11	121.0
C9—N3—C8	123.0 (2)	C10—C11—H11	121.0
C16—N4—C9	108.1 (2)	C11—C12—C13	120.8 (3)
C16—N4—Ge	125.96 (17)	C11—C12—H12	119.6
C9—N4—Ge	125.93 (16)	C13—C12—H12	119.6
N1—C1—N2	128.2 (2)	C14—C13—C12	121.6 (3)
N1—C1—C2	123.2 (2)	C14—C13—H13	119.2
N2—C1—C2	108.5 (2)	C12—C13—H13	119.2
C3—C2—C7	121.9 (2)	C13—C14—C15	117.7 (3)
C3—C2—C1	131.3 (3)	C13—C14—H14	121.2
C7—C2—C1	106.8 (2)	C15—C14—H14	121.2
C2—C3—C4	116.7 (3)	C14—C15—C10	121.2 (3)
C2—C3—H3	121.7	C14—C15—C16	132.1 (3)
C4—C3—H3	121.7	C10—C15—C16	106.7 (2)
C5—C4—C3	121.7 (3)	N1^i—C16—N4	127.6 (2)
C5—C4—H4	119.1	N1^i—C16—C15	123.4 (2)
C3—C4—H4	119.1	N4—C16—C15	109.0 (2)
C4—C5—C6	121.9 (3)

Symmetry code: (i) −x, −y, −z.