(2,2′-Bipyridine-κ²N,N′)dichlorido(dimethyl sulfoxide-κO)zinc(II)

In the title compound, [ZnCl₂(C₁₀H₈N₂)(C₂H₆OS)], the Zn atom is five-coordinate, forming a distorted trigonal–bipyramidal geometry involving one Cl atom, one dimethyl sulfoxide O atom and one 2,2′-bipyridine N atom in equatorial positions, with distances Zn—Cl = 2.2863 (7) Å, Zn—O = 2.1024 (15) Å and Zn—N = 2.1546 (16) Å. The axial positions are occupied by the other 2,2′-bipyridine N atom and a Cl atom, with distances N—Zn = 2.1604 (16) Å and Zn—Cl = 2.3123 (7) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.079
• Data-to-parameter ratio = 19.5

checkCIF/PLATON results

No syntax errors found



Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           27.93
           From the CIF: _diffrn_reflns_theta_full          27.93
           From the CIF: _reflns_number_total               3420
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         3609
           Completeness (_total/calc)             94.76%
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.87

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

The title compound, [ZnCl₂(Bipy)(DMSO)] (I), has triclinic (P1) symmetry. The asymetric unit of (I) contains one monomeric five–coordinate zinc complex. The Zn atom is coordinated by one 2,2'–bipyridine ligand via both N atoms, two Cl^- anions and one DMSO molecule via O atom. The complex exhibits a distorted trigonal bipyramidal geometry about the zinc atom, with atoms N2 and Cl2 in axial positions (Cl2—Zn1—N2 158.40 (5)°) and N1, Cl1 and O1 in equitorial positions. The Zn atom is 0.256 Å out of the equaitorial plane. The axial Zn—N and Zn—Cl bond lenghts are slightly longer than related equatorial bond lenghts. The Bipy ligand is slightly twisted, making an angle of 4.66° between the planes of two pyridine rings. The solid state of the molecule has a layer structure with the avrage distance of 3.397Å between 2,2'–bipyridins in closest layers. For related literature, see Lemoine et al. (2003) and Marjani et al. (2005).

Related literature

For related literature, see: Lemoine et al. (2003); Marjani et al. (2005).

S2. Experimental

To a solution of ZnCl₂ (0.136 g, 1 mmol) in freshly distilled ethanol (10 ml), was aded 2,2'–bipyridine (0.156 g, 1 mmol) and 2–mercaptopyridine (0.223 g, 2 mmol). The mixture was stirred under dinitrogen atmosphere for 4 h. Then resulted yellow suspension was filtered, washed with ethanol and dried in vacuo. The crude product was recrystalized from DMSO, yeild crystals of [ZnCl₂(C₁₀H₈N₂)(DMSO)], (0.28 g, 75.68%). M.p. = 593–598 K (decompose). Found: C, 38.66; H, 3.81; N, 6.75%. Calculated for C₁₂H₁₄C_l2N₂OSZn: C, 38.89; H, 3.81; N, 7.56%.

Computing details

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I) with the numbering scheme. Displacement ellipsoids drawn at the 50% probability level. H atoms are presented as a spheres of arbitrary radius.
	Fig. 2. The crystal packing of (I), showing its layer structure.

(2,2'-Bipyridine-κ²N,N')dichlorido(dimethyl sulfoxide-κO)zinc(II)

Crystal data

[ZnCl2(C10H8N2)(C2H6OS)]	V = 750.7 (3) Å^3
Mr = 370.61	Z = 2
Triclinic, P1	F(000) = 376
Hall symbol: -P 1	Dx = 1.640 Mg m^−3
a = 7.9553 (17) Å	Melting point: 593 K
b = 9.5504 (19) Å	Mo Kα radiation, λ = 0.71073 Å
c = 10.003 (2) Å	µ = 2.12 mm^−1
α = 84.042 (16)°	T = 293 K
β = 86.787 (17)°	Block, colourless
γ = 83.798 (17)°	0.5 × 0.5 × 0.45 mm

Data collection

Stoe IPDSII diffractometer	3420 independent reflections
Radiation source: fine–focus sealed tube	3325 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 0.15 pixels mm^-1	θmax = 27.9°, θmin = 2.1°
ω scans	h = −10→8
Absorption correction: numerical (X-RED32; Stoe & Cie, 2005)	k = −12→12
Tmin = 0.360, Tmax = 0.380	l = −13→13
7002 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)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0362P)^2 + 0.2984P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.013
3420 reflections	Δρmax = 0.54 e Å^−3
175 parameters	Δρmin = −0.48 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.127 (11)

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 > 2σ(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
C1	0.4259 (3)	−0.0788 (2)	0.2605 (2)	0.0447 (4)
H1	0.4517	−0.0535	0.1699	0.054*
C2	0.4984 (3)	−0.2067 (2)	0.3198 (3)	0.0540 (5)
H2	0.5710	−0.2666	0.2700	0.065*
C3	0.4610 (3)	−0.2435 (2)	0.4539 (3)	0.0557 (6)
H3	0.5084	−0.3289	0.4960	0.067*
C4	0.3527 (3)	−0.1527 (2)	0.5255 (2)	0.0473 (5)
H4	0.3259	−0.1761	0.6162	0.057*
C5	0.2844 (2)	−0.02600 (18)	0.45973 (18)	0.0342 (3)
C6	0.1691 (2)	0.07944 (19)	0.52816 (17)	0.0338 (3)
C7	0.1270 (3)	0.0653 (2)	0.6656 (2)	0.0471 (5)
H7	0.1680	−0.0149	0.7197	0.057*
C8	0.0234 (3)	0.1726 (3)	0.7201 (2)	0.0545 (6)
H8	−0.0066	0.1650	0.8116	0.065*
C9	−0.0351 (3)	0.2901 (3)	0.6387 (2)	0.0528 (5)
H9	−0.1031	0.3641	0.6741	0.063*
C10	0.0094 (3)	0.2960 (2)	0.5028 (2)	0.0466 (4)
H10	−0.0317	0.3748	0.4470	0.056*
C11	−0.2481 (3)	0.5039 (2)	0.1321 (3)	0.0540 (5)
H11A	−0.1767	0.5631	0.1698	0.065*
H11B	−0.3323	0.4750	0.1988	0.065*
H11C	−0.3026	0.5557	0.0562	0.065*
C12	−0.2877 (3)	0.2621 (3)	0.0277 (3)	0.0559 (5)
H12A	−0.3768	0.2600	0.0965	0.067*
H12B	−0.2441	0.1670	0.0127	0.067*
H12C	−0.3313	0.3103	−0.0541	0.067*
N1	0.32037 (19)	0.00978 (16)	0.32836 (16)	0.0354 (3)
N2	0.1092 (2)	0.19316 (16)	0.44821 (15)	0.0362 (3)
O1	−0.06662 (18)	0.26907 (18)	0.21056 (15)	0.0500 (4)
Zn1	0.19104 (2)	0.20350 (2)	0.238136 (19)	0.03318 (11)
S1	−0.12365 (6)	0.35232 (5)	0.07942 (5)	0.03847 (13)
Cl1	0.32074 (7)	0.40566 (5)	0.23911 (6)	0.04915 (15)
Cl2	0.23552 (10)	0.13441 (6)	0.02310 (5)	0.06124 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0436 (10)	0.0488 (10)	0.0407 (10)	0.0033 (8)	−0.0032 (8)	−0.0069 (8)
C2	0.0479 (11)	0.0471 (11)	0.0662 (14)	0.0107 (9)	−0.0106 (10)	−0.0135 (10)
C3	0.0575 (13)	0.0400 (10)	0.0673 (15)	0.0045 (9)	−0.0174 (11)	0.0032 (10)
C4	0.0534 (11)	0.0442 (10)	0.0432 (11)	−0.0069 (8)	−0.0113 (9)	0.0085 (8)
C5	0.0352 (8)	0.0365 (8)	0.0317 (8)	−0.0088 (6)	−0.0070 (6)	0.0004 (6)
C6	0.0350 (8)	0.0402 (8)	0.0280 (8)	−0.0122 (6)	−0.0032 (6)	−0.0016 (6)
C7	0.0514 (11)	0.0603 (12)	0.0302 (9)	−0.0148 (9)	−0.0026 (8)	0.0026 (8)
C8	0.0534 (12)	0.0832 (16)	0.0305 (9)	−0.0173 (11)	0.0039 (8)	−0.0144 (10)
C9	0.0498 (11)	0.0642 (13)	0.0477 (12)	−0.0071 (10)	0.0060 (9)	−0.0247 (10)
C10	0.0523 (11)	0.0443 (10)	0.0431 (10)	−0.0017 (8)	0.0016 (8)	−0.0094 (8)
C11	0.0581 (13)	0.0422 (10)	0.0605 (14)	−0.0043 (9)	0.0048 (10)	−0.0049 (9)
C12	0.0603 (13)	0.0563 (12)	0.0531 (13)	−0.0065 (10)	−0.0126 (10)	−0.0101 (10)
N1	0.0369 (7)	0.0368 (7)	0.0319 (7)	−0.0023 (6)	−0.0035 (6)	−0.0020 (6)
N2	0.0406 (8)	0.0377 (7)	0.0303 (7)	−0.0055 (6)	0.0006 (6)	−0.0033 (6)
O1	0.0365 (7)	0.0688 (10)	0.0399 (8)	−0.0023 (6)	−0.0026 (6)	0.0141 (7)
Zn1	0.03600 (14)	0.03394 (14)	0.02856 (14)	−0.00156 (8)	−0.00143 (8)	−0.00035 (8)
S1	0.0346 (2)	0.0440 (2)	0.0339 (2)	−0.00181 (17)	0.00193 (16)	0.00573 (17)
Cl1	0.0550 (3)	0.0430 (3)	0.0505 (3)	−0.0150 (2)	0.0055 (2)	−0.0035 (2)
Cl2	0.0945 (5)	0.0534 (3)	0.0326 (3)	0.0171 (3)	−0.0126 (3)	−0.0099 (2)

Geometric parameters (Å, º)

C1—N1	1.335 (3)	C9—H9	0.9300
C1—C2	1.383 (3)	C10—N2	1.337 (3)
C1—H1	0.9300	C10—H10	0.9300
C2—C3	1.375 (4)	C11—S1	1.773 (2)
C2—H2	0.9300	C11—H11A	0.9600
C3—C4	1.380 (3)	C11—H11B	0.9600
C3—H3	0.9300	C11—H11C	0.9600
C4—C5	1.388 (3)	C12—S1	1.768 (2)
C4—H4	0.9300	C12—H12A	0.9600
C5—N1	1.346 (2)	C12—H12B	0.9600
C5—C6	1.482 (3)	C12—H12C	0.9600
C6—N2	1.341 (2)	N1—Zn1	2.1546 (16)
C6—C7	1.393 (3)	N2—Zn1	2.1604 (16)
C7—C8	1.382 (3)	O1—S1	1.5268 (15)
C7—H7	0.9300	O1—Zn1	2.1024 (15)
C8—C9	1.371 (4)	Zn1—Cl1	2.2863 (7)
C8—H8	0.9300	Zn1—Cl2	2.3123 (7)
C9—C10	1.383 (3)
N1—C1—C2	122.4 (2)	S1—C11—H11B	109.5
N1—C1—H1	118.8	H11A—C11—H11B	109.5
C2—C1—H1	118.8	S1—C11—H11C	109.5
C3—C2—C1	118.7 (2)	H11A—C11—H11C	109.5
C3—C2—H2	120.7	H11B—C11—H11C	109.5
C1—C2—H2	120.7	S1—C12—H12A	109.5
C2—C3—C4	119.53 (19)	S1—C12—H12B	109.5
C2—C3—H3	120.2	H12A—C12—H12B	109.5
C4—C3—H3	120.2	S1—C12—H12C	109.5
C3—C4—C5	118.8 (2)	H12A—C12—H12C	109.5
C3—C4—H4	120.6	H12B—C12—H12C	109.5
C5—C4—H4	120.6	C1—N1—C5	118.86 (16)
N1—C5—C4	121.69 (18)	C1—N1—Zn1	123.98 (13)
N1—C5—C6	115.39 (15)	C5—N1—Zn1	117.07 (12)
C4—C5—C6	122.92 (17)	C10—N2—C6	118.90 (17)
N2—C6—C7	121.45 (18)	C10—N2—Zn1	123.67 (14)
N2—C6—C5	115.02 (15)	C6—N2—Zn1	117.35 (12)
C7—C6—C5	123.51 (17)	S1—O1—Zn1	120.57 (8)
C8—C7—C6	118.8 (2)	O1—Zn1—N1	132.24 (6)
C8—C7—H7	120.6	O1—Zn1—N2	82.67 (6)
C6—C7—H7	120.6	N1—Zn1—N2	75.01 (6)
C9—C8—C7	119.7 (2)	O1—Zn1—Cl1	106.16 (5)
C9—C8—H8	120.2	N1—Zn1—Cl1	117.33 (5)
C7—C8—H8	120.2	N2—Zn1—Cl1	95.19 (5)
C8—C9—C10	118.4 (2)	O1—Zn1—Cl2	93.00 (5)
C8—C9—H9	120.8	N1—Zn1—Cl2	92.94 (5)
C10—C9—H9	120.8	N2—Zn1—Cl2	158.40 (5)
N2—C10—C9	122.7 (2)	Cl1—Zn1—Cl2	106.32 (3)
N2—C10—H10	118.6	O1—S1—C12	105.02 (11)
C9—C10—H10	118.6	O1—S1—C11	104.08 (11)
S1—C11—H11A	109.5	C12—S1—C11	98.71 (12)
N1—C1—C2—C3	−0.4 (3)	C7—C6—N2—Zn1	178.26 (14)
C1—C2—C3—C4	0.1 (4)	C5—C6—N2—Zn1	−0.48 (19)
C2—C3—C4—C5	−0.1 (3)	S1—O1—Zn1—N1	−139.32 (10)
C3—C4—C5—N1	0.4 (3)	S1—O1—Zn1—N2	158.65 (12)
C3—C4—C5—C6	−179.00 (19)	S1—O1—Zn1—Cl1	65.35 (12)
N1—C5—C6—N2	3.3 (2)	S1—O1—Zn1—Cl2	−42.60 (11)
C4—C5—C6—N2	−177.26 (17)	C1—N1—Zn1—O1	114.68 (16)
N1—C5—C6—C7	−175.40 (17)	C5—N1—Zn1—O1	−61.81 (15)
C4—C5—C6—C7	4.0 (3)	C1—N1—Zn1—N2	179.75 (17)
N2—C6—C7—C8	−1.1 (3)	C5—N1—Zn1—N2	3.26 (12)
C5—C6—C7—C8	177.55 (18)	C1—N1—Zn1—Cl1	−92.14 (16)
C6—C7—C8—C9	−0.2 (3)	C5—N1—Zn1—Cl1	91.37 (13)
C7—C8—C9—C10	1.3 (3)	C1—N1—Zn1—Cl2	17.94 (16)
C8—C9—C10—N2	−1.2 (3)	C5—N1—Zn1—Cl2	−158.55 (12)
C2—C1—N1—C5	0.7 (3)	C10—N2—Zn1—O1	−47.13 (17)
C2—C1—N1—Zn1	−175.75 (16)	C6—N2—Zn1—O1	136.01 (13)
C4—C5—N1—C1	−0.7 (3)	C10—N2—Zn1—N1	175.47 (17)
C6—C5—N1—C1	178.77 (16)	C6—N2—Zn1—N1	−1.38 (12)
C4—C5—N1—Zn1	175.99 (14)	C10—N2—Zn1—Cl1	58.54 (16)
C6—C5—N1—Zn1	−4.56 (19)	C6—N2—Zn1—Cl1	−118.31 (12)
C9—C10—N2—C6	−0.1 (3)	C10—N2—Zn1—Cl2	−126.67 (16)
C9—C10—N2—Zn1	−176.92 (17)	C6—N2—Zn1—Cl2	56.5 (2)
C7—C6—N2—C10	1.2 (3)	Zn1—O1—S1—C12	129.40 (13)
C5—C6—N2—C10	−177.49 (17)	Zn1—O1—S1—C11	−127.36 (12)