catena-Poly[[(2,2′-dimethyl-4,4′-bi-1,3-thia­zole-κ²N,N′)cadmium]-di-μ-bromido]

In the title coordination polymer, [CdBr₂(C₈H₈N₂S₂)]_n, the Cd^II atom is six-coordinated in a distorted octa­hedral geometry by two N atoms from a 2,2′-dimethyl-4,4′-bi-1,3-thia­zole ligand and four bridging Br atoms. The bridging function of the Br atoms leads to a chain structure along [100]. Inter­chain C—H...Br hydrogen bonds and π–π contacts between the thia­zole rings [centroid–centroid distances = 3.810 (5) and 3.679 (5) Å] are observed.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.015 Å
• R factor = 0.081
• wR factor = 0.232
• Data-to-parameter ratio = 25.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          3
PLAT972_ALERT_2_B Large Calcd. Non-Metal Negative Residual Density      -3.04 eA-3
PLAT972_ALERT_2_B Large Calcd. Non-Metal Negative Residual Density      -2.98 eA-3
PLAT972_ALERT_2_B Large Calcd. Non-Metal Negative Residual Density      -2.93 eA-3
PLAT972_ALERT_2_B Large Calcd. Non-Metal Negative Residual Density      -2.86 eA-3

Alert level C
DIFMN02_ALERT_2_C  The minimum difference density is < -0.1*ZMAX*0.75
            _refine_diff_density_min given =     -4.781
            Test value =     -3.600
DIFMN03_ALERT_1_C  The minimum difference density is < -0.1*ZMAX*0.75
            The relevant atom site should be identified.
RINTA01_ALERT_3_C  The value of Rint is greater than 0.12
            Rint given   0.160
PLAT020_ALERT_3_C The value of Rint is greater than 0.12 .........       0.16
PLAT098_ALERT_2_C Large Reported Min.  (Negative) Residual Density      -4.78 eA-3
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         15
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         24
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1
PLAT918_ALERT_3_C Reflection(s) # with I(obs) much smaller I(calc)          3
PLAT971_ALERT_2_C Large Calcd. Non-Metal Positive Residual Density       1.84 eA-3
PLAT972_ALERT_2_C Large Calcd. Non-Metal Negative Residual Density      -1.64 eA-3

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT Unusually Large.       0.15
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cd1    --  Br1_b   ..       6.83 su
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C1
PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C8

   0 ALERT level A = Most likely a serious problem - resolve or explain
   5 ALERT level B = A potentially serious problem, consider carefully
  11 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

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

---

S1. Comment

Recently, we reported the synthesis and crystal structures of [HgI₂(dm4bt)] (Abedi & Yahyazade Bali, 2010) and [HgBr₂(dm4bt)] (Abedi, 2011) (dm4bt = 2,2'-dimethyl-4,4'-bi-1,3-thiazole). Dm4bt is a good bidentate ligand, and numerous complexes with dm4bt have been prepared, such as that of zinc (Khavasi et al., 2008), thallium (Notash et al., 2008), cadmium (Notash et al., 2009), mercury (Safari et al., 2009) and copper (Al-Hashemi et al., 2009, 2010). For further investigation of dm4bt, we synthesized the title complex and report herein its crystal structure.

In the title coordination polymer (Fig. 1), the Cd^II atom is six-coordinated in a distorted octahedral geometry by two N atoms from a dm4bt ligand and four bridging Br atoms (Table 1). The bridging function of the bromide atoms leads to a one-dimensional chain structure along [1 0 0] (Fig. 2).

In the crystal structure, intermolecular C—H···Br hydrogen bonds (Table 2) and π–π contacts (Fig. 2) between the thiazole rings, Cg4···Cg5ⁱ = 3.810 (5) and Cg5···Cg5ⁱⁱ = 3.679 (5) Å [symmetry codes: (i) 1-x, 2-y, 1-z; (ii) -x, 2-y, 1-z. Cg4 and Cg5 are the centroids of the S1/C2/N1/C4/C3 and S2/C6/C5/N2/C7 rings], stabilize the structure.

Related literature

For metal complexes with 2,2'-dimethyl-4,4'-bi-1,3-thiazole, see: Abedi (2011); Abedi & Yahyazade Bali (2010); Al-Hashemi et al. (2009, 2010); Khavasi et al. (2008); Notash et al. (2008, 2009); Safari et al. (2009).

S2. Experimental

For the preparation of the title compound, a solution of dm4bt (0.26 g, 1.3 mmol) in methanol (15 ml) was added to a solution of CdBr₂.4H₂O (0.44 g, 1.3 mmol) in methanol (15 ml) at room temperature. The suitable crystals for X-ray diffraction experiment were obtained by methanol diffusion into a colorless solution in DMF. The crystals were isolated after one week (yield: 0.45 g, 73.9%).

S3. Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 (CH) and 0.96 (CH₃) Å and with U_iso(H) = 1.2(1.5 for methyl)U_eq(C). The highest residual electron density was found at 0.89 Å from Cd1 atom and the deepest hole at 0.88 Å from Cd1 atom.

Computing details

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. Part of the chain structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (a) -x, 1-y, 1-z; (b) 1-x, 1-y, 1-z.]
	Fig. 2. The packing diagram for the title compound.

catena-Poly[[(2,2'-dimethyl-4,4'-bi-1,3-thiazole- κ²N,N')cadmium]-di-µ-bromido]

Crystal data

[CdBr2(C8H8N2S2)]	Z = 2
Mr = 468.51	F(000) = 440
Triclinic, P1	Dx = 2.454 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.1936 (10) Å	Cell parameters from 7003 reflections
b = 9.5775 (11) Å	θ = 2.2–29.2°
c = 10.4218 (14) Å	µ = 8.32 mm^−1
α = 112.714 (9)°	T = 298 K
β = 104.149 (11)°	Block, colorless
γ = 92.68 (1)°	0.28 × 0.18 × 0.13 mm
V = 634.20 (16) Å^3

Data collection

Bruker APEX CCD diffractometer	3400 independent reflections
Radiation source: fine-focus sealed tube	2495 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.160
ϕ and ω scans	θmax = 29.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.180, Tmax = 0.340	k = −13→12
7003 measured reflections	l = −14→14

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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.232	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.149P)^2] where P = (Fo^2 + 2Fc^2)/3
3400 reflections	(Δ/σ)max = 0.005
136 parameters	Δρmax = 2.22 e Å^−3
0 restraints	Δρmin = −4.78 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2848 (18)	0.4579 (13)	0.0750 (12)	0.050 (3)
H1A	0.1742	0.3946	0.0710	0.060*
H1B	0.4015	0.4317	0.1221	0.060*
H1C	0.2854	0.4415	−0.0218	0.060*
C2	0.2745 (13)	0.6214 (11)	0.1579 (9)	0.0338 (18)
C3	0.2515 (14)	0.8908 (11)	0.2347 (10)	0.0362 (19)
H3	0.2437	0.9918	0.2478	0.043*
C4	0.2597 (11)	0.8389 (10)	0.3383 (9)	0.0277 (16)
C5	0.2502 (11)	0.9274 (9)	0.4849 (9)	0.0262 (15)
C6	0.2499 (13)	1.0824 (10)	0.5464 (10)	0.0342 (18)
H6	0.2571	1.1478	0.5004	0.041*
C7	0.2327 (13)	0.9521 (11)	0.7021 (10)	0.0332 (18)
C8	0.220 (2)	0.9124 (16)	0.8265 (12)	0.057 (3)
H8C	0.2207	0.8045	0.7987	0.068*
H8B	0.1028	0.9388	0.8511	0.068*
H8A	0.3300	0.9686	0.9089	0.068*
N1	0.2720 (11)	0.6838 (9)	0.2955 (8)	0.0298 (14)
N2	0.2379 (10)	0.8540 (8)	0.5760 (8)	0.0282 (14)
Cd1	0.24677 (9)	0.58678 (7)	0.47579 (7)	0.0302 (2)
Br1	0.36362 (13)	0.31498 (11)	0.34631 (11)	0.0364 (3)
Br2	0.14395 (13)	0.49070 (11)	0.67291 (10)	0.0353 (3)
S1	0.2574 (4)	0.7476 (3)	0.0763 (2)	0.0420 (6)
S2	0.2347 (4)	1.1375 (3)	0.7182 (2)	0.0364 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.056 (6)	0.038 (5)	0.047 (6)	0.009 (5)	0.019 (5)	0.007 (4)
C2	0.034 (4)	0.035 (5)	0.030 (4)	0.007 (4)	0.009 (3)	0.011 (3)
C3	0.041 (5)	0.032 (5)	0.038 (4)	0.009 (4)	0.013 (4)	0.016 (4)
C4	0.023 (4)	0.033 (4)	0.031 (4)	0.010 (3)	0.012 (3)	0.014 (3)
C5	0.022 (4)	0.021 (4)	0.036 (4)	0.005 (3)	0.008 (3)	0.012 (3)
C6	0.035 (5)	0.026 (4)	0.045 (5)	0.007 (3)	0.016 (4)	0.016 (4)
C7	0.032 (4)	0.030 (4)	0.039 (4)	0.007 (3)	0.011 (3)	0.014 (4)
C8	0.084 (9)	0.059 (7)	0.037 (5)	0.032 (7)	0.026 (5)	0.021 (5)
N1	0.031 (4)	0.031 (4)	0.031 (3)	0.004 (3)	0.013 (3)	0.013 (3)
N2	0.025 (3)	0.028 (3)	0.035 (3)	0.011 (3)	0.011 (3)	0.014 (3)
Cd1	0.0309 (4)	0.0278 (4)	0.0387 (4)	0.0106 (2)	0.0152 (3)	0.0168 (3)
Br1	0.0350 (5)	0.0295 (5)	0.0480 (5)	0.0114 (4)	0.0154 (4)	0.0163 (4)
Br2	0.0306 (5)	0.0426 (6)	0.0383 (5)	0.0062 (4)	0.0109 (4)	0.0220 (4)
S1	0.0533 (15)	0.0470 (14)	0.0313 (11)	0.0098 (11)	0.0142 (10)	0.0205 (10)
S2	0.0375 (12)	0.0300 (11)	0.0378 (11)	0.0091 (9)	0.0129 (9)	0.0082 (9)

Geometric parameters (Å, º)

C1—C2	1.484 (14)	C6—H6	0.9300
C1—H1A	0.9600	C7—N2	1.298 (11)
C1—H1B	0.9600	C7—C8	1.505 (14)
C1—H1C	0.9600	C7—S2	1.717 (10)
C2—N1	1.329 (11)	C8—H8C	0.9600
C2—S1	1.719 (10)	C8—H8B	0.9600
C3—C4	1.343 (13)	C8—H8A	0.9600
C3—S1	1.703 (9)	Cd1—N1	2.435 (7)
C3—H3	0.9300	Cd1—N2	2.372 (7)
C4—N1	1.390 (11)	Cd1—Br1	2.7112 (11)
C4—C5	1.454 (11)	Cd1—Br2^i	2.7640 (12)
C5—C6	1.372 (12)	Cd1—Br1^ii	2.8362 (12)
C5—N2	1.397 (11)	Cd1—Br2	2.7845 (12)
C6—S2	1.693 (10)
C2—C1—H1A	109.5	H8C—C8—H8A	109.5
C2—C1—H1B	109.5	H8B—C8—H8A	109.5
H1A—C1—H1B	109.5	C2—N1—C4	110.3 (8)
C2—C1—H1C	109.5	C2—N1—Cd1	135.3 (7)
H1A—C1—H1C	109.5	C4—N1—Cd1	114.0 (5)
H1B—C1—H1C	109.5	C7—N2—C5	110.7 (8)
N1—C2—C1	125.4 (9)	C7—N2—Cd1	134.0 (6)
N1—C2—S1	113.9 (7)	C5—N2—Cd1	115.2 (5)
C1—C2—S1	120.7 (7)	N2—Cd1—N1	71.9 (2)
C4—C3—S1	111.2 (7)	N2—Cd1—Br1	161.12 (17)
C4—C3—H3	124.4	N1—Cd1—Br1	96.12 (18)
S1—C3—H3	124.4	N2—Cd1—Br2^i	94.19 (17)
C3—C4—N1	114.9 (7)	N1—Cd1—Br2^i	84.58 (18)
C3—C4—C5	126.3 (8)	Br1—Cd1—Br2^i	99.26 (4)
N1—C4—C5	118.8 (7)	N2—Cd1—Br2	103.26 (18)
C6—C5—N2	114.2 (8)	N1—Cd1—Br2	168.62 (18)
C6—C5—C4	125.9 (8)	Br1—Cd1—Br2	91.01 (4)
N2—C5—C4	120.0 (7)	Br2^i—Cd1—Br2	85.52 (3)
C5—C6—S2	110.2 (7)	N2—Cd1—Br1^ii	82.02 (17)
C5—C6—H6	124.9	N1—Cd1—Br1^ii	98.39 (18)
S2—C6—H6	124.9	Br1—Cd1—Br1^ii	85.48 (4)
N2—C7—C8	124.8 (9)	Br2^i—Cd1—Br1^ii	174.15 (3)
N2—C7—S2	114.6 (7)	Br2—Cd1—Br1^ii	90.99 (3)
C8—C7—S2	120.6 (7)	Cd1—Br1—Cd1^ii	94.52 (4)
C7—C8—H8C	109.5	Cd1^i—Br2—Cd1	94.48 (3)
C7—C8—H8B	109.5	C3—S1—C2	89.8 (4)
H8C—C8—H8B	109.5	C6—S2—C7	90.3 (4)
C7—C8—H8A	109.5
S1—C3—C4—N1	0.4 (10)	C7—N2—Cd1—Br2	14.8 (8)
S1—C3—C4—C5	−177.4 (7)	C5—N2—Cd1—Br2	−169.0 (5)
C3—C4—C5—C6	−6.7 (14)	C7—N2—Cd1—Br1^ii	−74.4 (8)
N1—C4—C5—C6	175.7 (8)	C5—N2—Cd1—Br1^ii	101.8 (5)
C3—C4—C5—N2	172.6 (8)	C2—N1—Cd1—N2	−174.0 (9)
N1—C4—C5—N2	−5.1 (11)	C4—N1—Cd1—N2	−2.8 (5)
N2—C5—C6—S2	0.1 (9)	C2—N1—Cd1—Br1	21.0 (9)
C4—C5—C6—S2	179.4 (7)	C4—N1—Cd1—Br1	−167.8 (5)
C1—C2—N1—C4	−179.4 (9)	C2—N1—Cd1—Br2^i	−77.8 (8)
S1—C2—N1—C4	−1.2 (10)	C4—N1—Cd1—Br2^i	93.4 (6)
C1—C2—N1—Cd1	−8.0 (15)	C2—N1—Cd1—Br2	−107.5 (11)
S1—C2—N1—Cd1	170.3 (5)	C4—N1—Cd1—Br2	63.8 (12)
C3—C4—N1—C2	0.5 (11)	C2—N1—Cd1—Br1^ii	107.3 (8)
C5—C4—N1—C2	178.5 (7)	C4—N1—Cd1—Br1^ii	−81.5 (6)
C3—C4—N1—Cd1	−172.9 (6)	N2—Cd1—Br1—Cd1^ii	48.6 (6)
C5—C4—N1—Cd1	5.0 (9)	N1—Cd1—Br1—Cd1^ii	97.98 (18)
C8—C7—N2—C5	−179.7 (10)	Br2^i—Cd1—Br1—Cd1^ii	−176.54 (3)
S2—C7—N2—C5	1.9 (10)	Br2—Cd1—Br1—Cd1^ii	−90.92 (4)
C8—C7—N2—Cd1	−3.4 (15)	Br1^ii—Cd1—Br1—Cd1^ii	0.0
S2—C7—N2—Cd1	178.2 (4)	N2—Cd1—Br2—Cd1^i	93.26 (18)
C6—C5—N2—C7	−1.3 (10)	N1—Cd1—Br2—Cd1^i	29.7 (9)
C4—C5—N2—C7	179.4 (7)	Br1—Cd1—Br2—Cd1^i	−99.21 (4)
C6—C5—N2—Cd1	−178.4 (6)	Br2^i—Cd1—Br2—Cd1^i	0.0
C4—C5—N2—Cd1	2.3 (9)	Br1^ii—Cd1—Br2—Cd1^i	175.30 (3)
C7—N2—Cd1—N1	−176.0 (9)	C4—C3—S1—C2	−0.8 (7)
C5—N2—Cd1—N1	0.2 (5)	N1—C2—S1—C3	1.2 (7)
C7—N2—Cd1—Br1	−123.4 (8)	C1—C2—S1—C3	179.5 (9)
C5—N2—Cd1—Br1	52.8 (9)	C5—C6—S2—C7	0.8 (7)
C7—N2—Cd1—Br2^i	101.1 (8)	N2—C7—S2—C6	−1.6 (8)
C5—N2—Cd1—Br2^i	−82.7 (5)	C8—C7—S2—C6	179.9 (9)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Br1^iii	0.93	2.87	3.754 (11)	159
C6—H6···Br1^iii	0.93	2.86	3.772 (10)	166
C8—H8C···Br2	0.96	2.74	3.681 (16)	167

Symmetry code: (iii) x, y+1, z.