cis-Dichloro­bis(2,2'-diamino-4,4'-bi-1,3-thia­zole)manganese(II) methanol solvate

In the title compound, [MnCl₂(C₆H₆N₄S₂)₂]·CH₃OH, the Mn^II ion is coordinated by two 2,2'-diamino-4,4'-bithia­zole ligands and two Cl^- anions in cis positions to form a distorted octa­hedral coordination geometry. In the crystal structure, a three-dimensional supra­molecular structure involving hydrogen bonding and aromatic packing is observed.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.057
• wR factor = 0.136
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S2     -   C5      ..       7.23 su

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C2      ..       5.16 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   Cl1     ..       5.51 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         S1
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT322_ALERT_2_C Check Hybridisation of  S3     in Main Residue .          ?
PLAT322_ALERT_2_C Check Hybridisation of  S4     in Main Residue .          ?
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          7
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl2    ..  S2      ..       3.34 Ang.

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

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

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Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: WinGX (Farrugia, 1999).

cis-Dichlorobis(2,2'-diamino-4,4'-bi-1,3-thiazole)manganese(II) methanol solvate

Crystal data

[MnCl2(C6H6N4S2)2]·CH4O	F(000) = 1124
Mr = 554.42	Dx = 1.672 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4763 reflections
a = 11.451 (2) Å	θ = 2.4–27.8°
b = 13.614 (3) Å	µ = 1.24 mm^−1
c = 14.892 (3) Å	T = 296 K
β = 108.39 (3)°	Prism, yellow
V = 2203.0 (9) Å^3	0.26 × 0.10 × 0.08 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer	3992 independent reflections
Radiation source: fine-focus sealed tube	3543 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 25.2°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −13→13
Tmin = 0.738, Tmax = 0.907	k = −15→16
16004 measured reflections	l = −17→17

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0542P)^2 + 3.4155P] where P = (Fo^2 + 2Fc^2)/3
3992 reflections	(Δ/σ)max < 0.001
263 parameters	Δρmax = 0.74 e Å^−3
0 restraints	Δρmin = −0.50 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
Mn1	0.21349 (5)	0.15786 (4)	0.29063 (4)	0.03584 (19)
Cl1	0.06956 (10)	0.19672 (8)	0.38513 (8)	0.0489 (3)
Cl2	0.38139 (10)	0.26968 (8)	0.38847 (8)	0.0478 (3)
N1	0.3358 (3)	0.0958 (3)	0.2115 (3)	0.0458 (9)
N2	0.3005 (3)	0.0227 (2)	0.3706 (3)	0.0437 (9)
N3	0.3183 (4)	0.2065 (4)	0.0872 (3)	0.0698 (13)
H3A	0.2779	0.2485	0.1090	0.084*
H3B	0.3347	0.2187	0.0359	0.084*
N4	0.2464 (4)	0.0247 (3)	0.5094 (3)	0.0622 (11)
H4A	0.2000	0.0753	0.4912	0.075*
H4B	0.2539	−0.0017	0.5634	0.075*
N5	0.0548 (3)	0.0761 (2)	0.1757 (2)	0.0404 (8)
N6	0.1158 (3)	0.2732 (2)	0.1851 (2)	0.0403 (8)
N7	0.0826 (4)	−0.0939 (3)	0.1972 (3)	0.0617 (11)
H7A	0.1515	−0.0868	0.2416	0.074*
H7B	0.0542	−0.1517	0.1801	0.074*
N8	0.2297 (4)	0.4181 (3)	0.2337 (3)	0.0651 (12)
H8A	0.2911	0.3872	0.2716	0.078*
H8B	0.2323	0.4809	0.2285	0.078*
S1	0.43960 (14)	0.03567 (15)	0.09235 (12)	0.0857 (6)
S2	0.40131 (12)	−0.11306 (10)	0.49067 (12)	0.0708 (5)
S3	−0.11698 (13)	−0.02778 (11)	0.06307 (11)	0.0709 (4)
S4	0.00675 (12)	0.42925 (9)	0.10428 (10)	0.0589 (4)
C1	0.3559 (4)	0.1210 (4)	0.1340 (4)	0.0547 (12)
C2	0.4469 (5)	−0.0373 (5)	0.1888 (5)	0.0768 (17)
H2	0.4861	−0.0980	0.2007	0.092*
C3	0.3888 (4)	0.0047 (4)	0.2442 (4)	0.0547 (13)
C4	0.3053 (4)	−0.0120 (3)	0.4552 (4)	0.0485 (11)
C5	0.4368 (4)	−0.1079 (4)	0.3902 (5)	0.0714 (18)
H5	0.4894	−0.1517	0.3743	0.086*
C6	0.3782 (4)	−0.0300 (3)	0.3333 (4)	0.0525 (12)
C7	0.0197 (4)	−0.0149 (3)	0.1550 (3)	0.0472 (11)
C8	−0.1251 (5)	0.0975 (4)	0.0513 (4)	0.0683 (15)
H8	−0.1882	0.1312	0.0071	0.082*
C9	−0.0272 (4)	0.1405 (3)	0.1150 (3)	0.0466 (11)
C10	0.1302 (4)	0.3685 (3)	0.1830 (3)	0.0453 (10)
C11	−0.0671 (4)	0.3184 (4)	0.0748 (4)	0.0551 (12)
H11	−0.1448	0.3105	0.0308	0.066*
C12	0.0018 (4)	0.2448 (3)	0.1234 (3)	0.0454 (10)
C13	0.2887 (8)	0.6906 (6)	0.2152 (7)	0.130 (4)
H13A	0.2738	0.7517	0.1813	0.194*
H13B	0.3718	0.6698	0.2243	0.194*
H13C	0.2766	0.6991	0.2756	0.194*
O1	0.2069 (4)	0.6192 (3)	0.1631 (3)	0.0806 (12)
H1	0.1360	0.6377	0.1539	0.121*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0335 (3)	0.0301 (3)	0.0417 (4)	0.0049 (2)	0.0087 (3)	0.0020 (3)
Cl1	0.0507 (6)	0.0415 (6)	0.0596 (7)	0.0067 (5)	0.0245 (5)	0.0066 (5)
Cl2	0.0425 (6)	0.0424 (6)	0.0524 (6)	−0.0032 (5)	0.0064 (5)	0.0020 (5)
N1	0.0384 (19)	0.051 (2)	0.049 (2)	−0.0009 (17)	0.0159 (17)	−0.0123 (17)
N2	0.0319 (18)	0.0335 (19)	0.059 (2)	0.0020 (15)	0.0043 (16)	0.0022 (17)
N3	0.073 (3)	0.092 (4)	0.054 (3)	−0.007 (3)	0.034 (2)	−0.007 (3)
N4	0.054 (2)	0.067 (3)	0.060 (3)	0.007 (2)	0.012 (2)	0.022 (2)
N5	0.0374 (18)	0.0367 (19)	0.044 (2)	−0.0009 (15)	0.0088 (16)	−0.0045 (15)
N6	0.0389 (19)	0.0345 (19)	0.044 (2)	0.0040 (15)	0.0088 (16)	0.0053 (15)
N7	0.061 (3)	0.035 (2)	0.077 (3)	−0.0085 (19)	0.005 (2)	−0.008 (2)
N8	0.060 (3)	0.040 (2)	0.079 (3)	−0.001 (2)	−0.002 (2)	0.011 (2)
S1	0.0613 (9)	0.1192 (14)	0.0860 (11)	0.0032 (9)	0.0368 (8)	−0.0425 (10)
S2	0.0480 (7)	0.0489 (8)	0.0975 (11)	0.0086 (6)	−0.0029 (7)	0.0244 (7)
S3	0.0601 (8)	0.0628 (9)	0.0715 (9)	−0.0196 (7)	−0.0053 (7)	−0.0103 (7)
S4	0.0594 (8)	0.0453 (7)	0.0662 (8)	0.0158 (6)	0.0114 (6)	0.0137 (6)
C1	0.037 (2)	0.067 (3)	0.060 (3)	−0.008 (2)	0.016 (2)	−0.024 (3)
C2	0.058 (3)	0.078 (4)	0.093 (4)	0.017 (3)	0.022 (3)	−0.022 (3)
C3	0.033 (2)	0.048 (3)	0.080 (4)	0.005 (2)	0.014 (2)	−0.023 (3)
C4	0.034 (2)	0.037 (2)	0.061 (3)	−0.0031 (19)	−0.003 (2)	0.011 (2)
C5	0.032 (2)	0.041 (3)	0.123 (5)	0.011 (2)	−0.002 (3)	−0.018 (3)
C6	0.033 (2)	0.039 (2)	0.075 (3)	0.0007 (19)	0.001 (2)	−0.009 (2)
C7	0.046 (2)	0.044 (3)	0.051 (3)	−0.008 (2)	0.016 (2)	−0.009 (2)
C8	0.050 (3)	0.066 (3)	0.072 (4)	−0.003 (3)	−0.006 (3)	0.003 (3)
C9	0.038 (2)	0.054 (3)	0.045 (2)	0.002 (2)	0.009 (2)	−0.001 (2)
C10	0.046 (2)	0.039 (2)	0.050 (3)	0.008 (2)	0.013 (2)	0.0069 (19)
C11	0.044 (3)	0.054 (3)	0.058 (3)	0.010 (2)	0.003 (2)	0.004 (2)
C12	0.040 (2)	0.051 (3)	0.044 (2)	0.007 (2)	0.012 (2)	0.003 (2)
C13	0.113 (7)	0.076 (5)	0.154 (8)	−0.003 (4)	−0.022 (6)	−0.024 (5)
O1	0.068 (2)	0.052 (2)	0.104 (3)	0.0089 (19)	0.002 (2)	−0.002 (2)

Geometric parameters (Å, º)

Mn1—Cl1	2.5378 (14)	N8—H8B	0.8600
Mn1—Cl2	2.5239 (14)	S1—C2	1.726 (7)
Mn1—N1	2.259 (4)	S1—C1	1.740 (5)
Mn1—N2	2.247 (3)	S2—C5	1.671 (7)
Mn1—N5	2.347 (3)	S2—C4	1.736 (5)
Mn1—N6	2.253 (3)	S3—C8	1.714 (6)
N1—C1	1.293 (6)	S3—C7	1.733 (5)
N1—C3	1.398 (6)	S4—C11	1.719 (5)
N2—C4	1.331 (6)	S4—C10	1.735 (4)
N2—C6	1.387 (6)	C2—C3	1.341 (7)
N3—C1	1.355 (7)	C2—H2	0.9300
N3—H3A	0.8600	C3—C6	1.450 (8)
N3—H3B	0.8600	C5—C6	1.391 (7)
N4—C4	1.304 (6)	C5—H5	0.9300
N4—H4A	0.8600	C8—C9	1.353 (7)
N4—H4B	0.8600	C8—H8	0.9300
N5—C7	1.309 (5)	C9—C12	1.455 (6)
N5—C9	1.391 (6)	C11—C12	1.338 (6)
N6—C10	1.310 (6)	C11—H11	0.9300
N6—C12	1.393 (5)	C13—O1	1.402 (8)
N7—C7	1.336 (6)	C13—H13A	0.9600
N7—H7A	0.8600	C13—H13B	0.9600
N7—H7B	0.8600	C13—H13C	0.9600
N8—C10	1.334 (6)	O1—H1	0.8200
N8—H8A	0.8600
N1—Mn1—N2	74.07 (14)	N1—C1—N3	124.7 (4)
N1—Mn1—N5	84.68 (13)	N1—C1—S1	114.5 (4)
N1—Mn1—N6	98.62 (14)	N3—C1—S1	120.8 (4)
N1—Mn1—Cl1	170.06 (11)	C3—C2—S1	111.3 (5)
N1—Mn1—Cl2	92.41 (10)	C3—C2—H2	124.4
N2—Mn1—N5	96.31 (12)	S1—C2—H2	124.4
N2—Mn1—N6	168.48 (13)	C2—C3—N1	114.2 (5)
N2—Mn1—Cl1	97.71 (10)	C2—C3—C6	128.7 (5)
N2—Mn1—Cl2	93.34 (10)	N1—C3—C6	117.1 (4)
N5—Mn1—N6	73.87 (13)	N4—C4—N2	125.1 (4)
N5—Mn1—Cl1	90.81 (9)	N4—C4—S2	121.2 (4)
N5—Mn1—Cl2	168.73 (9)	N2—C4—S2	113.7 (4)
N6—Mn1—Cl1	88.59 (10)	C6—C5—S2	111.7 (4)
N6—Mn1—Cl2	95.88 (10)	C6—C5—H5	124.1
Cl1—Mn1—Cl2	93.66 (5)	S2—C5—H5	124.1
C1—N1—C3	111.4 (4)	N2—C6—C5	113.4 (5)
C1—N1—Mn1	132.9 (3)	N2—C6—C3	116.6 (4)
C3—N1—Mn1	115.0 (3)	C5—C6—C3	130.0 (5)
C4—N2—C6	110.8 (4)	N5—C7—N7	124.8 (4)
C4—N2—Mn1	132.2 (3)	N5—C7—S3	114.6 (4)
C6—N2—Mn1	116.4 (3)	N7—C7—S3	120.6 (3)
C1—N3—H3A	120.0	C9—C8—S3	110.6 (4)
C1—N3—H3B	120.0	C9—C8—H8	124.7
H3A—N3—H3B	120.0	S3—C8—H8	124.7
C4—N4—H4A	120.0	C8—C9—N5	115.0 (4)
C4—N4—H4B	120.0	C8—C9—C12	126.8 (4)
H4A—N4—H4B	120.0	N5—C9—C12	118.1 (4)
C7—N5—C9	110.4 (4)	N6—C10—N8	125.3 (4)
C7—N5—Mn1	136.9 (3)	N6—C10—S4	114.0 (3)
C9—N5—Mn1	112.6 (3)	N8—C10—S4	120.6 (3)
C10—N6—C12	110.9 (4)	C12—C11—S4	111.1 (4)
C10—N6—Mn1	132.0 (3)	C12—C11—H11	124.4
C12—N6—Mn1	115.0 (3)	S4—C11—H11	124.4
C7—N7—H7A	120.0	C11—C12—N6	114.8 (4)
C7—N7—H7B	120.0	C11—C12—C9	127.2 (4)
H7A—N7—H7B	120.0	N6—C12—C9	117.9 (4)
C10—N8—H8A	120.0	O1—C13—H13A	109.5
C10—N8—H8B	120.0	O1—C13—H13B	109.5
H8A—N8—H8B	120.0	H13A—C13—H13B	109.5
C2—S1—C1	88.6 (3)	O1—C13—H13C	109.5
C5—S2—C4	90.2 (2)	H13A—C13—H13C	109.5
C8—S3—C7	89.3 (2)	H13B—C13—H13C	109.5
C11—S4—C10	89.1 (2)	C13—O1—H1	109.5
N2—Mn1—N1—C1	176.5 (4)	C1—N1—C3—C6	177.1 (4)
N6—Mn1—N1—C1	5.6 (4)	Mn1—N1—C3—C6	−10.9 (5)
N5—Mn1—N1—C1	78.4 (4)	C6—N2—C4—N4	177.1 (4)
Cl2—Mn1—N1—C1	−90.7 (4)	Mn1—N2—C4—N4	6.7 (7)
N2—Mn1—N1—C3	6.6 (3)	C6—N2—C4—S2	−2.0 (5)
N6—Mn1—N1—C3	−164.3 (3)	Mn1—N2—C4—S2	−172.4 (2)
N5—Mn1—N1—C3	−91.5 (3)	C5—S2—C4—N4	−178.6 (4)
Cl2—Mn1—N1—C3	99.4 (3)	C5—S2—C4—N2	0.5 (4)
N6—Mn1—N2—C4	−139.9 (6)	C4—S2—C5—C6	1.1 (4)
N1—Mn1—N2—C4	168.5 (4)	C4—N2—C6—C5	2.8 (5)
N5—Mn1—N2—C4	−108.9 (4)	Mn1—N2—C6—C5	174.9 (3)
Cl2—Mn1—N2—C4	76.9 (4)	C4—N2—C6—C3	−175.6 (4)
Cl1—Mn1—N2—C4	−17.3 (4)	Mn1—N2—C6—C3	−3.5 (5)
N6—Mn1—N2—C6	50.0 (8)	S2—C5—C6—N2	−2.4 (5)
N1—Mn1—N2—C6	−1.6 (3)	S2—C5—C6—C3	175.7 (4)
N5—Mn1—N2—C6	81.0 (3)	C2—C3—C6—N2	−172.8 (5)
Cl2—Mn1—N2—C6	−93.2 (3)	N1—C3—C6—N2	9.6 (6)
Cl1—Mn1—N2—C6	172.7 (3)	C2—C3—C6—C5	9.1 (9)
N2—Mn1—N5—C7	−1.7 (5)	N1—C3—C6—C5	−168.5 (5)
N6—Mn1—N5—C7	172.2 (5)	C9—N5—C7—N7	176.3 (4)
N1—Mn1—N5—C7	71.6 (4)	Mn1—N5—C7—N7	−6.6 (8)
Cl2—Mn1—N5—C7	147.0 (4)	C9—N5—C7—S3	−1.8 (5)
Cl1—Mn1—N5—C7	−99.6 (4)	Mn1—N5—C7—S3	175.3 (2)
N2—Mn1—N5—C9	175.3 (3)	C8—S3—C7—N5	1.0 (4)
N6—Mn1—N5—C9	−10.8 (3)	C8—S3—C7—N7	−177.3 (4)
N1—Mn1—N5—C9	−111.4 (3)	C7—S3—C8—C9	0.2 (5)
Cl2—Mn1—N5—C9	−36.0 (6)	S3—C8—C9—N5	−1.3 (6)
Cl1—Mn1—N5—C9	77.5 (3)	S3—C8—C9—C12	176.3 (4)
N2—Mn1—N6—C10	−151.9 (6)	C7—N5—C9—C8	2.0 (6)
N1—Mn1—N6—C10	−102.2 (4)	Mn1—N5—C9—C8	−175.8 (4)
N5—Mn1—N6—C10	176.0 (4)	C7—N5—C9—C12	−175.8 (4)
Cl2—Mn1—N6—C10	−8.8 (4)	Mn1—N5—C9—C12	6.4 (5)
Cl1—Mn1—N6—C10	84.7 (4)	C12—N6—C10—N8	−179.7 (5)
N2—Mn1—N6—C12	46.4 (8)	Mn1—N6—C10—N8	18.0 (7)
N1—Mn1—N6—C12	96.1 (3)	C12—N6—C10—S4	−1.0 (5)
N5—Mn1—N6—C12	14.3 (3)	Mn1—N6—C10—S4	−163.3 (2)
Cl2—Mn1—N6—C12	−170.5 (3)	C11—S4—C10—N6	0.6 (4)
Cl1—Mn1—N6—C12	−77.0 (3)	C11—S4—C10—N8	179.4 (4)
C3—N1—C1—N3	−178.3 (4)	C10—S4—C11—C12	0.0 (4)
Mn1—N1—C1—N3	11.6 (7)	S4—C11—C12—N6	−0.5 (6)
C3—N1—C1—S1	0.8 (5)	S4—C11—C12—C9	−177.3 (4)
Mn1—N1—C1—S1	−169.4 (2)	C10—N6—C12—C11	1.0 (6)
C2—S1—C1—N1	−0.4 (4)	Mn1—N6—C12—C11	166.5 (3)
C2—S1—C1—N3	178.7 (4)	C10—N6—C12—C9	178.1 (4)
C1—S1—C2—C3	−0.1 (4)	Mn1—N6—C12—C9	−16.3 (5)
S1—C2—C3—N1	0.5 (6)	C8—C9—C12—C11	5.6 (9)
S1—C2—C3—C6	−177.1 (4)	N5—C9—C12—C11	−176.9 (5)
C1—N1—C3—C2	−0.8 (6)	C8—C9—C12—N6	−171.2 (5)
Mn1—N1—C3—C2	171.2 (4)	N5—C9—C12—N6	6.3 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl1^i	0.82	2.38	3.197 (4)	175
N3—H3A···N6	0.86	2.48	3.233 (6)	146
N3—H3B···Cl2^ii	0.86	2.42	3.277 (4)	173
N4—H4A···Cl1	0.86	2.44	3.263 (4)	160
N4—H4B···O1^iii	0.86	2.36	3.152 (6)	154
N7—H7A···N2	0.86	2.60	3.369 (5)	150
N7—H7B···Cl1^iv	0.86	2.52	3.364 (4)	168
N8—H8A···Cl2	0.86	2.35	3.144 (4)	154
N8—H8B···O1	0.86	2.10	2.915 (6)	159

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, −y+1/2, z+1/2; (iv) −x, y−1/2, −z+1/2.