Diaqua­bis(2,5-di-3-pyrid­yl-1,3,4-oxadiazole)dithio­cyanato­manganese(II): a three-dimensional supra­molecular network formed through O—H...N and C—H...S inter­actions

The mol­ecular structure of the neutral mononuclear title complex, [Mn(NCS)₂(C₁₂H₈N₄O)₂(H₂O)₂], is centrosymmetric; the Mn^II atom lies on an inversion center and is six-coordinate (MnN₄O₂), with an octa­hedral geometry comprising two trans monodentate 2,5-di-3-pyrid­yl-1,3,4-oxadiazole ligands, two thio­cyanate ligands and two bound water mol­ecules. Inter­molecular O—H...N hydrogen bonds between these monomeric units result in two-dimensional supramolecular layers with a parallel arrangement, which are stabilized by intra­layer aromatic stacking and further extended to a three-dimensional network via inter­layer weak C—H...S inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
Some non-H atoms missing
• R factor = 0.035
• wR factor = 0.099
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSMU01_ALERT_1_C  The ratio of given/expected absorption coefficient lies
               outside the range 0.99 <> 1.01
            Calculated value of mu =     0.657
            Value of mu given      =     0.648
CHEMW01_ALERT_1_C  The ratio of given/expected molecular weight as calculated
            from the _chemical_formula_sum lies outside
            the range 0.99 <> 1.01
            Calculated formula weight =   687.5654
            Formula weight given      =   655.5800
CHEMW01_ALERT_1_C  The difference between the given and expected weight for
            compound is greater 1 mass unit. Check that all hydrogen
            atoms have been taken into account.
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C13     ..       5.12 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   N5      ..       6.44 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C26 H20 Mn1 N10 O6 S2
            Atom count from the _atom_site data:  C26 H20 Mn1 N10 O4 S2
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z    1
           From the CIF: _chemical_formula_sum  C26 H20 Mn N10 O6 S2
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         26.00     26.00    0.00
           H         20.00     20.00    0.00
           Mn         1.00      1.00    0.00
           N         10.00     10.00    0.00
           O          6.00      4.00    2.00
           S          2.00      2.00    0.00

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

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

---

Computing details

Data collection: Apex II (Bruker, 2003); cell refinement: Apex II; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Diaquabis(2,5-di-3-pyridyl-1,3,4-oxadiazole)dithiocyanatomanganese(II)

Crystal data

[Mn(NCS)2(C12H8N4O2)2(H2O)2]	Z = 1
Mr = 655.58	F(000) = 335
Triclinic, P1	Dx = 1.494 Mg m^−3
a = 8.1951 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.762 (2) Å	Cell parameters from 1513 reflections
c = 10.619 (3) Å	θ = 2.6–26.7°
α = 82.472 (3)°	µ = 0.65 mm^−1
β = 77.181 (3)°	T = 293 K
γ = 79.873 (3)°	Block, colorless
V = 728.5 (3) Å^3	0.40 × 0.24 × 0.11 mm

Data collection

Bruker APEX-II CCD area-detector diffractometer	2540 independent reflections
Radiation source: fine-focus sealed tube	2005 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.772, Tmax = 0.931	k = −10→9
4203 measured reflections	l = −10→12

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0576P)^2 + 0.1207P] where P = (Fo^2 + 2Fc^2)/3
2540 reflections	(Δ/σ)max < 0.001
196 parameters	Δρmax = 0.43 e Å^−3
3 restraints	Δρmin = −0.36 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	0.5000	0.0000	0.5000	0.04117 (17)
S1	0.83885 (8)	0.33655 (9)	0.17907 (8)	0.0771 (3)
O1	0.42139 (18)	0.22308 (17)	−0.00282 (13)	0.0417 (4)
O2	0.67530 (19)	−0.21189 (18)	0.43958 (13)	0.0518 (4)
H2A	0.6905	−0.2269	0.3600	0.062*
H2B	0.6658	−0.2942	0.4911	0.062*
N1	0.6863 (3)	0.5355 (2)	−0.3704 (2)	0.0612 (6)
N2	0.3127 (2)	0.2409 (2)	−0.17602 (16)	0.0467 (5)
N3	0.2210 (2)	0.1467 (2)	−0.07675 (16)	0.0459 (5)
N4	0.3229 (2)	−0.0161 (2)	0.35803 (15)	0.0408 (4)
N5	0.6484 (2)	0.1369 (2)	0.35059 (18)	0.0559 (5)
C1	0.1073 (3)	−0.0160 (3)	0.1882 (2)	0.0454 (5)
H1	0.0353	−0.0161	0.1317	0.054*
C2	0.0761 (3)	−0.0896 (3)	0.3123 (2)	0.0482 (6)
H2	−0.0178	−0.1404	0.3412	0.058*
C3	0.1860 (3)	−0.0871 (3)	0.3930 (2)	0.0459 (5)
H3	0.1636	−0.1375	0.4762	0.055*
C4	0.3517 (3)	0.0557 (2)	0.23804 (19)	0.0401 (5)
H4	0.4457	0.1068	0.2120	0.048*
C5	0.2485 (2)	0.0579 (2)	0.15041 (18)	0.0370 (5)
C6	0.2894 (3)	0.1401 (2)	0.02165 (19)	0.0380 (5)
C7	0.4270 (3)	0.2823 (2)	−0.12854 (19)	0.0400 (5)
C8	0.5603 (3)	0.3748 (2)	−0.1877 (2)	0.0440 (5)
C9	0.6869 (3)	0.3857 (3)	−0.1240 (2)	0.0601 (7)
H9	0.6865	0.3363	−0.0409	0.072*
C10	0.8127 (4)	0.4698 (3)	−0.1843 (3)	0.0749 (8)
H10	0.8999	0.4780	−0.1436	0.090*
C11	0.8071 (4)	0.5422 (3)	−0.3068 (3)	0.0712 (8)
H11	0.8930	0.5992	−0.3475	0.085*
C12	0.5649 (3)	0.4527 (3)	−0.3110 (2)	0.0522 (6)
H12	0.4792	0.4465	−0.3538	0.063*
C13	0.7278 (3)	0.2203 (3)	0.2788 (2)	0.0436 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0430 (3)	0.0531 (3)	0.0307 (3)	−0.0230 (2)	−0.01120 (19)	0.01186 (19)
S1	0.0502 (4)	0.0729 (5)	0.0977 (6)	−0.0277 (4)	−0.0055 (4)	0.0385 (4)
O1	0.0464 (9)	0.0486 (9)	0.0330 (7)	−0.0165 (7)	−0.0122 (6)	0.0052 (6)
O2	0.0680 (11)	0.0561 (10)	0.0333 (8)	−0.0192 (8)	−0.0134 (7)	0.0070 (7)
N1	0.0692 (14)	0.0557 (13)	0.0554 (12)	−0.0234 (11)	−0.0072 (11)	0.0163 (10)
N2	0.0542 (11)	0.0539 (12)	0.0347 (9)	−0.0180 (9)	−0.0132 (8)	0.0064 (8)
N3	0.0515 (11)	0.0574 (12)	0.0324 (9)	−0.0198 (9)	−0.0130 (8)	0.0066 (8)
N4	0.0400 (10)	0.0511 (11)	0.0328 (9)	−0.0159 (8)	−0.0092 (7)	0.0056 (8)
N5	0.0540 (12)	0.0681 (14)	0.0475 (11)	−0.0274 (11)	−0.0135 (10)	0.0173 (10)
C1	0.0425 (12)	0.0562 (14)	0.0406 (12)	−0.0144 (11)	−0.0142 (10)	0.0032 (10)
C2	0.0390 (12)	0.0610 (15)	0.0460 (13)	−0.0216 (11)	−0.0083 (10)	0.0075 (10)
C3	0.0435 (12)	0.0572 (14)	0.0360 (11)	−0.0141 (11)	−0.0074 (10)	0.0069 (10)
C4	0.0381 (11)	0.0486 (13)	0.0352 (11)	−0.0148 (10)	−0.0089 (9)	0.0041 (9)
C5	0.0374 (11)	0.0433 (12)	0.0307 (10)	−0.0084 (9)	−0.0084 (8)	0.0010 (8)
C6	0.0386 (11)	0.0420 (12)	0.0351 (11)	−0.0124 (9)	−0.0086 (9)	0.0013 (9)
C7	0.0482 (12)	0.0390 (12)	0.0310 (11)	−0.0058 (10)	−0.0080 (9)	0.0027 (9)
C8	0.0494 (13)	0.0399 (12)	0.0414 (12)	−0.0119 (10)	−0.0066 (10)	0.0041 (9)
C9	0.0678 (17)	0.0614 (16)	0.0556 (15)	−0.0287 (13)	−0.0178 (13)	0.0129 (12)
C10	0.0761 (19)	0.080 (2)	0.0782 (19)	−0.0417 (16)	−0.0283 (15)	0.0181 (16)
C11	0.0733 (19)	0.0624 (18)	0.0777 (19)	−0.0336 (15)	−0.0089 (15)	0.0143 (14)
C12	0.0562 (15)	0.0490 (14)	0.0496 (13)	−0.0158 (11)	−0.0088 (11)	0.0084 (11)
C13	0.0376 (11)	0.0509 (14)	0.0441 (12)	−0.0148 (11)	−0.0136 (10)	0.0089 (10)

Geometric parameters (Å, º)

Mn1—N5	2.1431 (19)	C1—C5	1.382 (3)
Mn1—N5^i	2.1431 (19)	C1—C2	1.380 (3)
Mn1—O2^i	2.2107 (16)	C1—H1	0.9300
Mn1—O2	2.2107 (16)	C2—C3	1.378 (3)
Mn1—N4	2.3449 (17)	C2—H2	0.9300
Mn1—N4^i	2.3449 (17)	C3—H3	0.9300
S1—C13	1.613 (2)	C4—C5	1.386 (3)
O1—C7	1.361 (2)	C4—H4	0.9300
O1—C6	1.366 (2)	C5—C6	1.458 (3)
O2—H2A	0.8501	C7—C8	1.455 (3)
O2—H2B	0.8501	C8—C9	1.381 (3)
N1—C12	1.330 (3)	C8—C12	1.390 (3)
N1—C11	1.330 (4)	C9—C10	1.366 (3)
N2—C7	1.281 (3)	C9—H9	0.9300
N2—N3	1.413 (2)	C10—C11	1.377 (4)
N3—C6	1.282 (3)	C10—H10	0.9300
N4—C3	1.335 (3)	C11—H11	0.9300
N4—C4	1.336 (2)	C12—H12	0.9300
N5—C13	1.157 (3)
N5—Mn1—N5^i	180.00 (10)	N4—C3—C2	123.6 (2)
N5—Mn1—O2^i	90.61 (7)	N4—C3—H3	118.2
N5^i—Mn1—O2^i	89.39 (7)	C2—C3—H3	118.2
N5—Mn1—O2	89.39 (7)	N4—C4—C5	123.27 (19)
N5^i—Mn1—O2	90.61 (7)	N4—C4—H4	118.4
O2^i—Mn1—O2	180.0	C5—C4—H4	118.4
N5—Mn1—N4	89.80 (7)	C1—C5—C4	119.04 (19)
N5^i—Mn1—N4	90.20 (7)	C1—C5—C6	121.52 (19)
O2^i—Mn1—N4	86.54 (6)	C4—C5—C6	119.43 (19)
O2—Mn1—N4	93.46 (6)	N3—C6—O1	112.63 (17)
N5—Mn1—N4^i	90.20 (7)	N3—C6—C5	129.9 (2)
N5^i—Mn1—N4^i	89.80 (7)	O1—C6—C5	117.49 (17)
O2^i—Mn1—N4^i	93.46 (6)	N2—C7—O1	112.03 (18)
O2—Mn1—N4^i	86.54 (6)	N2—C7—C8	130.84 (19)
N4—Mn1—N4^i	180.0	O1—C7—C8	117.09 (19)
C7—O1—C6	102.77 (15)	C9—C8—C12	118.2 (2)
Mn1—O2—H2A	115.9	C9—C8—C7	121.0 (2)
Mn1—O2—H2B	116.3	C12—C8—C7	120.8 (2)
H2A—O2—H2B	113.7	C10—C9—C8	119.3 (2)
C12—N1—C11	117.1 (2)	C10—C9—H9	120.4
C7—N2—N3	106.88 (16)	C8—C9—H9	120.4
C6—N3—N2	105.70 (17)	C9—C10—C11	118.3 (3)
C3—N4—C4	116.95 (18)	C9—C10—H10	120.9
C3—N4—Mn1	123.21 (13)	C11—C10—H10	120.9
C4—N4—Mn1	119.73 (13)	N1—C11—C10	124.0 (2)
C13—N5—Mn1	173.4 (2)	N1—C11—H11	118.0
C5—C1—C2	117.98 (19)	C10—C11—H11	118.0
C5—C1—H1	121.0	N1—C12—C8	123.1 (2)
C2—C1—H1	121.0	N1—C12—H12	118.5
C1—C2—C3	119.2 (2)	C8—C12—H12	118.5
C1—C2—H2	120.4	N5—C13—S1	179.8 (2)
C3—C2—H2	120.4
C7—N2—N3—C6	−0.1 (2)	C7—O1—C6—C5	179.30 (18)
N5—Mn1—N4—C3	−177.16 (18)	C1—C5—C6—N3	−7.4 (4)
N5^i—Mn1—N4—C3	2.84 (18)	C4—C5—C6—N3	173.7 (2)
O2^i—Mn1—N4—C3	−86.53 (17)	C1—C5—C6—O1	173.49 (18)
O2—Mn1—N4—C3	93.47 (17)	C4—C5—C6—O1	−5.4 (3)
N5^i—Mn1—N4—C4	178.83 (16)	N3—N2—C7—O1	0.1 (2)
O2^i—Mn1—N4—C4	89.46 (16)	N3—N2—C7—C8	177.7 (2)
O2—Mn1—N4—C4	−90.54 (16)	C6—O1—C7—N2	−0.1 (2)
C5—C1—C2—C3	−0.1 (3)	C6—O1—C7—C8	−178.06 (17)
C4—N4—C3—C2	0.2 (3)	N2—C7—C8—C9	−169.9 (2)
Mn1—N4—C3—C2	176.29 (17)	O1—C7—C8—C9	7.6 (3)
C1—C2—C3—N4	0.2 (4)	N2—C7—C8—C12	9.1 (4)
C3—N4—C4—C5	−0.7 (3)	O1—C7—C8—C12	−173.42 (19)
Mn1—N4—C4—C5	−176.90 (15)	C12—C8—C9—C10	−1.0 (4)
C2—C1—C5—C4	−0.3 (3)	C7—C8—C9—C10	178.0 (2)
C2—C1—C5—C6	−179.2 (2)	C8—C9—C10—C11	0.6 (4)
N4—C4—C5—C1	0.7 (3)	C12—N1—C11—C10	−0.4 (4)
N4—C4—C5—C6	179.64 (19)	C9—C10—C11—N1	0.1 (5)
N2—N3—C6—O1	0.0 (2)	C11—N1—C12—C8	0.0 (4)
N2—N3—C6—C5	−179.1 (2)	C9—C8—C12—N1	0.7 (4)
C7—O1—C6—N3	0.0 (2)	C7—C8—C12—N1	−178.3 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N2^ii	0.85	1.98	2.822 (3)	170
O2—H2B···N1^iii	0.85	1.96	2.796 (3)	165
C10—H10···S1^iv	0.93	2.84	3.582 (4)	138

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