Diaqua­bis[2-(2-pyridylmeth­oxy)pyrazine-κN⁴]bis­(thio­cyanato-κN)manganese(II)

In the title complex, [Mn(NCS)₂(C₁₀H₉N₃O)₂(H₂O)₂], the Mn^II ion lies on a twofold rotation axis and assumes a distorted octa­hedral MnN₄O₂ coordination geometry. There is a weak π–π stacking inter­action between adjacent pyridyl and pyrazine rings [centroid-to-centroid distance 3.7457 (13) Å]. The mononuclear complexes are connected to each other by O—H...N and O—H...S hydrogen bonds. The dihedral angle between the pyridyl and pyrazine rings is 85.82 (9)°.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.030
• wR factor = 0.083
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S1     -   C1      ..       7.66 su

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C1      ..       5.29 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C22 H22 Mn N8 O4 S2

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (2)       2.07

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   1 ALERT type 5 Informative message, check

---

S1. Comment

Metal complexes containing N-heterocyclic ligands play a pivotal role in the area of coordination chemistry, but the ligand molecules that consist of pyridyl and pyrazyl groups are very limited (McMorran et al. 2002; Zhao et al., 2007a,b).

The title compound is shown in Fig. 1. In the mono-nuclear complex atom Mn1 is in a distorted octahedral geometry and is located on a twofold ratation axis. Between adjacent complexes there is a weak π-π stacking interaction between pyrazyl and pyridyl rings; the relevant distances are Cg1···Cg2ⁱ = 3.7457 (13) Å and Cg1···Cg2ⁱ_perp = 3.222 Å [symmetry codes: (i) X, 1-Y, 1/2+Z; Cg1 and Cg2 are the centroids of the N2,N3,C2,C3,C4,C5 and N4,C7,C8,C9,C10,C11 rings, respectively; Cg1···Cg2_perp is the perpendicular distance from ring Cg1 to ring Cg2]. Fig. 2 shows the O—H···N and O—H···S hydrogen bonds and Table 1 lists the geometric parameters. The dihedral angle between the pyridyl ring and the pyrazyl ring in 2-[(pyridin-2-yl)methoxy]pyrazine is 85.82 (9)°.

Related literature

For related structures, see: McMorran et al. (2002); Zhao et al. (2007a,b).

S2. Experimental

5 ml me thanol solution of 2-[(pyridin-2-yl)methoxy]pyrazine (0.0468 g, 0.250 mmol) was added into 10 ml H₂O solution containing Mn(ClO₄)₂.6H₂O (0.1021 g, 0.282 mmol) and NaSCN (0.0459 g, 0.566 mmol), and the mixed soulution was stirred for a few minutes. Colourless single crystals were obtained after the solution had been allowed to stand at room temperature for two weeks.

S3. Refinement

The H atoms from H₂O were found in a difference Fourier map, and placed in idealized positions with O—H = 0.894–0.895 Å. The C-bound H atom were placed in calculated positions, C—H = 0.93–0.97 Å. All H atoms were refined as riding, with U_iso(H) = 1.2–1.5U_eq(C,O).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the title complex, showing the the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level [symmetry code: (i) -x + 2, y, -z + 5/2].
	Fig. 2. Hydrogen bonds (dashed lines) between complexes.

Diaquabis[2-(2-pyridylmethoxy)pyrazine-κN⁴]bis(thiocyanato-κN)manganese(II)

Crystal data

[Mn(NCS)2(C10H9N3O)2(H2O)2]	F(000) = 1196
Mr = 581.54	Dx = 1.480 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4687 reflections
a = 20.060 (3) Å	θ = 2.2–28.3°
b = 10.1381 (12) Å	µ = 0.71 mm^−1
c = 13.7285 (17) Å	T = 298 K
β = 110.844 (2)°	Block, colourless
V = 2609.3 (6) Å^3	0.26 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	2317 independent reflections
Radiation source: fine-focus sealed tube	2133 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→22
Tmin = 0.837, Tmax = 0.895	k = −12→11
5374 measured reflections	l = −9→16

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) = 0.083	w = 1/[σ^2(Fo^2) + (0.0425P)^2 + 1.6969P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.010
2317 reflections	Δρmax = 0.44 e Å^−3
169 parameters	Δρmin = −0.45 e Å^−3
0 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0033 (4)

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	1.0000	0.79418 (3)	1.2500	0.03392 (15)
S1	1.03076 (5)	0.77723 (7)	0.91123 (5)	0.0820 (2)
N2	0.92253 (7)	0.61791 (14)	1.18728 (11)	0.0387 (3)
O1	0.80883 (7)	0.47898 (12)	0.94850 (9)	0.0490 (3)
N4	0.67814 (8)	0.44033 (15)	0.74592 (11)	0.0435 (4)
O2	0.91697 (7)	0.94209 (13)	1.17325 (9)	0.0493 (3)
H1	0.8847	0.9782	1.1964	0.074*
H6	0.9331	1.0103	1.1468	0.074*
N1	1.02389 (9)	0.79825 (16)	1.10881 (13)	0.0492 (4)
C5	0.84117 (9)	0.49147 (17)	1.05252 (13)	0.0387 (4)
C8	0.76848 (10)	0.28795 (18)	0.74656 (16)	0.0459 (4)
H8	0.8078	0.2371	0.7843	0.055*
N3	0.82651 (8)	0.40955 (15)	1.11682 (11)	0.0429 (4)
C1	1.02672 (10)	0.79049 (17)	1.02685 (15)	0.0423 (4)
C9	0.74294 (11)	0.28611 (19)	0.63920 (17)	0.0515 (5)
H9	0.7643	0.2330	0.6034	0.062*
C7	0.73497 (9)	0.36634 (16)	0.79734 (13)	0.0374 (4)
C3	0.86224 (10)	0.43152 (19)	1.21803 (14)	0.0472 (4)
H3	0.8549	0.3748	1.2664	0.057*
C4	0.88960 (9)	0.59529 (17)	1.08683 (13)	0.0385 (4)
H4	0.8988	0.6493	1.0383	0.046*
C6	0.76005 (10)	0.36903 (18)	0.91382 (14)	0.0467 (4)
H6A	0.7199	0.3801	0.9367	0.056*
H6B	0.7840	0.2871	0.9424	0.056*
C2	0.90920 (10)	0.53366 (19)	1.25373 (14)	0.0453 (4)
H2	0.9323	0.5450	1.3251	0.054*
C11	0.65489 (11)	0.4379 (2)	0.64193 (15)	0.0511 (5)
H11	0.6156	0.4895	0.6054	0.061*
C10	0.68574 (11)	0.3634 (2)	0.58593 (15)	0.0520 (5)
H10	0.6682	0.3655	0.5135	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0365 (2)	0.0357 (2)	0.0277 (2)	0.000	0.00914 (15)	0.000
S1	0.1351 (6)	0.0759 (5)	0.0542 (4)	0.0111 (4)	0.0571 (4)	0.0012 (3)
N2	0.0368 (7)	0.0388 (8)	0.0357 (7)	−0.0029 (6)	0.0070 (6)	0.0008 (6)
O1	0.0611 (8)	0.0431 (7)	0.0324 (6)	−0.0182 (6)	0.0040 (6)	0.0015 (5)
N4	0.0454 (8)	0.0435 (8)	0.0391 (8)	0.0011 (6)	0.0120 (7)	−0.0035 (6)
O2	0.0534 (7)	0.0538 (8)	0.0419 (7)	0.0150 (6)	0.0185 (6)	0.0082 (6)
N1	0.0614 (10)	0.0511 (10)	0.0407 (9)	−0.0029 (7)	0.0251 (8)	0.0007 (7)
C5	0.0408 (9)	0.0359 (9)	0.0345 (9)	−0.0011 (7)	0.0076 (7)	0.0002 (7)
C8	0.0418 (10)	0.0402 (10)	0.0536 (11)	−0.0006 (7)	0.0145 (8)	0.0000 (8)
N3	0.0469 (8)	0.0399 (8)	0.0380 (8)	−0.0081 (6)	0.0103 (6)	0.0010 (6)
C1	0.0465 (10)	0.0377 (10)	0.0454 (11)	0.0019 (7)	0.0197 (8)	0.0021 (7)
C9	0.0604 (12)	0.0501 (11)	0.0518 (11)	−0.0081 (9)	0.0295 (10)	−0.0130 (9)
C7	0.0403 (9)	0.0337 (9)	0.0356 (9)	−0.0101 (7)	0.0103 (7)	−0.0020 (7)
C3	0.0535 (10)	0.0476 (10)	0.0371 (9)	−0.0105 (8)	0.0119 (8)	0.0050 (8)
C4	0.0408 (9)	0.0363 (9)	0.0346 (9)	−0.0030 (7)	0.0087 (7)	0.0027 (7)
C6	0.0537 (10)	0.0423 (10)	0.0377 (9)	−0.0153 (8)	0.0083 (8)	−0.0003 (8)
C2	0.0477 (10)	0.0492 (11)	0.0334 (9)	−0.0076 (8)	0.0077 (8)	0.0010 (8)
C11	0.0512 (10)	0.0523 (11)	0.0411 (10)	0.0046 (9)	0.0058 (8)	0.0026 (8)
C10	0.0637 (12)	0.0551 (12)	0.0350 (9)	−0.0123 (10)	0.0151 (9)	−0.0059 (8)

Geometric parameters (Å, º)

Mn1—N1^i	2.1564 (16)	C5—C4	1.396 (2)
Mn1—N1	2.1564 (16)	C8—C9	1.378 (3)
Mn1—O2^i	2.2100 (13)	C8—C7	1.380 (3)
Mn1—O2	2.2100 (12)	C8—H8	0.9300
Mn1—N2	2.3233 (14)	N3—C3	1.336 (2)
Mn1—N2^i	2.3233 (14)	C9—C10	1.367 (3)
S1—C1	1.623 (2)	C9—H9	0.9300
N2—C4	1.320 (2)	C7—C6	1.496 (2)
N2—C2	1.344 (2)	C3—C2	1.368 (3)
O1—C5	1.348 (2)	C3—H3	0.9300
O1—C6	1.448 (2)	C4—H4	0.9300
N4—C11	1.335 (2)	C6—H6A	0.9700
N4—C7	1.337 (2)	C6—H6B	0.9700
O2—H1	0.8947	C2—H2	0.9300
O2—H6	0.8938	C11—C10	1.372 (3)
N1—C1	1.149 (3)	C11—H11	0.9300
C5—N3	1.319 (2)	C10—H10	0.9300
N1^i—Mn1—N1	177.81 (9)	C5—N3—C3	115.22 (15)
N1^i—Mn1—O2^i	85.95 (6)	N1—C1—S1	179.17 (17)
N1—Mn1—O2^i	92.56 (6)	C10—C9—C8	119.12 (18)
N1^i—Mn1—O2	92.56 (6)	C10—C9—H9	120.4
N1—Mn1—O2	85.95 (6)	C8—C9—H9	120.4
O2^i—Mn1—O2	94.55 (7)	N4—C7—C8	122.25 (16)
N1^i—Mn1—N2	90.83 (6)	N4—C7—C6	116.96 (16)
N1—Mn1—N2	90.85 (6)	C8—C7—C6	120.77 (17)
O2^i—Mn1—N2	171.83 (5)	N3—C3—C2	123.03 (17)
O2—Mn1—N2	93.09 (5)	N3—C3—H3	118.5
N1^i—Mn1—N2^i	90.85 (6)	C2—C3—H3	118.5
N1—Mn1—N2^i	90.83 (6)	N2—C4—C5	120.88 (16)
O2^i—Mn1—N2^i	93.09 (5)	N2—C4—H4	119.6
O2—Mn1—N2^i	171.83 (5)	C5—C4—H4	119.6
N2—Mn1—N2^i	79.44 (7)	O1—C6—C7	107.25 (14)
C4—N2—C2	116.88 (15)	O1—C6—H6A	110.3
C4—N2—Mn1	122.75 (11)	C7—C6—H6A	110.3
C2—N2—Mn1	120.37 (11)	O1—C6—H6B	110.3
C5—O1—C6	115.79 (13)	C7—C6—H6B	110.3
C11—N4—C7	117.52 (16)	H6A—C6—H6B	108.5
Mn1—O2—H1	128.8	N2—C2—C3	121.05 (16)
Mn1—O2—H6	113.5	N2—C2—H2	119.5
H1—O2—H6	103.9	C3—C2—H2	119.5
C1—N1—Mn1	169.40 (16)	N4—C11—C10	123.61 (18)
N3—C5—O1	120.80 (15)	N4—C11—H11	118.2
N3—C5—C4	122.89 (15)	C10—C11—H11	118.2
O1—C5—C4	116.31 (15)	C9—C10—C11	118.41 (18)
C9—C8—C7	119.06 (17)	C9—C10—H10	120.8
C9—C8—H8	120.5	C11—C10—H10	120.8
C7—C8—H8	120.5
N1^i—Mn1—N2—C4	152.48 (14)	C11—N4—C7—C6	−179.46 (16)
N1—Mn1—N2—C4	−26.12 (14)	C9—C8—C7—N4	0.4 (3)
O2—Mn1—N2—C4	59.87 (14)	C9—C8—C7—C6	178.70 (16)
N2^i—Mn1—N2—C4	−116.80 (15)	C5—N3—C3—C2	1.9 (3)
N1^i—Mn1—N2—C2	−27.27 (14)	C2—N2—C4—C5	2.5 (2)
N1—Mn1—N2—C2	154.13 (14)	Mn1—N2—C4—C5	−177.28 (12)
O2—Mn1—N2—C2	−119.88 (13)	N3—C5—C4—N2	−1.3 (3)
N2^i—Mn1—N2—C2	63.44 (12)	O1—C5—C4—N2	178.14 (15)
O2^i—Mn1—N1—C1	−165.5 (8)	C5—O1—C6—C7	−175.36 (15)
O2—Mn1—N1—C1	−71.1 (8)	N4—C7—C6—O1	−87.09 (19)
N2—Mn1—N1—C1	22.0 (8)	C8—C7—C6—O1	94.48 (19)
N2^i—Mn1—N1—C1	101.4 (8)	C4—N2—C2—C3	−1.6 (3)
C6—O1—C5—N3	−2.0 (2)	Mn1—N2—C2—C3	178.21 (14)
C6—O1—C5—C4	178.54 (15)	N3—C3—C2—N2	−0.7 (3)
O1—C5—N3—C3	179.65 (16)	C7—N4—C11—C10	0.5 (3)
C4—C5—N3—C3	−1.0 (3)	C8—C9—C10—C11	−1.5 (3)
C7—C8—C9—C10	0.9 (3)	N4—C11—C10—C9	0.8 (3)
C11—N4—C7—C8	−1.1 (3)

Symmetry code: (i) −x+2, y, −z+5/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H6···S1^ii	0.89	2.49	3.3776 (16)	171
O2—H1···N4^iii	0.89	1.90	2.793 (2)	176

Symmetry codes: (ii) −x+2, −y+2, −z+2; (iii) −x+3/2, −y+3/2, −z+2.