cis-Aqua­dichloro­(1,10-phenanthroline-κ²N,N′)(thio­urea-κS)manganese(II) thio­urea solvate

The title compound, [MnCl₂(C₁₂H₈N₂){(NH₂)₂CS}(H₂O)]·(NH₂)₂CS, displays a distorted octa­hedral coordination geometry. The coordinated thio­urea and water ligands are in trans positions, while the two Cl⁻ ions are in cis positions. In the crystal structure, a three-dimensional supra­molecular structure involving hydrogen bonding and aromatic stacking is observed.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.027
• wR factor = 0.072
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   Cl2     ..       5.61 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   S1      ..       8.19 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         C2
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3B    ...          ?

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

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

---

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) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

cis-Aquadichloro(1,10-phenanthroline-κ²N,N')(thiourea-κS)manganese(II) thiourea solvate

Crystal data

[MnCl2(C12H8N2)(CH4N2S)(H2O)]·CH4N2S	Z = 2
Mr = 476.30	F(000) = 486
Triclinic, P1	Dx = 1.560 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8590 (18) Å	Cell parameters from 3011 reflections
b = 9.811 (2) Å	θ = 2.6–25.1°
c = 11.706 (2) Å	µ = 1.14 mm^−1
α = 86.46 (3)°	T = 298 K
β = 87.04 (3)°	Prism, yellow
γ = 89.89 (3)°	0.25 × 0.15 × 0.10 mm
V = 1014.1 (3) Å^3

Data collection

Bruker APEX area-detector diffractometer	3619 independent reflections
Radiation source: fine-focus sealed tube	2984 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.011
φ and ω scans	θmax = 25.2°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −9→10
Tmin = 0.764, Tmax = 0.895	k = −11→9
5498 measured reflections	l = −11→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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0341P)^2 + 0.3271P] where P = (Fo^2 + 2Fc^2)/3
3619 reflections	(Δ/σ)max < 0.001
243 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.23 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	0.28545 (4)	0.26308 (3)	0.26181 (3)	0.03709 (11)
Cl1	0.50164 (6)	0.42523 (6)	0.25717 (5)	0.05098 (16)
Cl2	0.17702 (7)	0.30335 (6)	0.45622 (5)	0.05070 (16)
S1	0.11965 (6)	0.45665 (6)	0.15689 (5)	0.04532 (16)
S2	0.28419 (7)	0.86558 (6)	0.51450 (6)	0.05110 (17)
O1	0.4336 (2)	0.09899 (19)	0.33305 (15)	0.0469 (4)
H1C	0.387 (4)	0.037 (4)	0.377 (3)	0.092 (12)*
H1D	0.508 (4)	0.126 (3)	0.368 (3)	0.077 (10)*
N1	−0.1708 (2)	0.4935 (2)	0.13107 (17)	0.0536 (5)
H1B	−0.2648	0.4899	0.1534	0.064*
H1A	−0.1444	0.5277	0.0636	0.064*
N2	−0.1114 (2)	0.3953 (3)	0.30233 (19)	0.0742 (7)
H2A	−0.2061	0.3928	0.3228	0.089*
H2B	−0.0458	0.3642	0.3489	0.089*
N3	0.2171 (3)	0.6550 (3)	0.4019 (3)	0.0950 (10)
H3A	0.2375	0.5826	0.3663	0.114*
H3B	0.1251	0.6826	0.4098	0.114*
N4	0.4652 (3)	0.6769 (3)	0.4297 (2)	0.0811 (8)
H4A	0.4817	0.6041	0.3937	0.097*
H4B	0.5393	0.7194	0.4563	0.097*
N5	0.3480 (2)	0.20319 (18)	0.07874 (15)	0.0388 (4)
N6	0.1402 (2)	0.08208 (18)	0.23058 (15)	0.0397 (4)
C1	−0.0672 (2)	0.4467 (2)	0.20026 (19)	0.0409 (5)
C2	0.3262 (3)	0.7235 (3)	0.4441 (2)	0.0536 (6)
C3	0.4433 (3)	0.2666 (3)	0.0022 (2)	0.0483 (6)
H3	0.4895	0.3463	0.0218	0.058*
C4	0.4776 (3)	0.2201 (3)	−0.1060 (2)	0.0584 (7)
H4	0.5438	0.2687	−0.1576	0.070*
C5	0.4129 (3)	0.1023 (3)	−0.1350 (2)	0.0592 (7)
H5	0.4357	0.0691	−0.2066	0.071*
C6	0.3113 (3)	0.0305 (3)	−0.0568 (2)	0.0484 (6)
C7	0.2394 (3)	−0.0943 (3)	−0.0801 (2)	0.0621 (7)
H7	0.2613	−0.1328	−0.1497	0.075*
C8	0.1409 (3)	−0.1568 (3)	−0.0032 (3)	0.0627 (8)
H8	0.0963	−0.2383	−0.0204	0.075*
C9	0.1029 (3)	−0.1009 (2)	0.1044 (2)	0.0493 (6)
C10	−0.0032 (3)	−0.1596 (3)	0.1864 (3)	0.0596 (7)
H10	−0.0511	−0.2409	0.1727	0.072*
C11	−0.0357 (3)	−0.0984 (3)	0.2848 (3)	0.0588 (7)
H11	−0.1068	−0.1365	0.3387	0.071*
C12	0.0387 (3)	0.0230 (2)	0.3051 (2)	0.0484 (6)
H12	0.0160	0.0638	0.3735	0.058*
C13	0.1724 (2)	0.0210 (2)	0.13096 (19)	0.0392 (5)
C14	0.2799 (2)	0.0871 (2)	0.04910 (18)	0.0397 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.03750 (19)	0.03831 (19)	0.03530 (19)	−0.00208 (14)	0.00017 (14)	−0.00255 (13)
Cl1	0.0388 (3)	0.0534 (4)	0.0604 (4)	−0.0103 (3)	0.0043 (3)	−0.0064 (3)
Cl2	0.0549 (3)	0.0592 (4)	0.0371 (3)	0.0004 (3)	0.0043 (3)	−0.0008 (3)
S1	0.0339 (3)	0.0553 (4)	0.0442 (3)	0.0035 (3)	0.0032 (2)	0.0122 (3)
S2	0.0514 (4)	0.0479 (4)	0.0544 (4)	−0.0026 (3)	−0.0055 (3)	−0.0039 (3)
O1	0.0472 (10)	0.0454 (10)	0.0484 (10)	0.0010 (8)	−0.0079 (8)	−0.0013 (8)
N1	0.0356 (10)	0.0751 (15)	0.0481 (12)	0.0029 (10)	0.0020 (9)	0.0078 (10)
N2	0.0423 (12)	0.119 (2)	0.0550 (14)	0.0078 (13)	0.0115 (10)	0.0308 (14)
N3	0.109 (2)	0.0620 (17)	0.122 (2)	0.0071 (15)	−0.0559 (19)	−0.0326 (16)
N4	0.0814 (18)	0.091 (2)	0.0754 (17)	0.0201 (15)	−0.0098 (14)	−0.0336 (15)
N5	0.0396 (10)	0.0391 (10)	0.0375 (10)	0.0048 (8)	−0.0012 (8)	−0.0005 (8)
N6	0.0390 (10)	0.0406 (10)	0.0393 (10)	−0.0010 (8)	−0.0046 (8)	0.0006 (8)
C1	0.0391 (12)	0.0402 (12)	0.0425 (13)	−0.0017 (10)	0.0027 (10)	0.0005 (10)
C2	0.0696 (17)	0.0479 (14)	0.0435 (14)	0.0011 (13)	−0.0135 (12)	0.0042 (11)
C3	0.0500 (14)	0.0488 (14)	0.0447 (14)	0.0045 (11)	0.0042 (11)	0.0024 (11)
C4	0.0603 (16)	0.0695 (18)	0.0428 (14)	0.0145 (14)	0.0083 (12)	0.0080 (12)
C5	0.0644 (17)	0.0760 (19)	0.0376 (14)	0.0259 (15)	−0.0001 (12)	−0.0093 (13)
C6	0.0505 (14)	0.0538 (15)	0.0427 (14)	0.0214 (12)	−0.0112 (11)	−0.0114 (11)
C7	0.0731 (19)	0.0591 (17)	0.0584 (17)	0.0219 (15)	−0.0204 (15)	−0.0249 (14)
C8	0.0709 (18)	0.0443 (15)	0.078 (2)	0.0107 (13)	−0.0283 (16)	−0.0218 (14)
C9	0.0492 (14)	0.0362 (12)	0.0643 (16)	0.0068 (11)	−0.0204 (12)	−0.0026 (11)
C10	0.0592 (16)	0.0357 (13)	0.085 (2)	−0.0067 (12)	−0.0223 (15)	0.0041 (13)
C11	0.0527 (15)	0.0508 (16)	0.0708 (19)	−0.0113 (12)	−0.0079 (13)	0.0174 (13)
C12	0.0449 (13)	0.0525 (14)	0.0468 (14)	−0.0021 (11)	−0.0045 (11)	0.0057 (11)
C13	0.0386 (12)	0.0359 (12)	0.0441 (13)	0.0052 (9)	−0.0117 (10)	−0.0019 (9)
C14	0.0387 (12)	0.0417 (13)	0.0394 (12)	0.0141 (10)	−0.0073 (9)	−0.0042 (9)

Geometric parameters (Å, º)

Mn1—S1	2.6758 (11)	N5—C14	1.362 (3)
Mn1—Cl1	2.4884 (10)	N6—C12	1.328 (3)
Mn1—Cl2	2.4783 (9)	N6—C13	1.361 (3)
Mn1—O1	2.2247 (19)	C3—C4	1.391 (3)
Mn1—N5	2.2971 (18)	C3—H3	0.9300
Mn1—N6	2.2540 (19)	C4—C5	1.361 (4)
S1—C1	1.708 (2)	C4—H4	0.9300
S2—C2	1.694 (3)	C5—C6	1.407 (4)
N1—C1	1.319 (3)	C5—H5	0.9300
N2—C1	1.309 (3)	C6—C14	1.404 (3)
N3—C2	1.312 (4)	C6—C7	1.429 (4)
N4—C2	1.319 (3)	C7—C8	1.342 (4)
O1—H1C	0.87 (4)	C7—H7	0.9300
O1—H1D	0.84 (3)	C8—C9	1.429 (4)
N1—H1B	0.8600	C8—H8	0.9300
N1—H1A	0.8600	C9—C13	1.404 (3)
N2—H2A	0.8600	C9—C10	1.406 (4)
N2—H2B	0.8600	C10—C11	1.350 (4)
N3—H3A	0.8600	C10—H10	0.9300
N3—H3B	0.8600	C11—C12	1.401 (3)
N4—H4A	0.8600	C11—H11	0.9300
N4—H4B	0.8600	C12—H12	0.9300
N5—C3	1.326 (3)	C13—C14	1.442 (3)
Cl1—Mn1—Cl2	98.26 (4)	N3—C2—N4	117.7 (3)
N5—Mn1—N6	73.23 (7)	N3—C2—S2	119.5 (2)
O1—Mn1—S1	174.64 (5)	N4—C2—S2	122.9 (2)
C1—S1—Mn1	112.52 (8)	N5—C3—C4	123.4 (2)
O1—Mn1—N6	81.64 (7)	N5—C3—H3	118.3
O1—Mn1—N5	90.62 (7)	C4—C3—H3	118.3
O1—Mn1—Cl2	90.92 (6)	C5—C4—C3	118.9 (2)
N6—Mn1—Cl2	97.06 (6)	C5—C4—H4	120.6
N5—Mn1—Cl2	169.83 (5)	C3—C4—H4	120.6
O1—Mn1—Cl1	89.26 (6)	C4—C5—C6	120.1 (2)
N6—Mn1—Cl1	162.27 (5)	C4—C5—H5	120.0
N5—Mn1—Cl1	91.80 (6)	C6—C5—H5	120.0
N6—Mn1—S1	97.93 (5)	C14—C6—C5	117.1 (2)
N5—Mn1—S1	84.14 (5)	C14—C6—C7	119.3 (2)
Cl2—Mn1—S1	94.44 (3)	C5—C6—C7	123.6 (2)
Cl1—Mn1—S1	89.72 (3)	C8—C7—C6	121.1 (2)
Mn1—O1—H1C	115 (2)	C8—C7—H7	119.5
Mn1—O1—H1D	116 (2)	C6—C7—H7	119.5
H1C—O1—H1D	107 (3)	C7—C8—C9	121.5 (2)
C1—N1—H1B	120.0	C7—C8—H8	119.3
C1—N1—H1A	120.0	C9—C8—H8	119.3
H1B—N1—H1A	120.0	C13—C9—C10	117.0 (2)
C1—N2—H2A	120.0	C13—C9—C8	119.2 (2)
C1—N2—H2B	120.0	C10—C9—C8	123.8 (2)
H2A—N2—H2B	120.0	C11—C10—C9	120.2 (2)
C2—N3—H3A	120.0	C11—C10—H10	119.9
C2—N3—H3B	120.0	C9—C10—H10	119.9
H3A—N3—H3B	120.0	C10—C11—C12	119.4 (2)
C2—N4—H4A	120.0	C10—C11—H11	120.3
C2—N4—H4B	120.0	C12—C11—H11	120.3
H4A—N4—H4B	120.0	N6—C12—C11	122.7 (2)
C3—N5—C14	117.96 (19)	N6—C12—H12	118.7
C3—N5—Mn1	127.49 (16)	C11—C12—H12	118.7
C14—N5—Mn1	114.53 (14)	N6—C13—C9	122.7 (2)
C12—N6—C13	118.0 (2)	N6—C13—C14	117.86 (19)
C12—N6—Mn1	125.75 (16)	C9—C13—C14	119.4 (2)
C13—N6—Mn1	115.87 (14)	N5—C14—C6	122.5 (2)
N2—C1—N1	118.4 (2)	N5—C14—C13	117.86 (19)
N2—C1—S1	121.58 (19)	C6—C14—C13	119.6 (2)
N1—C1—S1	120.02 (17)
Mn1—S1—C1—N1	−153.46 (17)	C14—C6—C7—C8	1.1 (4)
Mn1—S1—C1—N2	27.8 (2)	C5—C6—C7—C8	−178.5 (2)
N6—Mn1—S1—C1	49.83 (10)	C6—C7—C8—C9	0.5 (4)
N5—Mn1—S1—C1	121.94 (10)	C7—C8—C9—C13	−1.1 (4)
Cl2—Mn1—S1—C1	−47.95 (9)	C7—C8—C9—C10	177.8 (2)
Cl1—Mn1—S1—C1	−146.22 (9)	C13—C9—C10—C11	0.7 (4)
O1—Mn1—N5—C3	−102.99 (19)	C8—C9—C10—C11	−178.2 (2)
N6—Mn1—N5—C3	175.93 (19)	C9—C10—C11—C12	−0.9 (4)
Cl2—Mn1—N5—C3	158.3 (2)	C13—N6—C12—C11	−0.1 (3)
Cl1—Mn1—N5—C3	−13.72 (18)	Mn1—N6—C12—C11	−172.69 (17)
S1—Mn1—N5—C3	75.81 (18)	C10—C11—C12—N6	0.6 (4)
O1—Mn1—N5—C14	75.45 (15)	C12—N6—C13—C9	0.0 (3)
N6—Mn1—N5—C14	−5.62 (13)	Mn1—N6—C13—C9	173.29 (16)
Cl2—Mn1—N5—C14	−23.3 (4)	C12—N6—C13—C14	178.55 (19)
Cl1—Mn1—N5—C14	164.73 (14)	Mn1—N6—C13—C14	−8.2 (2)
S1—Mn1—N5—C14	−105.74 (14)	C10—C9—C13—N6	−0.3 (3)
O1—Mn1—N6—C12	86.76 (18)	C8—C9—C13—N6	178.7 (2)
N5—Mn1—N6—C12	179.96 (19)	C10—C9—C13—C14	−178.8 (2)
Cl2—Mn1—N6—C12	−3.13 (18)	C8—C9—C13—C14	0.2 (3)
Cl1—Mn1—N6—C12	146.57 (16)	C3—N5—C14—C6	2.4 (3)
S1—Mn1—N6—C12	−98.64 (18)	Mn1—N5—C14—C6	−176.20 (16)
O1—Mn1—N6—C13	−85.94 (15)	C3—N5—C14—C13	−177.85 (19)
N5—Mn1—N6—C13	7.25 (14)	Mn1—N5—C14—C13	3.5 (2)
Cl2—Mn1—N6—C13	−175.84 (14)	C5—C6—C14—N5	−2.6 (3)
Cl1—Mn1—N6—C13	−26.1 (3)	C7—C6—C14—N5	177.8 (2)
S1—Mn1—N6—C13	88.65 (14)	C5—C6—C14—C13	177.6 (2)
C14—N5—C3—C4	−0.5 (3)	C7—C6—C14—C13	−2.0 (3)
Mn1—N5—C3—C4	177.94 (17)	N6—C13—C14—N5	3.0 (3)
N5—C3—C4—C5	−1.2 (4)	C9—C13—C14—N5	−178.39 (19)
C3—C4—C5—C6	0.9 (4)	N6—C13—C14—C6	−177.23 (18)
C4—C5—C6—C14	0.9 (4)	C9—C13—C14—C6	1.4 (3)
C4—C5—C6—C7	−179.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1^i	0.86	2.57	3.383 (2)	157
N1—H1B···Cl1^ii	0.86	2.41	3.239 (2)	162
N2—H2A···Cl1^ii	0.86	2.75	3.504 (2)	147
N2—H2B···Cl2	0.86	2.45	3.295 (3)	168
O1—H1C···S2^iii	0.87 (4)	2.40 (4)	3.260 (2)	173 (3)
O1—H1D···S2^iv	0.84 (3)	2.36 (3)	3.177 (2)	164 (3)
N4—H4A···Cl1	0.86	2.45	3.290 (3)	167
N4—H4B···Cl2^iv	0.86	2.77	3.513 (3)	146
C5—H5···O1^v	0.93	2.52	3.370 (3)	151

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