Tetra­aqua­phenanthrolinemanganese(II) sulfate dihydrate

In the title compound, [Mn(C₁₂H₈N₂)(H₂O)₄]SO₄·2H₂O, the Mn^II atom is coordinated by two N atoms of 1,10-phenanthroline and four water O atoms in a distorted octahedral geometry. The aqua ligands are connected to the sulfate anion and water mol­ecules of crystallization via O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.031
• wR factor = 0.069
• Data-to-parameter ratio = 12.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C3     -   C4      ..       6.15 su
PLAT731_ALERT_1_C Bond    Calc     0.82(2), Rep    0.823(9) ......       2.22 su-Rat
              O1   -H1B     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.83(2), Rep    0.829(9) ......       2.22 su-Rat
              O2   -H2B     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc   0.814(19), Rep    0.813(9) ......       2.11 su-Rat
              O3   -H3A     1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.82(3), Rep   0.818(10) ......       3.00 su-Rat
              O6   -H6B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(2), Rep    0.823(9) ......       2.22 su-Rat
              O1   -H1B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.83(2), Rep    0.829(9) ......       2.22 su-Rat
              O2   -H2B     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc   0.814(19), Rep    0.813(9) ......       2.11 su-Rat
              O3   -H3A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(3), Rep   0.818(10) ......       3.00 su-Rat
              O6   -H6B     1.555   1.555

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

   9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Tetraaquaphenanthrolinemanganese(II) sulfate dihydrate

Crystal data

[Mn(C12H8N2)(H2O)4]SO4·2H2O	F(000) = 1816.0
Mr = 439.30	Dx = 1.607 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 31 reflections
a = 8.877 (1) Å	θ = 4.1–13.6°
b = 18.508 (3) Å	µ = 0.90 mm^−1
c = 22.098 (3) Å	T = 295 K
V = 3630.6 (9) Å^3	Prism, yellow
Z = 8	0.56 × 0.44 × 0.40 mm

Data collection

Siemens P4 diffractometer	2501 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 26.0°, θmin = 1.8°
ω scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→22
Tmin = 0.608, Tmax = 0.699	l = −1→27
4394 measured reflections	3 standard reflections every 97 reflections
3568 independent reflections	intensity decay: 7.5%

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.069	w = 1/[σ^2(Fo^2) + (0.0341P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max = 0.001
3568 reflections	Δρmax = 0.23 e Å^−3
284 parameters	Δρmin = −0.29 e Å^−3
18 restraints	Extinction correction: SHELXL97
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0076 (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
Mn	0.36579 (4)	0.411978 (17)	0.414764 (15)	0.02919 (11)
S	0.08884 (6)	0.65596 (3)	0.46790 (3)	0.03150 (15)
O1	0.2157 (2)	0.32103 (8)	0.42482 (8)	0.0376 (4)
O2	0.23617 (19)	0.46317 (9)	0.48810 (9)	0.0409 (4)
O3	0.5136 (2)	0.50550 (9)	0.42458 (9)	0.0405 (4)
O4	0.5248 (2)	0.35400 (9)	0.47004 (9)	0.0437 (4)
O5	0.4450 (2)	0.63036 (9)	0.36978 (9)	0.0481 (5)
O6	0.7041 (2)	0.70377 (13)	0.40313 (10)	0.0585 (5)
O7	0.17135 (18)	0.68761 (8)	0.41684 (8)	0.0421 (4)
O8	0.04059 (18)	0.71413 (8)	0.50961 (8)	0.0430 (4)
O9	−0.04452 (17)	0.61715 (9)	0.44576 (8)	0.0445 (4)
O10	0.18736 (18)	0.60551 (8)	0.50068 (8)	0.0461 (5)
N1	0.2610 (2)	0.47053 (10)	0.33601 (9)	0.0353 (5)
N2	0.4530 (2)	0.35775 (10)	0.32930 (9)	0.0356 (5)
C1	0.1689 (3)	0.52690 (13)	0.33923 (13)	0.0488 (7)
H1	0.1370	0.5424	0.3772	0.059*
C2	0.1178 (3)	0.56410 (16)	0.28791 (16)	0.0663 (9)
H2	0.0551	0.6041	0.2918	0.080*
C3	0.1618 (4)	0.54040 (18)	0.23224 (16)	0.0698 (10)
H3	0.1287	0.5644	0.1977	0.084*
C4	0.2556 (3)	0.48064 (16)	0.22658 (12)	0.0527 (7)
C5	0.3034 (4)	0.4515 (2)	0.16958 (13)	0.0690 (10)
H5	0.2713	0.4734	0.1339	0.083*
C6	0.3933 (3)	0.3936 (2)	0.16666 (13)	0.0707 (10)
H6	0.4208	0.3755	0.1290	0.085*
C7	0.4477 (3)	0.35897 (16)	0.21967 (12)	0.0494 (7)
C8	0.5416 (3)	0.29828 (17)	0.21971 (15)	0.0638 (9)
H8	0.5712	0.2778	0.1832	0.077*
C9	0.5895 (3)	0.26940 (16)	0.27201 (15)	0.0612 (8)
H9	0.6522	0.2291	0.2720	0.073*
C10	0.5434 (3)	0.30104 (14)	0.32658 (13)	0.0487 (7)
H10	0.5781	0.2812	0.3626	0.058*
C11	0.4044 (3)	0.38674 (13)	0.27672 (11)	0.0356 (6)
C12	0.3054 (3)	0.44759 (13)	0.28015 (11)	0.0367 (6)
H1A	0.258 (2)	0.2821 (8)	0.4202 (11)	0.053 (8)*
H1B	0.141 (2)	0.3146 (13)	0.4459 (11)	0.071 (11)*
H2A	0.216 (3)	0.5068 (6)	0.4881 (15)	0.113 (14)*
H2B	0.168 (2)	0.4421 (11)	0.5066 (11)	0.060 (9)*
H3A	0.485 (3)	0.5425 (9)	0.4083 (11)	0.067 (10)*
H3B	0.578 (2)	0.5142 (12)	0.4498 (8)	0.048 (9)*
H4A	0.6128 (14)	0.3664 (12)	0.4752 (12)	0.058 (9)*
H4B	0.515 (3)	0.3126 (7)	0.4819 (13)	0.070 (10)*
H5A	0.5160 (15)	0.6566 (10)	0.3790 (10)	0.034 (7)*
H5B	0.3675 (14)	0.6486 (11)	0.3838 (11)	0.049 (8)*
H6A	0.775 (2)	0.6790 (14)	0.4139 (13)	0.084 (13)*
H6B	0.681 (4)	0.7325 (16)	0.4297 (12)	0.131 (19)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0331 (2)	0.02436 (17)	0.03011 (19)	0.00109 (15)	−0.00059 (16)	0.00090 (16)
S	0.0270 (3)	0.0208 (3)	0.0467 (4)	−0.0001 (2)	0.0059 (3)	0.0008 (3)
O1	0.0350 (10)	0.0249 (9)	0.0527 (12)	0.0023 (8)	0.0067 (9)	0.0013 (8)
O2	0.0433 (11)	0.0265 (9)	0.0527 (11)	−0.0008 (8)	0.0163 (9)	0.0000 (9)
O3	0.0416 (11)	0.0323 (9)	0.0476 (12)	−0.0068 (8)	−0.0087 (9)	0.0027 (9)
O4	0.0376 (10)	0.0323 (10)	0.0610 (12)	−0.0048 (8)	−0.0152 (10)	0.0147 (9)
O5	0.0427 (11)	0.0388 (10)	0.0628 (13)	−0.0013 (10)	0.0115 (11)	−0.0037 (10)
O6	0.0464 (13)	0.0612 (13)	0.0679 (15)	−0.0023 (11)	−0.0024 (11)	0.0015 (12)
O7	0.0439 (10)	0.0285 (8)	0.0540 (11)	−0.0077 (8)	0.0172 (9)	−0.0017 (8)
O8	0.0475 (10)	0.0269 (8)	0.0545 (11)	0.0053 (8)	0.0156 (9)	−0.0045 (8)
O9	0.0336 (10)	0.0407 (9)	0.0594 (11)	−0.0107 (8)	0.0014 (9)	0.0012 (9)
O10	0.0405 (10)	0.0263 (8)	0.0716 (13)	0.0049 (7)	−0.0078 (9)	0.0036 (9)
N1	0.0356 (11)	0.0299 (10)	0.0404 (12)	−0.0005 (9)	−0.0068 (10)	0.0017 (9)
N2	0.0337 (11)	0.0360 (11)	0.0371 (11)	−0.0012 (9)	0.0032 (9)	−0.0026 (9)
C1	0.0490 (16)	0.0364 (14)	0.0609 (19)	0.0043 (13)	−0.0129 (14)	0.0019 (13)
C2	0.0549 (19)	0.0476 (16)	0.096 (3)	0.0067 (15)	−0.030 (2)	0.0150 (18)
C3	0.063 (2)	0.077 (2)	0.069 (2)	−0.0112 (18)	−0.0317 (19)	0.0327 (19)
C4	0.0411 (15)	0.0674 (18)	0.0496 (17)	−0.0133 (15)	−0.0166 (14)	0.0169 (16)
C5	0.062 (2)	0.111 (3)	0.0332 (17)	−0.019 (2)	−0.0128 (16)	0.0149 (18)
C6	0.059 (2)	0.117 (3)	0.0359 (17)	−0.026 (2)	0.0043 (16)	−0.0065 (19)
C7	0.0418 (16)	0.0711 (19)	0.0354 (15)	−0.0229 (15)	0.0043 (13)	−0.0090 (14)
C8	0.061 (2)	0.068 (2)	0.062 (2)	−0.0134 (17)	0.0210 (17)	−0.0325 (18)
C9	0.0575 (19)	0.0514 (17)	0.075 (2)	0.0002 (15)	0.0189 (18)	−0.0168 (17)
C10	0.0475 (16)	0.0431 (15)	0.0555 (17)	0.0066 (13)	0.0060 (14)	−0.0031 (14)
C11	0.0288 (12)	0.0434 (13)	0.0347 (13)	−0.0125 (11)	0.0012 (11)	−0.0024 (11)
C12	0.0320 (13)	0.0448 (14)	0.0333 (14)	−0.0137 (12)	−0.0079 (11)	0.0062 (12)

Geometric parameters (Å, º)

Mn—O4	2.1530 (16)	N1—C12	1.364 (3)
Mn—O1	2.1580 (16)	N2—C10	1.322 (3)
Mn—O3	2.1829 (17)	N2—C11	1.351 (3)
Mn—O2	2.2018 (17)	C1—C2	1.402 (4)
Mn—N1	2.2513 (19)	C1—H1	0.9300
Mn—N2	2.2747 (19)	C2—C3	1.363 (4)
S—O7	1.4672 (16)	C2—H2	0.9300
S—O9	1.4686 (16)	C3—C4	1.390 (4)
S—O10	1.4703 (16)	C3—H3	0.9300
S—O8	1.4805 (16)	C4—C12	1.404 (3)
O1—H1A	0.818 (9)	C4—C5	1.434 (4)
O1—H1B	0.823 (9)	C5—C6	1.339 (4)
O2—H2A	0.826 (10)	C5—H5	0.9300
O2—H2B	0.829 (9)	C6—C7	1.420 (4)
O3—H3A	0.813 (9)	C6—H6	0.9300
O3—H3B	0.814 (9)	C7—C8	1.399 (4)
O4—H4A	0.823 (9)	C7—C11	1.415 (3)
O4—H4B	0.815 (9)	C8—C9	1.342 (4)
O5—H5A	0.822 (9)	C8—H8	0.9300
O5—H5B	0.827 (9)	C9—C10	1.402 (4)
O6—H6A	0.816 (10)	C9—H9	0.9300
O6—H6B	0.818 (10)	C10—H10	0.9300
N1—C1	1.327 (3)	C11—C12	1.430 (3)
O4—Mn—O1	87.56 (7)	C10—N2—Mn	126.47 (18)
O4—Mn—O3	86.83 (7)	C11—N2—Mn	115.47 (15)
O1—Mn—O3	168.33 (7)	N1—C1—C2	122.8 (3)
O4—Mn—O2	98.01 (8)	N1—C1—H1	118.6
O1—Mn—O2	86.40 (7)	C2—C1—H1	118.6
O3—Mn—O2	84.25 (7)	C3—C2—C1	118.6 (3)
O4—Mn—N1	161.69 (8)	C3—C2—H2	120.7
O1—Mn—N1	101.53 (7)	C1—C2—H2	120.7
O3—Mn—N1	86.76 (7)	C2—C3—C4	120.6 (3)
O2—Mn—N1	98.39 (7)	C2—C3—H3	119.7
O4—Mn—N2	91.60 (8)	C4—C3—H3	119.7
O1—Mn—N2	87.22 (7)	C3—C4—C12	117.4 (3)
O3—Mn—N2	103.16 (7)	C3—C4—C5	123.7 (3)
O2—Mn—N2	168.22 (7)	C12—C4—C5	118.9 (3)
N1—Mn—N2	73.22 (7)	C6—C5—C4	121.3 (3)
O7—S—O9	109.97 (10)	C6—C5—H5	119.3
O7—S—O10	109.60 (10)	C4—C5—H5	119.3
O9—S—O10	109.44 (9)	C5—C6—C7	121.6 (3)
O7—S—O8	109.45 (9)	C5—C6—H6	119.2
O9—S—O8	109.26 (10)	C7—C6—H6	119.2
O10—S—O8	109.10 (10)	C8—C7—C11	116.9 (3)
Mn—O1—H1A	113.1 (16)	C8—C7—C6	124.4 (3)
Mn—O1—H1B	132.2 (18)	C11—C7—C6	118.6 (3)
H1A—O1—H1B	108.3 (15)	C9—C8—C7	120.6 (3)
Mn—O2—H2A	122 (2)	C9—C8—H8	119.7
Mn—O2—H2B	122.8 (18)	C7—C8—H8	119.7
H2A—O2—H2B	107.7 (15)	C8—C9—C10	118.8 (3)
Mn—O3—H3A	116.0 (17)	C8—C9—H9	120.6
Mn—O3—H3B	130.2 (16)	C10—C9—H9	120.6
H3A—O3—H3B	110.7 (16)	N2—C10—C9	123.2 (3)
Mn—O4—H4A	124.2 (17)	N2—C10—H10	118.4
Mn—O4—H4B	125.7 (17)	C9—C10—H10	118.4
H4A—O4—H4B	108.5 (15)	N2—C11—C7	122.4 (2)
H5A—O5—H5B	107.6 (14)	N2—C11—C12	117.6 (2)
H6A—O6—H6B	110.4 (17)	C7—C11—C12	120.0 (2)
C1—N1—C12	118.1 (2)	N1—C12—C4	122.4 (2)
C1—N1—Mn	126.26 (18)	N1—C12—C11	118.1 (2)
C12—N1—Mn	115.49 (15)	C4—C12—C11	119.5 (2)
C10—N2—C11	118.0 (2)
O4—Mn—N1—C1	−143.5 (2)	C5—C6—C7—C8	179.9 (3)
O1—Mn—N1—C1	97.9 (2)	C5—C6—C7—C11	0.3 (4)
O3—Mn—N1—C1	−73.8 (2)	C11—C7—C8—C9	−1.2 (4)
O2—Mn—N1—C1	9.9 (2)	C6—C7—C8—C9	179.2 (3)
N2—Mn—N1—C1	−178.6 (2)	C7—C8—C9—C10	0.1 (4)
O4—Mn—N1—C12	32.3 (3)	C11—N2—C10—C9	−0.6 (4)
O1—Mn—N1—C12	−86.31 (16)	Mn—N2—C10—C9	178.3 (2)
O3—Mn—N1—C12	101.98 (16)	C8—C9—C10—N2	0.9 (4)
O2—Mn—N1—C12	−174.32 (16)	C10—N2—C11—C7	−0.5 (3)
N2—Mn—N1—C12	−2.81 (15)	Mn—N2—C11—C7	−179.63 (17)
O4—Mn—N2—C10	12.73 (19)	C10—N2—C11—C12	179.4 (2)
O1—Mn—N2—C10	−74.75 (19)	Mn—N2—C11—C12	0.3 (3)
O3—Mn—N2—C10	99.85 (19)	C8—C7—C11—N2	1.5 (4)
O2—Mn—N2—C10	−132.1 (3)	C6—C7—C11—N2	−178.9 (2)
N1—Mn—N2—C10	−177.7 (2)	C8—C7—C11—C12	−178.5 (2)
O4—Mn—N2—C11	−168.28 (16)	C6—C7—C11—C12	1.2 (4)
O1—Mn—N2—C11	104.24 (16)	C1—N1—C12—C4	−1.0 (3)
O3—Mn—N2—C11	−81.16 (16)	Mn—N1—C12—C4	−177.12 (18)
O2—Mn—N2—C11	46.9 (4)	C1—N1—C12—C11	−179.9 (2)
N1—Mn—N2—C11	1.31 (15)	Mn—N1—C12—C11	4.0 (3)
C12—N1—C1—C2	−0.9 (4)	C3—C4—C12—N1	2.3 (4)
Mn—N1—C1—C2	174.7 (2)	C5—C4—C12—N1	−177.7 (2)
N1—C1—C2—C3	1.5 (4)	C3—C4—C12—C11	−178.9 (2)
C1—C2—C3—C4	−0.1 (5)	C5—C4—C12—C11	1.1 (4)
C2—C3—C4—C12	−1.7 (4)	N2—C11—C12—N1	−2.9 (3)
C2—C3—C4—C5	178.4 (3)	C7—C11—C12—N1	177.0 (2)
C3—C4—C5—C6	−179.6 (3)	N2—C11—C12—C4	178.2 (2)
C12—C4—C5—C6	0.4 (4)	C7—C11—C12—C4	−1.9 (3)
C4—C5—C6—C7	−1.1 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O7^i	0.82 (1)	1.86 (1)	2.671 (2)	171 (2)
O1—H1B···O8^ii	0.82 (1)	1.96 (1)	2.775 (2)	172 (3)
O2—H2B···O9^ii	0.83 (1)	1.87 (1)	2.691 (2)	169 (3)
O2—H2A···O10	0.83 (1)	1.87 (1)	2.684 (2)	171 (4)
O3—H3A···O5	0.81 (1)	1.87 (1)	2.679 (3)	173 (3)
O3—H3B···O2^iii	0.81 (1)	2.19 (1)	2.999 (3)	175 (2)
O4—H4B···O8^i	0.82 (1)	1.99 (1)	2.793 (2)	171 (2)
O4—H4A···O10^iii	0.82 (1)	1.92 (1)	2.740 (2)	172 (3)
O5—H5A···O6	0.82 (1)	1.96 (1)	2.771 (3)	170 (2)
O5—H5B···O7	0.83 (1)	2.02 (1)	2.847 (2)	176 (2)
O6—H6B···O8^iv	0.82 (1)	2.08 (2)	2.852 (3)	157 (4)
O6—H6A···O9^v	0.82 (1)	2.09 (1)	2.905 (3)	177 (3)

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x+1/2, −y+3/2, −z+1; (v) x+1, y, z.