Tetra­aqua(1,10-phenanthroline-5,6-dione-κ²N,N′)manganese(II) sulfate dihydrate

The title compound, [Mn(C₁₂H₆N₂O₂)(H₂O)₄]SO₄·2H₂O, was obtained by the reaction of manganese(II) sulfate with an equivalent of 1,10-phenanthroline-5,6-dione in aqueous solution. Mn(II) is hexa­coordinated in a distorted octa­hedral geometry by the two N atoms from the phenanthroline-dione ligand and the O atoms from four coordinated water mol­ecules. Both the cation and anion lie about mirror planes. The structure is stabilized by an extensive network of O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in solvent or counterion
• R factor = 0.040
• wR factor = 0.107
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT432_ALERT_2_A Short Inter X...Y Contact  O7     ..  C6      ..       2.71 Ang.

Author Response: May be caused by the intermolecular hydrogen bonds formation between the sulfate oxygens and the water oxygens.

PLAT432_ALERT_2_A Short Inter X...Y Contact  O7     ..  C6      ..       2.71 Ang.

Author Response: May be caused by the intermolecular hydrogen bonds formation between the sulfate oxygens and the water oxygens.

Alert level C
PLAT214_ALERT_2_C Atom O1#     (Anion/Solvent) ADP max/min Ratio         4.50 prola
PLAT214_ALERT_2_C Atom O8      (Anion/Solvent) ADP max/min Ratio         4.50 prola
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Mn
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for          S
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.74
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      18.00 Perc.
PLAT369_ALERT_2_C Long   C(sp2)-C(sp2) Bond  C6     -   C6_b   ...       1.54 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O6     ..  C5      ..       2.94 Ang.

Author Response: May be caused by the intermolecular hydrogen bonds formation between the sulfate oxygens and the water oxygens.

PLAT432_ALERT_2_C Short Inter X...Y Contact  O6     ..  C5      ..       2.94 Ang.

Author Response: May be caused by the intermolecular hydrogen bonds formation between the sulfate oxygens and the water oxygens.

PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   9 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Tetraaqua-(1,10-phenanthroline-5,6-dione-N,N')manganese(II) sulfate hydrate

Crystal data

C12H14MnN2O6·O4S·H4O2	F(000) = 964
Mr = 469.28	Dx = 1.692 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 3587 reflections
a = 9.6237 (4) Å	θ = 2.6–29.4°
b = 13.9117 (6) Å	µ = 0.90 mm^−1
c = 13.8744 (6) Å	T = 293 K
β = 97.317 (3)°	Block, yellow
V = 1842.41 (14) Å^3	0.30 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	1906 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 27.5°, θmin = 1.5°
φ and ω scans	h = −11→12
10376 measured reflections	k = −18→18
2205 independent reflections	l = −18→18

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.107	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0445P)^2 + 3.5719P] where P = (Fo^2 + 2Fc^2)/3
2205 reflections	(Δ/σ)max < 0.001
158 parameters	Δρmax = 0.63 e Å^−3
11 restraints	Δρmin = −0.44 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	Occ. (<1)
O8	0.2157 (8)	0.0851 (6)	0.3649 (11)	0.126 (10)	0.35 (2)
O8'	0.2004 (12)	0.0320 (11)	0.3953 (5)	0.084 (8)	0.331 (14)
O8''	0.261 (3)	0.1095 (8)	0.3231 (11)	0.181 (11)	0.319 (15)
C1	0.1513 (3)	0.69232 (19)	0.2146 (2)	0.0415 (6)
H1	0.2263	0.7225	0.2515	0.050*
C2	0.0481 (3)	0.7495 (2)	0.1646 (2)	0.0485 (7)
H2	0.0547	0.8162	0.1669	0.058*
C3	−0.0641 (3)	0.7050 (2)	0.1116 (2)	0.0443 (6)
H3	−0.1350	0.7413	0.0772	0.053*
C4	−0.0705 (2)	0.60576 (18)	0.10989 (16)	0.0328 (5)
C5	0.0386 (2)	0.55302 (16)	0.16119 (15)	0.0270 (4)
C6	−0.1905 (3)	0.5552 (2)	0.05441 (17)	0.0391 (6)
Mn	0.31165 (5)	0.5000	0.29690 (4)	0.03150 (18)
N	0.1488 (2)	0.59675 (14)	0.21260 (14)	0.0312 (4)
O1	−0.2848 (2)	0.59738 (19)	0.00612 (16)	0.0621 (6)
O2	0.4378 (3)	0.5000	0.17485 (18)	0.0450 (7)
H21	0.5285	0.5000	0.1820	0.054*
H22	0.4095	0.5000	0.1153	0.054*
O3	0.1880 (3)	0.5000	0.4152 (2)	0.0668 (10)
H31	0.0915	0.5000	0.4069	0.080*
H32	0.2126	0.5000	0.4776	0.080*
O4	0.4434 (2)	0.61274 (16)	0.35852 (17)	0.0592 (6)
H41	0.4188	0.6661	0.3883	0.071*
H42	0.5197	0.6022	0.3749	0.071*
S	0.27286 (9)	0.0000	0.32154 (6)	0.0395 (2)
O6	0.4203 (3)	0.0000	0.3394 (3)	0.111 (2)
O7	0.2144 (3)	0.0000	0.22185 (19)	0.0980 (18)
O5	0.3641 (3)	0.77055 (19)	0.4503 (2)	0.0797 (8)
H51	0.3290	0.8285	0.4209	0.096*
H52	0.4510	0.7977	0.4760	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O8	0.020 (5)	0.141 (17)	0.22 (2)	−0.019 (6)	0.015 (7)	−0.135 (15)
O8'	0.068 (6)	0.16 (2)	0.027 (3)	0.064 (9)	0.004 (3)	0.003 (5)
O8''	0.40 (3)	0.038 (5)	0.072 (8)	0.014 (11)	−0.095 (12)	0.015 (5)
C1	0.0406 (14)	0.0337 (13)	0.0494 (15)	−0.0029 (10)	0.0027 (11)	−0.0027 (11)
C2	0.0543 (17)	0.0326 (13)	0.0584 (17)	0.0049 (12)	0.0065 (14)	0.0037 (12)
C3	0.0452 (15)	0.0437 (15)	0.0436 (14)	0.0151 (12)	0.0043 (12)	0.0086 (12)
C4	0.0300 (12)	0.0413 (13)	0.0271 (11)	0.0050 (9)	0.0037 (9)	0.0049 (9)
C5	0.0233 (10)	0.0336 (12)	0.0245 (10)	0.0019 (8)	0.0045 (8)	0.0009 (8)
C6	0.0301 (12)	0.0589 (16)	0.0273 (11)	0.0050 (11)	0.0003 (9)	0.0019 (11)
Mn	0.0227 (3)	0.0376 (3)	0.0329 (3)	0.000	−0.00153 (19)	0.000
N	0.0269 (10)	0.0318 (10)	0.0342 (10)	−0.0012 (8)	0.0014 (8)	−0.0007 (8)
O1	0.0469 (13)	0.0778 (16)	0.0547 (12)	0.0140 (11)	−0.0205 (10)	0.0064 (11)
O2	0.0278 (13)	0.075 (2)	0.0316 (13)	0.000	0.0014 (10)	0.000
O3	0.0312 (15)	0.137 (3)	0.0324 (14)	0.000	0.0032 (11)	0.000
O4	0.0346 (10)	0.0607 (13)	0.0801 (15)	−0.0028 (9)	−0.0014 (10)	−0.0320 (12)
S	0.0243 (4)	0.0645 (6)	0.0289 (4)	0.000	0.0007 (3)	0.000
O6	0.0261 (16)	0.257 (7)	0.049 (2)	0.000	−0.0024 (14)	0.000
O7	0.0309 (16)	0.231 (6)	0.0305 (16)	0.000	0.0000 (12)	0.000
O5	0.0826 (18)	0.0573 (14)	0.0912 (19)	0.0227 (13)	−0.0203 (15)	−0.0208 (13)

Geometric parameters (Å, º)

O8—S	1.467 (3)	Mn—O4^ii	2.127 (2)
O8'—O8'^i	0.89 (3)	Mn—O3	2.146 (3)
O8'—S	1.383 (8)	Mn—O2	2.206 (2)
O8''—S	1.528 (11)	Mn—N^ii	2.273 (2)
C1—N	1.330 (3)	Mn—N	2.273 (2)
C1—C2	1.387 (4)	O2—H21	0.8662
C1—H1	0.9300	O2—H22	0.8361
C2—C3	1.374 (4)	O3—H31	0.9211
C2—H2	0.9300	O3—H32	0.8680
C3—C4	1.382 (4)	O4—H41	0.8955
C3—H3	0.9300	O4—H42	0.7549
C4—C5	1.399 (3)	S—O8'^i	1.383 (8)
C4—C6	1.481 (3)	S—O6	1.409 (3)
C5—N	1.346 (3)	S—O7	1.425 (3)
C5—C5^ii	1.475 (4)	S—O8^i	1.467 (3)
C6—O1	1.209 (3)	S—O8''^i	1.528 (11)
C6—C6^ii	1.537 (6)	O5—H51	0.9464
Mn—O4	2.127 (2)	O5—H52	0.9460
O8'^i—O8'—S	71.3 (6)	C1—N—Mn	124.89 (17)
N—C1—C2	123.6 (3)	C5—N—Mn	116.76 (15)
N—C1—H1	118.2	Mn—O2—H21	123.9
C2—C1—H1	118.2	Mn—O2—H22	128.1
C3—C2—C1	118.3 (3)	H21—O2—H22	108.0
C3—C2—H2	120.9	Mn—O3—H31	123.6
C1—C2—H2	120.9	Mn—O3—H32	130.9
C2—C3—C4	119.2 (2)	H31—O3—H32	105.4
C2—C3—H3	120.4	Mn—O4—H41	128.1
C4—C3—H3	120.4	Mn—O4—H42	119.0
C3—C4—C5	119.1 (2)	H41—O4—H42	109.0
C3—C4—C6	120.8 (2)	O8'—S—O6	117.5 (5)
C5—C4—C6	120.0 (2)	O8'^i—S—O6	117.5 (5)
N—C5—C4	121.5 (2)	O8'—S—O7	123.0 (4)
N—C5—C5^ii	116.87 (13)	O8'^i—S—O7	123.0 (4)
C4—C5—C5^ii	121.64 (14)	O6—S—O7	115.7 (2)
O1—C6—C4	122.6 (3)	O8'^i—S—O8	72.8 (10)
O1—C6—C6^ii	118.99 (18)	O6—S—O8	110.5 (4)
C4—C6—C6^ii	118.32 (14)	O7—S—O8	106.0 (6)
O4—Mn—O4^ii	95.04 (13)	O8'—S—O8^i	72.8 (10)
O4—Mn—O3	93.02 (8)	O6—S—O8^i	110.5 (3)
O4^ii—Mn—O3	93.02 (8)	O7—S—O8^i	106.0 (6)
O4—Mn—O2	87.15 (8)	O8—S—O8^i	107.6 (10)
O4^ii—Mn—O2	87.15 (8)	O8'—S—O8''^i	105.3 (10)
O3—Mn—O2	179.73 (10)	O8'^i—S—O8''^i	67.9 (14)
O4—Mn—N^ii	168.55 (8)	O6—S—O8''^i	94.1 (11)
O4^ii—Mn—N^ii	96.13 (8)	O7—S—O8''^i	89.6 (4)
O3—Mn—N^ii	88.88 (8)	O8—S—O8''^i	140.0 (13)
O2—Mn—N^ii	90.90 (7)	O8'—S—O8''	67.9 (14)
O4—Mn—N	96.13 (8)	O8'^i—S—O8''	105.3 (10)
O4^ii—Mn—N	168.55 (8)	O6—S—O8''	94.1 (11)
O3—Mn—N	88.88 (8)	O7—S—O8''	89.6 (4)
O2—Mn—N	90.90 (7)	O8^i—S—O8''	140.0 (13)
N^ii—Mn—N	72.61 (10)	O8''^i—S—O8''	171 (2)
C1—N—C5	118.3 (2)	H51—O5—H52	94.1

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41···O5	0.90	1.80	2.697 (3)	178
O2—H21···O7^iii	0.87	1.80	2.659 (4)	169
O3—H31···O6^iv	0.92	1.79	2.656 (4)	156
O3—H32···O8′^v	0.87	1.91	2.747 (8)	163
O3—H32···O8′^vi	0.87	1.91	2.747 (8)	163
O4—H42···O8^iii	0.75	1.92	2.639 (8)	158
O4—H42···O8′^iii	0.75	1.98	2.705 (9)	160
O5—H51···O8′′^ii	0.95	1.67	2.537 (13)	151
O5—H51···O8^ii	0.95	1.74	2.654 (8)	162
O5—H52···O5^vii	0.95	1.97	2.798 (5)	145

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