Hexaaqua­manganese(II) dichloride 4,4′-bipyridine N,N′-dioxide disolvate dihydrate

The asymmetric unit of the title compound, [Mn(H₂O)₆]Cl₂·2C₁₀H₈N₂O₂·2H₂O, consists of one half of the [Mn(H₂O)₆]²⁺ cation, with the Mn atom on a centre of inversion, a chloride anion, a 4,4′-bipyridine N,N′-dioxide solvate and a solvent water mol­ecule. 4,4′-Bipyridine N,N′-dioxide mol­ecules link [Mn(H₂O)₆]²⁺ cations through O—H...O hydrogen bonds into a two-dimensional sheet. These sheets are further connected by solvent water mol­ecules and Cl⁻ anions into a three-dimensional network via O—H...Cl and O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.041
• wR factor = 0.120
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mn1    -   O3      ..      17.30 su

Author Response: Outer atoms moving about the metal centre, room temperature measurement.

PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mn1    -   O4      ..      10.49 su

Author Response: Outer atoms moving about the metal centre, room temperature measurement.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.83
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   N1      ..       5.96 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N2     -   C9      ..       6.10 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mn1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.26
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              C10 H8 N2 O2

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.830
            Tmax scaled      0.828 Tmin scaled      0.812

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Hexaaquamanganese(II) dichloride 4,4'-bipyridine N,N'-dioxide disolvate dihydrate

Crystal data

[Mn(H2O)6]Cl2·2C10H8N2O2·2H2O	Z = 1
Mr = 646.34	F(000) = 335
Triclinic, P1	Dx = 1.529 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8062 (2) Å	Cell parameters from 25 reflections
b = 10.2999 (5) Å	θ = 8.7–15.7°
c = 10.5095 (6) Å	µ = 0.73 mm^−1
α = 83.965 (5)°	T = 298 K
β = 73.407 (4)°	Block, yellow
γ = 88.769 (4)°	0.35 × 0.28 × 0.26 mm
V = 702.13 (6) Å^3

Data collection

Enraf–Nonius CAD-4 MACH3 diffractometer	2684 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.008
Graphite monochromator	θmax = 27.0°, θmin = 2.0°
φ and ω scans	h = −8→8
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	k = −13→0
Tmin = 0.978, Tmax = 0.997	l = −13→13
3249 measured reflections	3 standard reflections every 120 min
3075 independent reflections	intensity decay: 1.1%

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)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0578P)^2 + 0.5777P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.032
3075 reflections	Δρmax = 0.58 e Å^−3
206 parameters	Δρmin = −0.35 e Å^−3
11 restraints	Extinction correction: SHELXTL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0441 (15)

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	0.0000	0.5000	0.5000	0.03734 (5)
Cl1	0.20550 (5)	0.10671 (3)	0.56334 (3)	0.05730 (8)
O1	0.18127 (14)	0.30795 (6)	0.13229 (7)	0.0540 (2)
O2	0.36764 (12)	−0.52983 (6)	−0.22457 (7)	0.0460 (2)
O3	0.08514 (13)	0.38457 (7)	0.66624 (7)	0.0536 (2)
O4	0.30097 (13)	0.59057 (8)	0.43039 (10)	0.0651 (3)
O5	0.09776 (16)	0.33810 (7)	0.38612 (7)	0.0661 (3)
O6	0.65215 (16)	0.14828 (9)	0.59151 (10)	0.0757 (3)
N1	0.20546 (12)	0.19269 (7)	0.08677 (7)	0.0353 (2)
N2	0.33961 (12)	−0.41496 (7)	−0.17525 (7)	0.03492 (19)
C1	0.16868 (16)	0.08173 (9)	0.17018 (9)	0.0407 (3)
H1A	0.1254	0.0861	0.2619	0.049*
C2	0.19445 (14)	−0.03803 (9)	0.12107 (9)	0.0371 (2)
H2A	0.1687	−0.1136	0.1803	0.044*
C3	0.25819 (12)	−0.04823 (8)	−0.01532 (8)	0.0293 (2)
C4	0.29464 (14)	0.06909 (9)	−0.09798 (8)	0.0359 (2)
H4A	0.3379	0.0672	−0.1901	0.043*
C5	0.26803 (15)	0.18694 (8)	−0.04634 (8)	0.0367 (2)
H5A	0.2933	0.2638	−0.1036	0.044*
C6	0.28563 (12)	−0.17630 (8)	−0.07069 (8)	0.0303 (2)
C7	0.25538 (15)	−0.29378 (9)	0.01118 (9)	0.0392 (3)
H7A	0.2161	−0.2926	0.1034	0.047*
C8	0.28266 (16)	−0.41170 (9)	−0.04213 (9)	0.0407 (3)
H8A	0.2616	−0.4892	0.0141	0.049*
C9	0.36924 (16)	−0.30406 (9)	−0.25739 (9)	0.0422 (3)
H9A	0.4076	−0.3077	−0.3493	0.051*
C10	0.34354 (16)	−0.18518 (9)	−0.20717 (9)	0.0409 (3)
H10A	0.3653	−0.1092	−0.2657	0.049*
H9	0.2071 (12)	0.4205 (13)	0.6701 (14)	0.100 (2)*
H10	0.151 (2)	0.3091 (9)	0.6337 (14)	0.100 (2)*
H13	0.130 (2)	0.3271 (15)	0.2965 (8)	0.100 (2)*
H14	0.1429 (19)	0.2614 (9)	0.4236 (13)	0.100 (2)*
H16	0.7395 (17)	0.0816 (7)	0.5506 (10)	0.100 (2)*
H15	0.5387 (9)	0.1372 (15)	0.5617 (11)	0.100 (2)*
H12	0.347 (3)	0.5818 (10)	0.3362 (7)	0.135 (7)*
H11	0.300 (3)	0.6855 (7)	0.4384 (11)	0.131 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.04815 (10)	0.02898 (8)	0.03251 (8)	0.00230 (8)	−0.00592 (7)	−0.00850 (7)
Cl1	0.08489 (17)	0.03639 (12)	0.05079 (13)	0.00955 (12)	−0.02019 (12)	−0.00477 (10)
O1	0.0995 (5)	0.0249 (3)	0.0352 (3)	0.0026 (3)	−0.0130 (3)	−0.0108 (2)
O2	0.0668 (4)	0.0253 (3)	0.0440 (3)	0.0027 (3)	−0.0098 (3)	−0.0118 (2)
O3	0.0761 (4)	0.0402 (4)	0.0488 (3)	0.0030 (3)	−0.0231 (3)	−0.0096 (3)
O4	0.0568 (4)	0.0453 (4)	0.0810 (5)	−0.0049 (3)	0.0044 (4)	−0.0185 (4)
O5	0.1249 (6)	0.0406 (3)	0.0322 (3)	0.0281 (4)	−0.0194 (4)	−0.0144 (3)
O6	0.0941 (6)	0.0451 (4)	0.0753 (6)	0.0011 (4)	−0.0013 (5)	−0.0145 (4)
N1	0.0504 (4)	0.0259 (3)	0.0301 (3)	0.0020 (3)	−0.0111 (3)	−0.0071 (3)
N2	0.0442 (4)	0.0260 (3)	0.0342 (3)	0.0023 (3)	−0.0087 (3)	−0.0088 (3)
C1	0.0597 (5)	0.0317 (4)	0.0275 (4)	−0.0012 (4)	−0.0070 (4)	−0.0037 (3)
C2	0.0518 (5)	0.0262 (4)	0.0304 (4)	−0.0006 (4)	−0.0080 (3)	−0.0010 (3)
C3	0.0327 (3)	0.0255 (3)	0.0299 (3)	0.0008 (3)	−0.0087 (3)	−0.0046 (3)
C4	0.0512 (4)	0.0287 (4)	0.0264 (3)	0.0000 (3)	−0.0085 (3)	−0.0038 (3)
C5	0.0552 (5)	0.0263 (4)	0.0274 (4)	−0.0003 (4)	−0.0096 (3)	−0.0023 (3)
C6	0.0343 (3)	0.0251 (3)	0.0312 (3)	0.0004 (3)	−0.0081 (3)	−0.0048 (3)
C7	0.0580 (5)	0.0296 (4)	0.0266 (4)	0.0003 (4)	−0.0066 (4)	−0.0029 (3)
C8	0.0593 (5)	0.0258 (4)	0.0332 (4)	−0.0002 (4)	−0.0074 (4)	−0.0015 (3)
C9	0.0664 (5)	0.0301 (4)	0.0279 (4)	0.0013 (4)	−0.0092 (4)	−0.0043 (3)
C10	0.0632 (5)	0.0266 (4)	0.0302 (4)	0.0023 (4)	−0.0099 (4)	−0.0011 (3)

Geometric parameters (Å, º)

Mn1—O5	2.1384 (8)	N2—C8	1.3447 (12)
Mn1—O5^i	2.1384 (8)	C1—C2	1.3754 (13)
Mn1—O4^i	2.1644 (8)	C1—H1A	0.9300
Mn1—O4	2.1644 (8)	C2—C3	1.3886 (12)
Mn1—O3	2.2167 (8)	C2—H2A	0.9300
Mn1—O3^i	2.2167 (8)	C3—C4	1.3948 (11)
O1—N1	1.3158 (10)	C3—C6	1.4840 (12)
O2—N2	1.3295 (10)	C4—C5	1.3688 (13)
O3—H9	0.929 (10)	C4—H4A	0.9300
O3—H10	0.936 (10)	C5—H5A	0.9300
O4—H12	0.962 (7)	C6—C10	1.3872 (12)
O4—H11	0.990 (7)	C6—C7	1.3919 (12)
O5—H13	0.923 (8)	C7—C8	1.3775 (13)
O5—H14	0.931 (10)	C7—H7A	0.9300
O6—H16	0.953 (8)	C8—H8A	0.9300
O6—H15	0.926 (8)	C9—C10	1.3720 (13)
N1—C1	1.3467 (11)	C9—H9A	0.9300
N1—C5	1.3483 (11)	C10—H10A	0.9300
N2—C9	1.3393 (11)
O5—Mn1—O5^i	180.00 (3)	N1—C1—C2	120.67 (8)
O5—Mn1—O4^i	87.46 (4)	N1—C1—H1A	119.7
O5^i—Mn1—O4^i	92.54 (4)	C2—C1—H1A	119.7
O5—Mn1—O4	92.54 (4)	C1—C2—C3	121.20 (8)
O5^i—Mn1—O4	87.46 (4)	C1—C2—H2A	119.4
O4^i—Mn1—O4	180.00 (4)	C3—C2—H2A	119.4
O5—Mn1—O3	87.38 (3)	C2—C3—C4	116.19 (8)
O5^i—Mn1—O3	92.62 (3)	C2—C3—C6	122.18 (7)
O4^i—Mn1—O3	89.08 (3)	C4—C3—C6	121.62 (7)
O4—Mn1—O3	90.92 (3)	C5—C4—C3	121.36 (8)
O5—Mn1—O3^i	92.62 (3)	C5—C4—H4A	119.3
O5^i—Mn1—O3^i	87.38 (3)	C3—C4—H4A	119.3
O4^i—Mn1—O3^i	90.92 (3)	N1—C5—C4	120.64 (8)
O4—Mn1—O3^i	89.08 (3)	N1—C5—H5A	119.7
O3—Mn1—O3^i	180.00 (2)	C4—C5—H5A	119.7
Mn1—O3—H9	106.3 (9)	C10—C6—C7	116.42 (8)
Mn1—O3—H10	107.8 (9)	C10—C6—C3	121.64 (7)
H9—O3—H10	92.0 (12)	C7—C6—C3	121.94 (8)
Mn1—O4—H12	105.4 (11)	C8—C7—C6	121.08 (8)
Mn1—O4—H11	113.6 (11)	C8—C7—H7A	119.5
H12—O4—H11	105.9 (8)	C6—C7—H7A	119.5
Mn1—O5—H13	134.3 (10)	N2—C8—C7	120.16 (8)
Mn1—O5—H14	121.1 (8)	N2—C8—H8A	119.9
H13—O5—H14	103.6 (13)	C7—C8—H8A	119.9
H16—O6—H15	100.9 (12)	N2—C9—C10	120.57 (8)
O1—N1—C1	121.35 (7)	N2—C9—H9A	119.7
O1—N1—C5	118.71 (7)	C10—C9—H9A	119.7
C1—N1—C5	119.93 (8)	C9—C10—C6	121.20 (8)
O2—N2—C9	120.27 (7)	C9—C10—H10A	119.4
O2—N2—C8	119.16 (7)	C6—C10—H10A	119.4
C9—N2—C8	120.56 (8)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H12···O2^ii	0.96 (1)	2.05 (2)	2.7559 (11)	128 (2)
O5—H13···O1	0.92 (1)	1.69 (1)	2.6146 (10)	178 (2)
O3—H9···O2^iii	0.93 (1)	1.88 (1)	2.7087 (12)	148 (1)
O4—H11···O6^iv	0.99 (1)	1.73 (1)	2.6934 (12)	164 (1)
O3—H10···Cl1	0.94 (1)	2.27 (1)	3.1741 (8)	162 (1)
O5—H14···Cl1	0.93 (1)	2.17 (1)	3.0754 (9)	164 (1)
O6—H15···Cl1	0.93 (1)	2.29 (1)	3.1795 (12)	161 (1)
O6—H16···Cl1^v	0.95 (1)	2.35 (1)	3.2209 (10)	151 (1)

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