The title manganese complex, [Mn(C
9H
10NO
2)
2(C
6H
6N
2O)
2(H
2O)
2]·2H
2O, is monomeric and centrosymmetric. It contains two 4-(dimethylamino)benzoate (DMAB) and two nicotinamide (NA) ligands, two coordinated and two uncoordinated water molecules, all ligands being monodentate. The four O atoms in the equatorial plane around the Mn atom form a slightly distorted square-planar arrangement, while the distorted octahedral coordination is completed by the two NA N atoms in the axial positions. In the crystal structure, intermolecular O—H
O and N—H
O hydrogen bonds link the molecules to form a supramolecular structure.
Supporting information
CCDC reference: 647470
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.005 Å
- R factor = 0.072
- wR factor = 0.190
- Data-to-parameter ratio = 12.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 6
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.15
PLAT420_ALERT_2_C D-H Without Acceptor N3 - H32 ... ?
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
4 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
2 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
1 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Diaquabis[4-(dimethylamino)benzoato-
κO](nicotinamide-
κN1)manganese(II) dihydrate
top
Crystal data top
[Mn(C9H10NO2)2(C6H6N2O)2(H2O)2]·2H2O | Z = 1 |
Mr = 699.62 | F(000) = 367 |
Triclinic, P1 | Dx = 1.444 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54184 Å |
a = 8.1979 (2) Å | Cell parameters from 25 reflections |
b = 10.0888 (2) Å | θ = 5.5–21.4° |
c = 10.2559 (3) Å | µ = 3.90 mm−1 |
α = 76.465 (2)° | T = 294 K |
β = 88.984 (3)° | Block, yellow |
γ = 77.442 (3)° | 0.30 × 0.28 × 0.13 mm |
V = 804.46 (4) Å3 | |
Data collection top
Enraf–Nonius TurboCAD-4 diffractometer | 2724 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 74.2°, θmin = 4.4° |
nonprofiled ω scans | h = −10→0 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→12 |
Tmin = 0.362, Tmax = 0.602 | l = −12→12 |
3375 measured reflections | 3 standard reflections every 120 min |
3186 independent reflections | intensity decay: 1% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.190 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.141P)2 + 0.1598P] where P = (Fo2 + 2Fc2)/3 |
3186 reflections | (Δ/σ)max < 0.001 |
264 parameters | Δρmax = 1.38 e Å−3 |
8 restraints | Δρmin = −0.99 e Å−3 |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Mn | 0.0000 | 0.0000 | 0.0000 | 0.0342 (3) | |
O1 | 0.1520 (3) | −0.1400 (2) | 0.1588 (2) | 0.0434 (6) | |
O2 | 0.0219 (4) | −0.1211 (3) | 0.3481 (3) | 0.0542 (7) | |
O3 | 0.2278 (4) | 0.6318 (3) | −0.1241 (3) | 0.0560 (7) | |
O4 | 0.1668 (3) | −0.0842 (2) | −0.1487 (3) | 0.0421 (6) | |
O5 | 0.1013 (5) | 0.1354 (3) | 0.3873 (3) | 0.0675 (9) | |
N1 | 0.4571 (5) | −0.7506 (3) | 0.5091 (3) | 0.0509 (8) | |
N2 | 0.1600 (4) | 0.1624 (3) | −0.0100 (3) | 0.0383 (6) | |
N3 | 0.0032 (5) | 0.5883 (3) | −0.2160 (3) | 0.0464 (7) | |
C1 | 0.1193 (4) | −0.1909 (3) | 0.2796 (3) | 0.0375 (7) | |
C2 | 0.2030 (4) | −0.3379 (3) | 0.3390 (3) | 0.0363 (7) | |
C3 | 0.3173 (5) | −0.4137 (4) | 0.2662 (4) | 0.0433 (8) | |
C4 | 0.3999 (5) | −0.5494 (4) | 0.3199 (4) | 0.0452 (8) | |
C5 | 0.3718 (5) | −0.6177 (3) | 0.4528 (4) | 0.0401 (7) | |
C6 | 0.2532 (6) | −0.5423 (4) | 0.5237 (4) | 0.0489 (9) | |
C7 | 0.1721 (6) | −0.4063 (4) | 0.4682 (4) | 0.0471 (9) | |
C8 | 0.4263 (7) | −0.8195 (4) | 0.6443 (4) | 0.0605 (11) | |
C9 | 0.5772 (7) | −0.8256 (4) | 0.4335 (5) | 0.0676 (13) | |
C10 | 0.3149 (5) | 0.1211 (4) | 0.0452 (4) | 0.0457 (8) | |
C11 | 0.4209 (5) | 0.2106 (4) | 0.0415 (5) | 0.0528 (9) | |
C12 | 0.3648 (5) | 0.3498 (4) | −0.0191 (4) | 0.0453 (8) | |
C13 | 0.2049 (4) | 0.3961 (3) | −0.0773 (3) | 0.0353 (7) | |
C14 | 0.1080 (4) | 0.2980 (3) | −0.0696 (3) | 0.0355 (7) | |
C15 | 0.1456 (5) | 0.5487 (3) | −0.1425 (3) | 0.0397 (7) | |
H3 | 0.342 (6) | −0.356 (5) | 0.168 (5) | 0.064 (14)* | |
H4 | 0.477 (5) | −0.595 (4) | 0.265 (4) | 0.040 (10)* | |
H6 | 0.218 (6) | −0.585 (5) | 0.610 (5) | 0.057 (13)* | |
H7 | 0.091 (8) | −0.356 (6) | 0.505 (6) | 0.083 (18)* | |
H8A | 0.4517 | −0.7673 | 0.7055 | 0.091* | |
H8B | 0.4959 | −0.9120 | 0.6668 | 0.091* | |
H8C | 0.3109 | −0.8251 | 0.6507 | 0.091* | |
H9A | 0.5234 | −0.8325 | 0.3537 | 0.101* | |
H9B | 0.6229 | −0.9176 | 0.4871 | 0.101* | |
H9C | 0.6656 | −0.7767 | 0.4092 | 0.101* | |
H10 | 0.351 (5) | 0.028 (5) | 0.080 (4) | 0.042 (11)* | |
H11 | 0.5286 | 0.1775 | 0.0794 | 0.063* | |
H12 | 0.430 (5) | 0.410 (4) | −0.018 (4) | 0.044 (11)* | |
H14 | 0.0005 | 0.3282 | −0.1081 | 0.043* | |
H31 | −0.032 (6) | 0.680 (5) | −0.261 (5) | 0.052 (12)* | |
H32 | −0.058 (7) | 0.521 (6) | −0.227 (5) | 0.067 (15)* | |
H41 | 0.110 (6) | −0.027 (4) | −0.233 (3) | 0.066 (14)* | |
H42 | 0.175 (5) | −0.178 (2) | −0.152 (4) | 0.045 (11)* | |
H51 | 0.090 (10) | 0.045 (4) | 0.375 (7) | 0.12 (3)* | |
H52 | 0.062 (10) | 0.141 (7) | 0.471 (4) | 0.13 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Mn | 0.0449 (4) | 0.0177 (4) | 0.0362 (4) | −0.0062 (3) | −0.0016 (3) | 0.0007 (2) |
O1 | 0.0506 (14) | 0.0298 (12) | 0.0406 (12) | −0.0033 (10) | 0.0008 (10) | 0.0044 (9) |
O2 | 0.081 (2) | 0.0295 (12) | 0.0424 (13) | 0.0039 (12) | 0.0038 (13) | −0.0051 (10) |
O3 | 0.0662 (18) | 0.0259 (12) | 0.0779 (19) | −0.0154 (12) | 0.0031 (15) | −0.0114 (12) |
O4 | 0.0524 (14) | 0.0246 (11) | 0.0461 (13) | −0.0019 (10) | 0.0009 (11) | −0.0081 (10) |
O5 | 0.107 (3) | 0.0342 (15) | 0.0565 (18) | −0.0109 (16) | 0.0025 (18) | −0.0048 (13) |
N1 | 0.061 (2) | 0.0285 (15) | 0.0522 (18) | 0.0036 (13) | −0.0053 (15) | −0.0001 (13) |
N2 | 0.0467 (15) | 0.0243 (13) | 0.0423 (14) | −0.0086 (11) | −0.0002 (12) | −0.0035 (11) |
N3 | 0.062 (2) | 0.0265 (14) | 0.0465 (16) | −0.0086 (13) | 0.0010 (14) | −0.0016 (12) |
C1 | 0.0499 (18) | 0.0250 (15) | 0.0340 (15) | −0.0066 (13) | −0.0032 (13) | −0.0008 (12) |
C2 | 0.0484 (18) | 0.0242 (15) | 0.0331 (15) | −0.0062 (13) | −0.0021 (13) | −0.0020 (12) |
C3 | 0.053 (2) | 0.0333 (18) | 0.0375 (17) | −0.0041 (15) | 0.0048 (14) | −0.0025 (13) |
C4 | 0.052 (2) | 0.0332 (17) | 0.0442 (18) | −0.0007 (15) | 0.0042 (15) | −0.0049 (14) |
C5 | 0.0483 (18) | 0.0236 (15) | 0.0440 (17) | −0.0025 (13) | −0.0051 (14) | −0.0037 (13) |
C6 | 0.067 (2) | 0.0326 (18) | 0.0376 (18) | −0.0013 (16) | 0.0079 (16) | 0.0019 (14) |
C7 | 0.067 (2) | 0.0279 (17) | 0.0393 (18) | 0.0004 (16) | 0.0102 (16) | −0.0034 (14) |
C8 | 0.085 (3) | 0.0278 (18) | 0.056 (2) | −0.0015 (18) | −0.009 (2) | 0.0054 (16) |
C9 | 0.078 (3) | 0.034 (2) | 0.077 (3) | 0.015 (2) | −0.006 (2) | −0.010 (2) |
C10 | 0.048 (2) | 0.0286 (17) | 0.055 (2) | −0.0064 (14) | −0.0065 (16) | −0.0007 (15) |
C11 | 0.048 (2) | 0.040 (2) | 0.067 (2) | −0.0083 (16) | −0.0074 (18) | −0.0085 (18) |
C12 | 0.0475 (19) | 0.0349 (18) | 0.058 (2) | −0.0165 (15) | 0.0033 (16) | −0.0122 (16) |
C13 | 0.0473 (18) | 0.0231 (15) | 0.0362 (15) | −0.0080 (13) | 0.0068 (13) | −0.0083 (12) |
C14 | 0.0427 (17) | 0.0249 (15) | 0.0397 (16) | −0.0085 (13) | 0.0024 (13) | −0.0082 (12) |
C15 | 0.055 (2) | 0.0233 (15) | 0.0424 (17) | −0.0102 (14) | 0.0133 (15) | −0.0096 (13) |
Geometric parameters (Å, º) top
Mn—O1i | 2.105 (2) | C3—H3 | 1.08 (5) |
Mn—O1 | 2.105 (2) | C4—H4 | 0.96 (4) |
Mn—O4i | 2.224 (2) | C5—N1 | 1.365 (4) |
Mn—O4 | 2.224 (2) | C5—C4 | 1.416 (5) |
Mn—N2i | 2.295 (3) | C5—C6 | 1.401 (5) |
Mn—N2 | 2.295 (3) | C6—H6 | 0.96 (5) |
O1—C1 | 1.272 (4) | C7—C6 | 1.379 (5) |
O2—C1 | 1.263 (4) | C7—H7 | 0.88 (6) |
O3—C15 | 1.231 (4) | C8—H8A | 0.9600 |
O4—H42 | 0.942 (19) | C8—H8B | 0.9600 |
O4—H41 | 0.983 (18) | C8—H8C | 0.9600 |
O5—H51 | 0.97 (5) | C9—H9A | 0.9600 |
O5—H52 | 0.92 (5) | C9—H9B | 0.9600 |
N1—C8 | 1.443 (5) | C9—H9C | 0.9600 |
N1—C9 | 1.438 (6) | C10—C11 | 1.377 (6) |
N2—C10 | 1.339 (5) | C10—H10 | 0.91 (4) |
N2—C14 | 1.338 (4) | C11—H11 | 0.9300 |
N3—C15 | 1.333 (5) | C12—C11 | 1.375 (5) |
N3—H31 | 0.92 (5) | C12—H12 | 0.90 (4) |
N3—H32 | 0.95 (5) | C13—C14 | 1.386 (4) |
C1—C2 | 1.480 (4) | C13—C12 | 1.387 (5) |
C2—C3 | 1.397 (5) | C13—C15 | 1.502 (4) |
C2—C7 | 1.390 (5) | C14—H14 | 0.9300 |
C3—C4 | 1.375 (5) | | |
| | | |
O1i—Mn—O1 | 180.0 (2) | C5—C4—H4 | 121 (2) |
O1i—Mn—O4i | 90.55 (9) | N1—C5—C6 | 121.7 (3) |
O1—Mn—O4i | 89.45 (9) | N1—C5—C4 | 121.4 (3) |
O1i—Mn—O4 | 89.45 (9) | C6—C5—C4 | 116.9 (3) |
O1—Mn—O4 | 90.55 (9) | C5—C6—H6 | 122 (3) |
O4i—Mn—O4 | 180.00 (14) | C7—C6—C5 | 121.5 (3) |
O1i—Mn—N2i | 91.34 (10) | C7—C6—H6 | 116 (3) |
O1—Mn—N2i | 88.66 (10) | C2—C7—H7 | 113 (4) |
O1i—Mn—N2 | 88.66 (10) | C6—C7—C2 | 121.6 (3) |
O1—Mn—N2 | 91.34 (10) | C6—C7—H7 | 125 (4) |
O4i—Mn—N2i | 87.74 (10) | N1—C8—H8A | 109.5 |
O4—Mn—N2i | 92.26 (10) | N1—C8—H8B | 109.5 |
O4i—Mn—N2 | 92.26 (10) | H8A—C8—H8B | 109.5 |
O4—Mn—N2 | 87.74 (10) | N1—C8—H8C | 109.5 |
N2i—Mn—N2 | 180.00 (8) | H8A—C8—H8C | 109.5 |
C1—O1—Mn | 131.3 (2) | H8B—C8—H8C | 109.5 |
Mn—O4—H42 | 118 (3) | N1—C9—H9A | 109.5 |
Mn—O4—H41 | 101 (3) | N1—C9—H9B | 109.5 |
H42—O4—H41 | 107 (3) | H9A—C9—H9B | 109.5 |
H51—O5—H52 | 106 (4) | N1—C9—H9C | 109.5 |
C5—N1—C9 | 120.4 (3) | H9A—C9—H9C | 109.5 |
C5—N1—C8 | 120.8 (3) | H9B—C9—H9C | 109.5 |
C9—N1—C8 | 118.7 (3) | N2—C10—C11 | 123.1 (3) |
C10—N2—Mn | 119.1 (2) | N2—C10—H10 | 116 (3) |
C14—N2—C10 | 117.2 (3) | C11—C10—H10 | 120 (3) |
C14—N2—Mn | 123.7 (2) | C10—C11—H11 | 120.6 |
C15—N3—H31 | 119 (3) | C12—C11—C10 | 118.9 (4) |
C15—N3—H32 | 121 (3) | C12—C11—H11 | 120.6 |
H31—N3—H32 | 120 (4) | C11—C12—C13 | 119.5 (3) |
O1—C1—C2 | 116.9 (3) | C11—C12—H12 | 120 (3) |
O2—C1—O1 | 122.8 (3) | C13—C12—H12 | 121 (3) |
O2—C1—C2 | 120.3 (3) | C12—C13—C15 | 118.7 (3) |
C3—C2—C1 | 120.8 (3) | C14—C13—C12 | 117.5 (3) |
C7—C2—C1 | 122.0 (3) | C14—C13—C15 | 123.9 (3) |
C7—C2—C3 | 117.2 (3) | N2—C14—C13 | 123.9 (3) |
C2—C3—H3 | 115 (3) | N2—C14—H14 | 118.1 |
C4—C3—C2 | 122.1 (3) | C13—C14—H14 | 118.1 |
C4—C3—H3 | 122 (3) | O3—C15—N3 | 122.9 (3) |
C3—C4—C5 | 120.7 (3) | O3—C15—C13 | 119.1 (3) |
C3—C4—H4 | 118 (2) | N3—C15—C13 | 117.9 (3) |
| | | |
O4i—Mn—O1—C1 | 24.8 (3) | C1—C2—C3—C4 | 178.4 (4) |
O4—Mn—O1—C1 | −155.2 (3) | C3—C2—C7—C6 | 1.3 (6) |
N2i—Mn—O1—C1 | −62.9 (3) | C1—C2—C7—C6 | −178.7 (4) |
N2—Mn—O1—C1 | 117.1 (3) | C2—C3—C4—C5 | −0.1 (6) |
O1i—Mn—N2—C14 | 18.4 (3) | C6—C5—N1—C9 | 179.6 (4) |
O1—Mn—N2—C14 | −161.6 (3) | C4—C5—N1—C9 | −0.8 (6) |
O4i—Mn—N2—C14 | −72.1 (3) | C6—C5—N1—C8 | 0.9 (6) |
O4—Mn—N2—C14 | 107.9 (3) | C4—C5—N1—C8 | −179.5 (4) |
O1i—Mn—N2—C10 | −161.0 (3) | N1—C5—C4—C3 | −177.7 (4) |
O1—Mn—N2—C10 | 19.0 (3) | C6—C5—C4—C3 | 2.0 (6) |
O4i—Mn—N2—C10 | 108.5 (3) | N1—C5—C6—C7 | 177.4 (4) |
O4—Mn—N2—C10 | −71.5 (3) | C4—C5—C6—C7 | −2.2 (6) |
Mn—O1—C1—O2 | −37.7 (5) | C2—C7—C6—C5 | 0.6 (7) |
Mn—O1—C1—C2 | 143.0 (3) | N2—C10—C11—C12 | 1.4 (7) |
Mn—N2—C10—C11 | 178.6 (3) | C13—C12—C11—C10 | −1.3 (6) |
C14—N2—C10—C11 | −0.9 (6) | C14—C13—C15—O3 | 167.2 (3) |
Mn—N2—C14—C13 | −179.2 (2) | C12—C13—C15—O3 | −11.7 (5) |
C10—N2—C14—C13 | 0.2 (5) | C14—C13—C15—N3 | −11.5 (5) |
O2—C1—C2—C7 | 3.2 (5) | C12—C13—C15—N3 | 169.6 (3) |
O1—C1—C2—C7 | −177.5 (4) | C12—C13—C14—N2 | −0.2 (5) |
O2—C1—C2—C3 | −176.8 (4) | C15—C13—C14—N2 | −179.1 (3) |
O1—C1—C2—C3 | 2.5 (5) | C14—C13—C12—C11 | 0.7 (5) |
C7—C2—C3—C4 | −1.5 (6) | C15—C13—C12—C11 | 179.7 (3) |
Symmetry code: (i) −x, −y, −z. |
Table 1. Hydrogen-bond geometry (Å, °). topD—H···A | D—H | H···A | D···A | D—H···A |
O5—H51···O2 | 0.97 (5) | 1.96 (6) | 2.917 (4) | 169 (7) |
O5—H52···O2ii | 0.93 (5) | 1.94 (5) | 2.861 (4) | 171 (7)– |
O4—H41···O2iii | 0.98 (3) | 1.82 (4) | 2.757 (4) | 159 (3) |
O4—H42···O3iv | 0.94 (2) | 1.83 (2) | 2.751 (4) | 166 (3) |
N3—H31···O5v | 0.92 (5) | 1.98 (5) | 2.883 (4) | 170 (5) |
Symmetry codes: (ii) -x, -y, - z + 1; (iii) -x, -y, -z; (iv) x, y - 1, z;
(v) -x, -y + 1, -z. |