Tri­aqua(1,10-phenanthroline)­sulfatocadmium(II)

Hydro­thermal reaction of 3CdSO₄·8H₂O and phenanthroline (phen) in aqueous methanol resulted in the title mononuclear cadmium compound, [Cd(SO₄)(C₁₂H₈N₂)(H₂O)₃]. The coord­ination geometry around the Cd^II atom is distorted octahedral, in which one of the sulfate O atoms and an aqua ligand occupy the axial positions. Intermolecular O—H...O hydrogen bonds lead to the formation of a two-dimensional layer structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.015 Å
• R factor = 0.043
• wR factor = 0.109
• Data-to-parameter ratio = 11.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



PLAT_726  Alert A H...A   Calc     1.92768, Rep     1.97000, Dev.      0.04 Ang.
                     H7A  -O3      1.555   1.455


 Alert Level B:



ABSTM_02  Alert B The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
          Tmin and Tmax reported:      0.416     0.939
          Tmin' and Tmax expected:      0.563     0.939
          RR' =      0.739
          Please check that your absorption correction is appropriate.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.05
         From the CIF: _reflns_number_total               2500
         Count of symmetry unique reflns         1604
         Completeness (_total/calc)            155.86%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       896
         Fraction of Friedel pairs measured     0.559
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 1 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 0 Alert Level C = Please check

---

S1. Comment

The design and synthesis of novel inorganic-organic hybrid coordination complexes have attracted the attention of many chemists in recently several years owing to their potential application, such as selective guest absorption (Gardner et al., 1995), gas storage (Li et al., 1999), and heterogeneous catalysis (Dong et al., 2000). In the past years, cadmium complexes have been synthesized and characterized (Harvey et al., 2000). In this paper, we report the structure of the title compound, (I), which is a new cadmium coordination compound.

The Cd atom is six-coordinated by two N atoms from phenanthroline, three O atoms from water molecules and one O atom from sulfate ion (Fig. 1). The coordination geometry of the Cd^II atom can be regarded as distorted octahedral (Table 1), in which sulfate atom O1 and water atom O7 occupy the axial positions, while the equatorial plane is formed by N1, N2, O5 and O6. Through O—H···O hydrogen bonds, the crystal structure extends into a two-dimensional framework (Fig. 2).

S2. Experimental

A mixture of 3CdSO₄·8H₂O (0.2 mmol, 0.15 g), 1,10-phenanthroline (0.2 mmol, 0.04 g) and H₂O-EtOH (2:1 v/v, 15 ml) was sealed in a 25 ml Teflon-lined stainless-steel reactor and heated to 453 K for 72 h. After cooling, colorless crystals of the title compound, (I), were obtained (yield 68%).

S3. Refinement

One of the each water H atoms (H5C, H6C and H7B) was refined isotropically; the other H atoms were fixed. The positions of the H atoms bonded to C atoms were generated geometrically (C—H = 0.96 Å), assigned isotropic displacement parameters, and allowed to ride on their respective parent C atoms before the final cycle of least-squares refinement.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXTL (Siemens, 1994); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of (I), showing 50% displacement ellipsoids for non-H atoms.
	Fig. 2. The two-dimensional structure of (I) formed through hydrogen bonding.

Triaqua(1,10-phenanthroline)sulfatocadmium(II)

Crystal data

[Cd(SO4)(C12H8N2)(H2O)3]	Dx = 1.889 Mg m^−3
Mr = 442.71	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121	Cell parameters from 104 reflections
a = 8.1620 (5) Å	θ = 2.1–25.1°
b = 9.7458 (6) Å	µ = 1.57 mm^−1
c = 19.5727 (11) Å	T = 293 K
V = 1556.91 (16) Å^3	Block, light yellow
Z = 4	0.36 × 0.18 × 0.04 mm
F(000) = 880

Data collection

Siemens SMART CCD area-detector diffractometer	2500 independent reflections
Radiation source: fine-focus sealed tube	2357 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
ϕ and ω scans	θmax = 25.1°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.416, Tmax = 0.939	k = −11→8
5071 measured reflections	l = −20→23

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.043	w = 1/[σ^2(Fo^2) + (0.0555P)^2 + 5.0252P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.109	(Δ/σ)max = 0.001
S = 1.07	Δρmax = 0.73 e Å^−3
2500 reflections	Δρmin = −1.22 e Å^−3
221 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0049 (8)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 896 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: −0.05 (5)

Special details

Experimental. empirical from equivalent reflections (XEMP in SHELXTL; Siemens,1994)

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
Cd	0.36113 (6)	0.54794 (5)	0.81690 (3)	0.0327 (2)
S	0.7552 (2)	0.58389 (17)	0.76612 (11)	0.0355 (5)
O1	0.6020 (7)	0.6548 (5)	0.7864 (3)	0.0392 (13)
O2	0.7229 (8)	0.4940 (7)	0.7093 (4)	0.0621 (18)
O3	0.8113 (8)	0.5021 (7)	0.8243 (4)	0.0660 (19)
O4	0.8751 (7)	0.6885 (5)	0.7491 (3)	0.0473 (14)
O5	0.2055 (8)	0.7136 (6)	0.7694 (4)	0.0561 (18)
H5A	0.1099	0.6878	0.7677	0.084*
O6	0.3990 (8)	0.4356 (6)	0.7147 (3)	0.0426 (13)
H6A	0.4954	0.4415	0.7032	0.064*
O7	0.1244 (8)	0.4217 (6)	0.8295 (4)	0.0483 (15)
H7A	0.0448	0.4726	0.8260	0.072*
H7B	0.106 (11)	0.367 (9)	0.804 (4)	0.03 (3)*
C1	0.5097 (13)	0.2640 (10)	0.8823 (5)	0.054 (2)
H1A	0.5125	0.2352	0.8370	0.064*
C2	0.5570 (15)	0.1699 (11)	0.9334 (6)	0.069 (3)
H2B	0.5920	0.0820	0.9222	0.082*
C3	0.5497 (16)	0.2122 (12)	0.9997 (6)	0.071 (3)
H3B	0.5787	0.1518	1.0344	0.086*
C4	0.4999 (13)	0.3439 (11)	1.0159 (5)	0.054 (2)
C5	0.4935 (16)	0.3981 (13)	1.0855 (5)	0.070 (3)
H5B	0.5226	0.3412	1.1217	0.084*
C6	0.4478 (14)	0.5246 (15)	1.0985 (5)	0.074 (3)
H6B	0.4446	0.5551	1.1435	0.089*
C7	0.4028 (11)	0.6167 (11)	1.0444 (4)	0.054 (2)
C8	0.3594 (15)	0.7531 (11)	1.0562 (5)	0.070 (3)
H8A	0.3569	0.7868	1.1006	0.084*
C9	0.3206 (16)	0.8371 (11)	1.0028 (6)	0.073 (3)
H9A	0.2951	0.9289	1.0103	0.088*
C10	0.3200 (13)	0.7824 (10)	0.9364 (5)	0.057 (2)
H10A	0.2897	0.8388	0.9002	0.068*
C11	0.4041 (10)	0.5697 (9)	0.9764 (4)	0.0384 (18)
C12	0.4526 (9)	0.4327 (9)	0.9622 (4)	0.0381 (18)
N1	0.4621 (9)	0.3894 (7)	0.8952 (3)	0.0367 (15)
N2	0.3610 (10)	0.6535 (6)	0.9235 (3)	0.0422 (15)
H5C	0.194 (18)	0.805 (15)	0.769 (7)	0.11 (5)*
H6C	0.379 (16)	0.346 (13)	0.717 (6)	0.09 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd	0.0334 (3)	0.0319 (3)	0.0329 (3)	−0.0004 (2)	−0.0001 (2)	0.0030 (2)
S	0.0299 (9)	0.0283 (9)	0.0482 (11)	−0.0016 (8)	0.0067 (8)	−0.0046 (8)
O1	0.033 (3)	0.026 (2)	0.058 (3)	0.001 (2)	0.004 (3)	−0.006 (2)
O2	0.053 (4)	0.069 (4)	0.065 (4)	−0.010 (3)	0.007 (3)	−0.036 (3)
O3	0.051 (4)	0.064 (4)	0.083 (5)	0.014 (3)	0.000 (4)	0.032 (4)
O4	0.032 (3)	0.039 (3)	0.071 (4)	0.002 (3)	0.006 (3)	0.007 (3)
O5	0.041 (4)	0.037 (3)	0.091 (5)	−0.001 (3)	−0.015 (3)	0.019 (3)
O6	0.049 (3)	0.036 (3)	0.043 (3)	−0.008 (3)	−0.001 (3)	−0.003 (3)
O7	0.035 (3)	0.036 (3)	0.074 (4)	−0.003 (3)	−0.003 (3)	−0.002 (3)
C1	0.058 (6)	0.054 (5)	0.049 (5)	0.014 (5)	−0.003 (5)	−0.001 (4)
C2	0.078 (8)	0.053 (6)	0.075 (7)	0.021 (6)	−0.011 (6)	0.011 (5)
C3	0.078 (8)	0.067 (7)	0.069 (7)	0.013 (6)	−0.018 (6)	0.023 (6)
C4	0.051 (6)	0.067 (6)	0.044 (5)	0.001 (5)	−0.009 (4)	0.016 (5)
C5	0.080 (8)	0.087 (8)	0.042 (5)	0.006 (7)	−0.007 (6)	0.017 (6)
C6	0.072 (7)	0.117 (10)	0.033 (4)	0.005 (8)	−0.005 (4)	−0.004 (6)
C7	0.044 (5)	0.080 (6)	0.038 (4)	−0.004 (5)	0.000 (4)	−0.015 (5)
C8	0.070 (7)	0.083 (7)	0.055 (6)	0.002 (7)	0.001 (6)	−0.037 (6)
C9	0.088 (9)	0.059 (6)	0.073 (7)	0.004 (6)	0.014 (6)	−0.036 (6)
C10	0.054 (6)	0.054 (5)	0.062 (6)	0.007 (4)	−0.002 (5)	−0.007 (5)
C11	0.032 (4)	0.052 (5)	0.031 (3)	−0.005 (4)	0.002 (3)	−0.006 (4)
C12	0.034 (4)	0.050 (5)	0.030 (3)	−0.005 (4)	−0.007 (3)	−0.002 (4)
N1	0.041 (4)	0.034 (3)	0.035 (3)	0.005 (3)	−0.008 (3)	0.002 (3)
N2	0.043 (4)	0.040 (3)	0.043 (3)	0.006 (4)	0.000 (4)	−0.008 (3)

Geometric parameters (Å, º)

Cd—O5	2.255 (6)	C2—H2B	0.9300
Cd—O6	2.301 (5)	C3—C4	1.384 (16)
Cd—O1	2.303 (5)	C3—H3B	0.9300
Cd—O7	2.303 (6)	C4—C12	1.415 (12)
Cd—N2	2.325 (6)	C4—C5	1.461 (15)
Cd—N1	2.327 (6)	C5—C6	1.313 (17)
S—O2	1.440 (6)	C5—H5B	0.9300
S—O4	1.452 (6)	C6—C7	1.436 (15)
S—O3	1.464 (7)	C6—H6B	0.9300
S—O1	1.483 (6)	C7—C8	1.395 (14)
O5—H5A	0.8200	C7—C11	1.406 (11)
O5—H5C	0.89 (14)	C8—C9	1.365 (16)
O6—H6A	0.8200	C8—H8A	0.9300
O6—H6C	0.89 (13)	C9—C10	1.405 (14)
O7—H7A	0.8200	C9—H9A	0.9300
O7—H7B	0.75 (9)	C10—N2	1.325 (11)
C1—N1	1.307 (12)	C10—H10A	0.9300
C1—C2	1.410 (14)	C11—N2	1.366 (10)
C1—H1A	0.9300	C11—C12	1.419 (12)
C2—C3	1.363 (16)	C12—N1	1.381 (10)
O5—Cd—O6	93.3 (3)	C2—C3—C4	120.8 (9)
O5—Cd—O1	92.9 (2)	C2—C3—H3B	119.6
O6—Cd—O1	82.8 (2)	C4—C3—H3B	119.6
O5—Cd—O7	87.3 (2)	C3—C4—C12	118.5 (9)
O6—Cd—O7	87.2 (2)	C3—C4—C5	124.1 (9)
O1—Cd—O7	170.0 (2)	C12—C4—C5	117.5 (9)
O5—Cd—N2	93.0 (3)	C6—C5—C4	122.0 (10)
O6—Cd—N2	171.9 (3)	C6—C5—H5B	119.0
O1—Cd—N2	91.9 (2)	C4—C5—H5B	119.0
O7—Cd—N2	98.1 (3)	C5—C6—C7	121.1 (9)
O5—Cd—N1	161.2 (3)	C5—C6—H6B	119.5
O6—Cd—N1	102.1 (2)	C7—C6—H6B	119.5
O1—Cd—N1	99.7 (2)	C8—C7—C11	118.0 (9)
O7—Cd—N1	82.7 (2)	C8—C7—C6	122.5 (9)
N2—Cd—N1	72.7 (2)	C11—C7—C6	119.5 (10)
O2—S—O4	111.9 (4)	C9—C8—C7	120.3 (9)
O2—S—O3	109.1 (4)	C9—C8—H8A	119.9
O4—S—O3	110.5 (4)	C7—C8—H8A	119.9
O2—S—O1	109.6 (4)	C8—C9—C10	118.8 (9)
O4—S—O1	107.6 (3)	C8—C9—H9A	120.6
O3—S—O1	108.0 (4)	C10—C9—H9A	120.6
S—O1—Cd	125.3 (3)	N2—C10—C9	122.4 (10)
Cd—O5—H5A	109.5	N2—C10—H10A	118.8
Cd—O5—H5C	140 (9)	C9—C10—H10A	118.8
H5A—O5—H5C	101.8	N2—C11—C7	121.4 (8)
Cd—O6—H6A	109.5	N2—C11—C12	119.0 (6)
Cd—O6—H6C	114 (8)	C7—C11—C12	119.6 (8)
H6A—O6—H6C	104.8	N1—C12—C4	120.2 (8)
Cd—O7—H7A	109.5	N1—C12—C11	119.3 (7)
Cd—O7—H7B	119 (7)	C4—C12—C11	120.4 (7)
H7A—O7—H7B	103.0	C1—N1—C12	119.1 (7)
N1—C1—C2	123.6 (9)	C1—N1—Cd	126.8 (6)
N1—C1—H1A	118.2	C12—N1—Cd	113.7 (5)
C2—C1—H1A	118.2	C10—N2—C11	119.2 (7)
C3—C2—C1	117.8 (10)	C10—N2—Cd	126.2 (6)
C3—C2—H2B	121.1	C11—N2—Cd	114.6 (5)
C1—C2—H2B	121.1

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O4^i	0.82	1.95	2.736 (6)	160
O5—H5C···O2^ii	0.89 (14)	2.01 (10)	2.825 (6)	151 (4)
O6—H6A···O2	0.82	1.93	2.706 (6)	158
O6—H6C···O1^iii	0.89 (13)	1.87 (10)	2.737 (6)	164 (4)
O7—H7A···O3^i	0.82	1.97	2.674 (7)	151
O7—H7B···O4^iii	0.75 (9)	2.03 (10)	2.744 (6)	161 (3)

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