Crystal structure of di­aqua­bis­(7-di­ethyl­amino-3-formyl-2-oxo-2H-chromen-4-olato-[kappa]²O³,O⁴)zinc(II) dimethyl sulfoxide disolvate

The structure of the title coordination complex, [Zn(C₁₄H₁₄NO₄)₂(H₂O)₂]·2C₂H₆OS, shows that the Zn^II cation adopts an octa­hedral geometry and lies on an inversion center. Two organic ligands occupy the equatorial positions of the coordination sphere, forming a chelate ring motif via the O atom on the formyl group and another O atom of the carbonyl group (a pseudo-[beta]-diketone motif). Two water mol­ecules occupy the remaining coordination sites of the Zn^II cation in the axial positions. The water mol­ecules are each hydrogen bonded to a single dimethyl sulfoxide mol­ecule that has been entrapped in the crystal lattice.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.029
• wR factor = 0.074
• Data-to-parameter ratio = 34.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.21 Report
PLAT480_ALERT_4_C Long H...A H-Bond Reported H12B   ..  O3      ..       2.62 Ang.

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records          1 Report
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn1    --  O3      ..        5.5 s.u.
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Zn1    --  O4      ..        7.5 s.u.
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          7 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density          12 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

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

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Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Diaquabis(7-diethylamino-3-formyl-2-oxo-2H-chromen-4-olato-κ²O³,O⁴)zinc(II) dimethyl sulfoxide disolvate

Crystal data

[Zn(C14H14NO4)2(H2O)2]·2C2H6OS	F(000) = 816
Mr = 778.18	Dx = 1.512 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 5.2704 (2) Å	Cell parameters from 9942 reflections
b = 20.2885 (8) Å	θ = 2.7–35.6°
c = 16.0314 (8) Å	µ = 0.91 mm^−1
β = 94.210 (2)°	T = 90 K
V = 1709.59 (13) Å^3	Needle, colorless
Z = 2	0.42 × 0.13 × 0.06 mm

Data collection

Bruker Kappa APEXII CCD DUO diffractometer	7923 independent reflections
Radiation source: fine-focus sealed tube	6800 reflections with I > 2σ(I)
TRIUMPH curved graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 35.7°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −8→8
Tmin = 0.839, Tmax = 0.948	k = −32→33
52833 measured reflections	l = −26→26

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.037P)^2 + 0.4839P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
7923 reflections	Δρmax = 0.64 e Å^−3
233 parameters	Δρmin = −0.29 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	1.0000	0.5000	0.5000	0.00796 (3)
O1	0.76292 (12)	0.75420 (3)	0.39084 (4)	0.01077 (11)
O2	1.07150 (13)	0.72578 (3)	0.31308 (4)	0.01409 (12)
O3	0.84598 (12)	0.58615 (3)	0.53466 (4)	0.00965 (10)
O4	1.23910 (12)	0.55264 (3)	0.42845 (4)	0.01070 (11)
O5	0.71499 (13)	0.49969 (3)	0.39585 (4)	0.01339 (12)
H51	0.5673 (19)	0.5100 (7)	0.4057 (10)	0.020*
H52	0.697 (3)	0.4765 (7)	0.3534 (7)	0.020*
N1	0.08901 (14)	0.83166 (4)	0.54592 (5)	0.01113 (12)
C2	0.95013 (16)	0.71005 (4)	0.37136 (5)	0.00949 (13)
C3	0.97983 (15)	0.64990 (4)	0.42057 (5)	0.00849 (12)
C4	0.82637 (15)	0.63719 (4)	0.48897 (5)	0.00782 (12)
C4A	0.64144 (15)	0.68716 (4)	0.50673 (5)	0.00800 (12)
C5	0.48155 (16)	0.68183 (4)	0.57310 (5)	0.00925 (13)
H5	0.4947	0.6441	0.6082	0.011*
C6	0.30707 (16)	0.72985 (4)	0.58833 (5)	0.01032 (13)
H6	0.2068	0.7257	0.6349	0.012*
C7	0.27487 (16)	0.78592 (4)	0.53494 (5)	0.00915 (13)
C8	0.43691 (16)	0.79177 (4)	0.46922 (5)	0.00975 (13)
H8	0.4241	0.8291	0.4335	0.012*
C8A	0.61446 (16)	0.74331 (4)	0.45661 (5)	0.00859 (12)
C9	1.18006 (16)	0.60867 (4)	0.39914 (5)	0.00982 (13)
H9	1.2830	0.6251	0.3576	0.012*
C10	−0.05833 (17)	0.83018 (5)	0.61973 (6)	0.01397 (15)
H10A	−0.1134	0.7843	0.6292	0.017*
H10B	−0.2132	0.8573	0.6086	0.017*
C11	0.0875 (2)	0.85532 (6)	0.69888 (6)	0.0237 (2)
H11A	0.2527	0.8331	0.7061	0.036*
H11B	−0.0103	0.8461	0.7473	0.036*
H11C	0.1138	0.9030	0.6943	0.036*
C10'	0.05448 (17)	0.88743 (4)	0.48901 (6)	0.01302 (14)
H10C	−0.1202	0.9048	0.4918	0.016*
H10D	0.0711	0.8718	0.4312	0.016*
C11'	0.24407 (19)	0.94345 (5)	0.50790 (7)	0.01896 (18)
H11D	0.2154	0.9628	0.5624	0.028*
H11E	0.2204	0.9773	0.4644	0.028*
H11F	0.4179	0.9261	0.5089	0.028*
S1	0.92308 (4)	0.42229 (2)	0.19940 (2)	0.01629 (5)
O6	0.68156 (15)	0.43188 (5)	0.24310 (6)	0.0304 (2)
C12	1.0926 (2)	0.35719 (6)	0.25330 (6)	0.02078 (19)
H12A	1.0056	0.3153	0.2408	0.031*
H12B	1.0995	0.3654	0.3137	0.031*
H12C	1.2659	0.3551	0.2351	0.031*
C13	1.1280 (2)	0.48866 (6)	0.23282 (8)	0.0241 (2)
H13A	1.1447	0.4902	0.2941	0.036*
H13B	1.0559	0.5303	0.2110	0.036*
H13C	1.2959	0.4819	0.2117	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.00668 (6)	0.00682 (6)	0.01065 (6)	0.00185 (4)	0.00248 (4)	−0.00008 (4)
O1	0.0130 (3)	0.0096 (3)	0.0103 (2)	0.0026 (2)	0.0048 (2)	0.00221 (19)
O2	0.0158 (3)	0.0148 (3)	0.0124 (3)	0.0006 (2)	0.0065 (2)	0.0027 (2)
O3	0.0115 (3)	0.0071 (2)	0.0107 (2)	0.0026 (2)	0.00331 (19)	0.00131 (18)
O4	0.0085 (2)	0.0094 (2)	0.0147 (3)	0.0012 (2)	0.0038 (2)	−0.0001 (2)
O5	0.0082 (3)	0.0180 (3)	0.0140 (3)	0.0031 (2)	0.0009 (2)	−0.0041 (2)
N1	0.0107 (3)	0.0101 (3)	0.0127 (3)	0.0043 (2)	0.0020 (2)	0.0003 (2)
C2	0.0098 (3)	0.0096 (3)	0.0092 (3)	0.0001 (3)	0.0018 (2)	−0.0003 (2)
C3	0.0086 (3)	0.0084 (3)	0.0088 (3)	0.0007 (2)	0.0028 (2)	0.0002 (2)
C4	0.0074 (3)	0.0077 (3)	0.0084 (3)	0.0004 (2)	0.0008 (2)	−0.0006 (2)
C4A	0.0079 (3)	0.0073 (3)	0.0090 (3)	0.0012 (2)	0.0020 (2)	0.0001 (2)
C5	0.0094 (3)	0.0088 (3)	0.0097 (3)	0.0015 (2)	0.0024 (2)	0.0014 (2)
C6	0.0105 (3)	0.0095 (3)	0.0113 (3)	0.0024 (3)	0.0031 (3)	0.0013 (2)
C7	0.0088 (3)	0.0081 (3)	0.0105 (3)	0.0017 (2)	0.0006 (2)	−0.0009 (2)
C8	0.0110 (3)	0.0077 (3)	0.0107 (3)	0.0023 (3)	0.0017 (2)	0.0010 (2)
C8A	0.0094 (3)	0.0079 (3)	0.0086 (3)	0.0005 (2)	0.0019 (2)	0.0005 (2)
C9	0.0086 (3)	0.0102 (3)	0.0110 (3)	−0.0003 (3)	0.0031 (2)	−0.0008 (2)
C10	0.0112 (3)	0.0149 (4)	0.0163 (4)	0.0037 (3)	0.0041 (3)	−0.0010 (3)
C11	0.0239 (5)	0.0321 (6)	0.0155 (4)	0.0050 (4)	0.0034 (3)	−0.0067 (4)
C10'	0.0106 (3)	0.0103 (3)	0.0180 (4)	0.0031 (3)	0.0001 (3)	0.0014 (3)
C11'	0.0153 (4)	0.0106 (4)	0.0312 (5)	0.0008 (3)	0.0028 (4)	−0.0005 (3)
S1	0.00995 (9)	0.02305 (11)	0.01552 (9)	0.00354 (8)	−0.00148 (7)	−0.00841 (8)
O6	0.0089 (3)	0.0480 (5)	0.0346 (4)	0.0016 (3)	0.0025 (3)	−0.0249 (4)
C12	0.0204 (4)	0.0264 (5)	0.0155 (4)	0.0024 (4)	0.0017 (3)	0.0002 (3)
C13	0.0160 (4)	0.0238 (5)	0.0319 (5)	0.0009 (4)	−0.0015 (4)	−0.0105 (4)

Geometric parameters (Å, º)

Zn1—O3^i	2.0221 (6)	C7—C8	1.4090 (11)
Zn1—O3	2.0221 (6)	C8—C8A	1.3823 (11)
Zn1—O4	2.0631 (6)	C8—H8	0.9500
Zn1—O4^i	2.0632 (6)	C9—H9	0.9500
Zn1—O5	2.1624 (7)	C10—C11	1.5224 (14)
Zn1—O5^i	2.1624 (7)	C10—H10A	0.9900
O1—C8A	1.3762 (10)	C10—H10B	0.9900
O1—C2	1.3852 (10)	C11—H11A	0.9800
O2—C2	1.2132 (10)	C11—H11B	0.9800
O3—C4	1.2683 (10)	C11—H11C	0.9800
O4—C9	1.2603 (10)	C10'—C11'	1.5289 (14)
O5—H51	0.832 (9)	C10'—H10C	0.9900
O5—H52	0.827 (9)	C10'—H10D	0.9900
N1—C7	1.3700 (11)	C11'—H11D	0.9800
N1—C10'	1.4565 (11)	C11'—H11E	0.9800
N1—C10	1.4624 (12)	C11'—H11F	0.9800
C2—C3	1.4552 (11)	S1—O6	1.5100 (8)
C3—C9	1.4088 (11)	S1—C12	1.7822 (11)
C3—C4	1.4330 (11)	S1—C13	1.7836 (11)
C4—C4A	1.4490 (11)	C12—H12A	0.9800
C4A—C8A	1.3953 (11)	C12—H12B	0.9800
C4A—C5	1.4091 (11)	C12—H12C	0.9800
C5—C6	1.3739 (11)	C13—H13A	0.9800
C5—H5	0.9500	C13—H13B	0.9800
C6—C7	1.4263 (12)	C13—H13C	0.9800
C6—H6	0.9500
O3^i—Zn1—O3	180.00 (3)	C7—C8—H8	119.9
O3^i—Zn1—O4	91.19 (2)	O1—C8A—C8	115.27 (7)
O3—Zn1—O4	88.81 (2)	O1—C8A—C4A	122.18 (7)
O3^i—Zn1—O4^i	88.81 (2)	C8—C8A—C4A	122.55 (7)
O3—Zn1—O4^i	91.19 (2)	O4—C9—C3	127.84 (8)
O4—Zn1—O4^i	180.0	O4—C9—H9	116.1
O3^i—Zn1—O5	93.18 (3)	C3—C9—H9	116.1
O3—Zn1—O5	86.82 (3)	N1—C10—C11	113.70 (8)
O4—Zn1—O5	89.44 (3)	N1—C10—H10A	108.8
O4^i—Zn1—O5	90.56 (3)	C11—C10—H10A	108.8
O3^i—Zn1—O5^i	86.83 (3)	N1—C10—H10B	108.8
O3—Zn1—O5^i	93.17 (3)	C11—C10—H10B	108.8
O4—Zn1—O5^i	90.56 (3)	H10A—C10—H10B	107.7
O4^i—Zn1—O5^i	89.44 (3)	C10—C11—H11A	109.5
O5—Zn1—O5^i	180.00 (4)	C10—C11—H11B	109.5
C8A—O1—C2	121.56 (6)	H11A—C11—H11B	109.5
C4—O3—Zn1	124.36 (5)	C10—C11—H11C	109.5
C9—O4—Zn1	122.01 (5)	H11A—C11—H11C	109.5
Zn1—O5—H51	117.4 (11)	H11B—C11—H11C	109.5
Zn1—O5—H52	131.9 (11)	N1—C10'—C11'	113.80 (8)
H51—O5—H52	104.3 (15)	N1—C10'—H10C	108.8
C7—N1—C10'	120.21 (7)	C11'—C10'—H10C	108.8
C7—N1—C10	121.15 (7)	N1—C10'—H10D	108.8
C10'—N1—C10	118.26 (7)	C11'—C10'—H10D	108.8
O2—C2—O1	115.34 (7)	H10C—C10'—H10D	107.7
O2—C2—C3	126.61 (8)	C10'—C11'—H11D	109.5
O1—C2—C3	118.04 (7)	C10'—C11'—H11E	109.5
C9—C3—C4	123.69 (7)	H11D—C11'—H11E	109.5
C9—C3—C2	114.74 (7)	C10'—C11'—H11F	109.5
C4—C3—C2	121.43 (7)	H11D—C11'—H11F	109.5
O3—C4—C3	124.22 (7)	H11E—C11'—H11F	109.5
O3—C4—C4A	119.03 (7)	O6—S1—C12	106.27 (6)
C3—C4—C4A	116.75 (7)	O6—S1—C13	106.01 (5)
C8A—C4A—C5	117.14 (7)	C12—S1—C13	98.22 (6)
C8A—C4A—C4	119.98 (7)	S1—C12—H12A	109.5
C5—C4A—C4	122.88 (7)	S1—C12—H12B	109.5
C6—C5—C4A	121.67 (7)	H12A—C12—H12B	109.5
C6—C5—H5	119.2	S1—C12—H12C	109.5
C4A—C5—H5	119.2	H12A—C12—H12C	109.5
C5—C6—C7	120.71 (7)	H12B—C12—H12C	109.5
C5—C6—H6	119.6	S1—C13—H13A	109.5
C7—C6—H6	119.6	S1—C13—H13B	109.5
N1—C7—C8	121.16 (7)	H13A—C13—H13B	109.5
N1—C7—C6	121.18 (7)	S1—C13—H13C	109.5
C8—C7—C6	117.64 (7)	H13A—C13—H13C	109.5
C8A—C8—C7	120.23 (7)	H13B—C13—H13C	109.5
C8A—C8—H8	119.9
C8A—O1—C2—O2	−178.59 (8)	C10'—N1—C7—C6	−178.06 (8)
C8A—O1—C2—C3	2.40 (11)	C10—N1—C7—C6	9.15 (12)
O2—C2—C3—C9	3.39 (13)	C5—C6—C7—N1	175.22 (8)
O1—C2—C3—C9	−177.73 (7)	C5—C6—C7—C8	−3.26 (12)
O2—C2—C3—C4	179.19 (8)	N1—C7—C8—C8A	−176.64 (8)
O1—C2—C3—C4	−1.93 (11)	C6—C7—C8—C8A	1.84 (12)
Zn1—O3—C4—C3	−22.08 (11)	C2—O1—C8A—C8	179.44 (7)
Zn1—O3—C4—C4A	159.09 (6)	C2—O1—C8A—C4A	−0.73 (12)
C9—C3—C4—O3	−3.62 (13)	C7—C8—C8A—O1	−179.82 (7)
C2—C3—C4—O3	−179.04 (8)	C7—C8—C8A—C4A	0.35 (13)
C9—C3—C4—C4A	175.24 (7)	C5—C4A—C8A—O1	179.02 (7)
C2—C3—C4—C4A	−0.18 (11)	C4—C4A—C8A—O1	−1.52 (12)
O3—C4—C4A—C8A	−179.20 (7)	C5—C4A—C8A—C8	−1.16 (12)
C3—C4—C4A—C8A	1.88 (11)	C4—C4A—C8A—C8	178.30 (8)
O3—C4—C4A—C5	0.24 (12)	Zn1—O4—C9—C3	13.02 (12)
C3—C4—C4A—C5	−178.68 (7)	C4—C3—C9—O4	8.25 (14)
C8A—C4A—C5—C6	−0.29 (12)	C2—C3—C9—O4	−176.05 (8)
C4—C4A—C5—C6	−179.74 (8)	C7—N1—C10—C11	75.54 (11)
C4A—C5—C6—C7	2.53 (13)	C10'—N1—C10—C11	−97.39 (10)
C10'—N1—C7—C8	0.37 (12)	C7—N1—C10'—C11'	−80.01 (10)
C10—N1—C7—C8	−172.43 (8)	C10—N1—C10'—C11'	92.99 (10)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H52···O6	0.83 (1)	1.98 (1)	2.8030 (11)	171 (2)
O5—H51···O4^ii	0.83 (1)	1.99 (1)	2.8126 (9)	169 (1)
C12—H12B···O3^i	0.98	2.62	3.5805 (12)	167
C13—H13A···O4	0.98	2.52	3.4050 (13)	151
C13—H13C···O6^iii	0.98	2.29	3.1299 (14)	143

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