Dimethyl 2-[(E)-(hydroxy­imino)meth­yl]-6-methyl-4-(2-thien­yl)-1,4-dihydro­pyridine-3,5-dicarboxyl­ate

In the title compound, C₁₅H₁₆N₂O₅S, the substituted 1,4-dihydro­pyridine (1,4-DHP) ring has a flattened boat conformation. The 2-thio­phene ring is disordered over two essentially equally occupied sites and is approximately perpendicular to the 1,4-DHP ring. The carbonyl groups of the ester groups at positions 3 and 5 of the 1,4-DHP ring have cis–cis configurations with respect to the double bonds in the 1,4-DHP ring. The crystal packing is stabilized by intra­molecular N—H...N and C—H...O, and inter­molecular N—H...O and O—H...O, hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in main residue
• R factor = 0.034
• wR factor = 0.085
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C73

Alert level C
PLAT213_ALERT_2_C Atom C73     has ADP max/min Ratio .............       3.30 prola
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.74 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C44
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C72
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C41
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C51
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C74
PLAT245_ALERT_2_C U(iso) H43     Smaller than U(eq) C73     by ...       0.02 AngSq
PLAT301_ALERT_3_C Main Residue  Disorder .........................      15.00 Perc.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      12.00 Deg.
              C42  -C41  -S42     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......       9.90 Deg.
              C72  -C41  -S41     1.555   1.555   1.555

Alert level G
REFLT03_ALERT_4_G 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.
           From the CIF: _diffrn_reflns_theta_max           29.01
           From the CIF: _reflns_number_total               3981
           Count of symmetry unique reflns         2442
           Completeness (_total/calc)            163.02%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1539
           Fraction of Friedel pairs measured     0.630
           Are heavy atom types Z>Si present        yes

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 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

---

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97.

Dimethyl 2-[(E)-(hydroxyimino)methyl]-6-methyl-4-(2-thienyl)- 1,4-dihydropyridine-3,5-dicarboxylate

Crystal data

C15H16N2O5S	F(000) = 704
Mr = 336.36	Dx = 1.396 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 14100 reflections
a = 8.3272 (2) Å	θ = 3.2–28.9°
b = 10.0252 (2) Å	µ = 0.23 mm^−1
c = 19.1730 (4) Å	T = 295 K
V = 1600.60 (6) Å^3	Block, yellow
Z = 4	0.4 × 0.3 × 0.3 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer	3981 independent reflections
Radiation source: fine-focus sealed tube	2676 reflections with F^2 > 2σ(F^2)
Graphite monochromator	Rint = 0.026
Detector resolution: 10.4340 pixels mm^-1	θmax = 29.0°, θmin = 3.2°
Rotation method data acquisition using ω and φ scans	h = −11→11
Absorption correction: analytical (Clark & Reid, 1995)	k = −12→13
Tmin = 0.929, Tmax = 0.934	l = −25→25
31461 measured reflections

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)] = 0.034	H-atom parameters constrained
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0499P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.00	(Δ/σ)max < 0.001
3981 reflections	Δρmax = 0.22 e Å^−3
248 parameters	Δρmin = −0.17 e Å^−3
10 restraints	Absolute structure: Flack (1983), 1539 Friedel pairs????
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (8)

Special details

Experimental. face-indexed (CrysAlis RED; Oxford Diffraction Limited, 2006) IR (KBr): 3380 (N—H), 2951 (C—H), 1699, 1670 (C=O), 1482 cm^-1; ¹H NMR (DMSO-d₆) δ: 2.36 (s, 3H (CH₃)); 3.62 (s, 3H (CH₃O)); 3.68 (s, 3H (CH₃O)); 5.24 (s, 1H (H-4)); 6.71 (d, J = 3.0 Hz, 1H (H-3)); 6.86 (dd, J = 3.6 Hz, J = 4.5 Hz, 1 H (H-4)); 7.25 (d, J = 4.5 Hz, 1H (H-5)); 8.63 (s, 1H (CH=N)); 8.82 (bs, 1H (NH)); 11.95 (s, 1H (OH)). ¹³C NMR (DMSO-d₆) δ: 18.29, 33.84, 51.0, 51.64, 100.93, 105.08, 122.92, 124.04, 126.76, 138.82, 142.75, 146.77, 150.06, 166.23, 166.77. Anal. Calcd for C₁₅H₁₆N₂O₅S: C, 53.56; H, 4.79; N, 8.33; Found: C, 53.45; H, 4.60; N, 7.97.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S41	0.3184 (4)	0.5431 (2)	0.73281 (10)	0.0562 (5)	0.5039 (14)
C44	0.2280 (18)	0.4980 (8)	0.8085 (4)	0.081 (4)	0.5039 (14)
H44	0.1743	0.5612	0.8354	0.097*	0.5039 (14)
C43	0.2346 (12)	0.3735 (5)	0.8288 (4)	0.051 (3)	0.4961 (14)
H43	0.2013	0.3370	0.8710	0.061*	0.4961 (14)
C42	0.3051 (12)	0.3072 (5)	0.7706 (3)	0.056 (3)	0.4961 (14)
H42	0.3140	0.2148	0.7707	0.068*	0.4961 (14)
S42	0.2977 (3)	0.26033 (17)	0.77421 (9)	0.0471 (4)	0.4961 (14)
C72	0.3292 (15)	0.5001 (5)	0.7404 (4)	0.074 (4)	0.5039 (14)
H72	0.3539	0.5763	0.7149	0.089*	0.5039 (14)
C74	0.2583 (16)	0.5089 (6)	0.8074 (5)	0.050 (2)	0.5039 (14)
H74	0.2355	0.5861	0.8324	0.060*	0.5039 (14)
C73	0.2315 (14)	0.3858 (6)	0.8267 (4)	0.085 (5)	0.4961 (14)
H73	0.1777	0.3672	0.8681	0.103*	0.4961 (14)
C2	0.23476 (18)	0.37497 (16)	0.55166 (7)	0.0374 (4)
C3	0.29981 (18)	0.28708 (14)	0.59697 (7)	0.0335 (3)
C4	0.43168 (18)	0.33405 (14)	0.64630 (7)	0.0325 (3)
H4	0.5035	0.2586	0.6554	0.039*
C5	0.52919 (18)	0.44418 (13)	0.61229 (7)	0.0310 (3)
C6	0.45452 (18)	0.52759 (14)	0.56713 (7)	0.0344 (3)
C21	0.5229 (2)	0.64834 (15)	0.53621 (8)	0.0431 (4)
H21A	0.6263	0.6761	0.5475	0.052*
C31	0.69960 (19)	0.45773 (15)	0.62918 (7)	0.0364 (4)
C32	0.9153 (2)	0.3692 (2)	0.69486 (12)	0.0727 (6)
H32A	0.9346	0.3051	0.7311	0.109*
H32B	0.9424	0.4567	0.7114	0.109*
H32C	0.9801	0.3479	0.6550	0.109*
C41	0.35945 (17)	0.37803 (16)	0.71510 (7)	0.0353 (4)
C51	0.2446 (2)	0.14844 (17)	0.59951 (8)	0.0431 (4)
C52	0.3055 (3)	−0.06896 (17)	0.64005 (12)	0.0712 (6)
H52A	0.3841	−0.1135	0.6683	0.107*
H52B	0.3075	−0.1055	0.5938	0.107*
H52C	0.2008	−0.0815	0.6600	0.107*
C61	0.0972 (2)	0.35111 (18)	0.50248 (9)	0.0531 (5)
H61A	0.1062	0.4102	0.4633	0.080*
H61B	−0.0024	0.3676	0.5262	0.080*
H61C	0.0998	0.2604	0.4865	0.080*
N1	0.30104 (15)	0.49953 (12)	0.54632 (6)	0.0389 (3)
H1	0.2437	0.5629	0.5291	0.047*
N21	0.43786 (17)	0.71397 (13)	0.49369 (7)	0.0447 (4)
O21	0.51685 (15)	0.82638 (12)	0.46958 (8)	0.0694 (4)
H21	0.4588	0.8664	0.4421	0.104*
O31	0.79165 (14)	0.54034 (13)	0.60700 (6)	0.0575 (3)
O32	0.74710 (14)	0.36593 (13)	0.67536 (6)	0.0535 (3)
O51	0.1249 (2)	0.10426 (13)	0.57386 (10)	0.0993 (6)
O52	0.34177 (15)	0.07138 (10)	0.63715 (6)	0.0513 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S41	0.0692 (9)	0.0508 (9)	0.0485 (8)	−0.0062 (8)	0.0127 (8)	−0.0103 (7)
C44	0.060 (6)	0.144 (11)	0.038 (5)	0.005 (5)	0.003 (4)	−0.023 (5)
C43	0.060 (7)	0.035 (3)	0.059 (6)	−0.008 (3)	0.009 (5)	−0.004 (3)
C42	0.069 (4)	0.032 (4)	0.069 (4)	−0.001 (3)	−0.016 (3)	0.005 (3)
S42	0.0575 (8)	0.0459 (10)	0.0379 (6)	−0.0037 (8)	0.0082 (5)	0.0094 (6)
C72	0.077 (5)	0.080 (7)	0.065 (4)	−0.021 (5)	−0.008 (3)	0.026 (4)
C74	0.057 (5)	0.034 (3)	0.058 (5)	−0.012 (2)	0.000 (3)	−0.001 (3)
C73	0.055 (8)	0.181 (11)	0.020 (4)	0.002 (7)	−0.001 (4)	0.023 (5)
C2	0.0333 (8)	0.0388 (9)	0.0402 (8)	−0.0010 (7)	−0.0045 (7)	−0.0041 (7)
C3	0.0299 (8)	0.0368 (8)	0.0339 (7)	−0.0009 (7)	−0.0009 (7)	−0.0036 (6)
C4	0.0254 (8)	0.0328 (7)	0.0394 (8)	0.0014 (6)	−0.0025 (6)	0.0024 (6)
C5	0.0271 (7)	0.0338 (7)	0.0321 (7)	−0.0011 (6)	0.0008 (6)	−0.0013 (6)
C6	0.0326 (9)	0.0330 (8)	0.0377 (8)	0.0009 (7)	−0.0017 (6)	−0.0027 (7)
C21	0.0346 (9)	0.0414 (9)	0.0535 (10)	−0.0032 (8)	−0.0079 (8)	0.0098 (8)
C31	0.0306 (8)	0.0414 (9)	0.0372 (8)	0.0009 (8)	0.0015 (7)	0.0014 (7)
C32	0.0336 (10)	0.1039 (16)	0.0806 (14)	−0.0013 (10)	−0.0163 (10)	0.0258 (13)
C41	0.0300 (8)	0.0378 (9)	0.0381 (9)	−0.0043 (7)	−0.0060 (7)	0.0033 (8)
C51	0.0453 (10)	0.0402 (9)	0.0438 (9)	−0.0077 (8)	−0.0054 (8)	−0.0028 (8)
C52	0.0933 (16)	0.0388 (10)	0.0814 (13)	−0.0066 (11)	−0.0066 (13)	0.0082 (9)
C61	0.0491 (11)	0.0516 (10)	0.0585 (11)	−0.0078 (9)	−0.0219 (8)	0.0010 (9)
N1	0.0331 (7)	0.0351 (7)	0.0484 (7)	0.0015 (6)	−0.0121 (6)	0.0064 (5)
N21	0.0426 (8)	0.0375 (7)	0.0540 (8)	−0.0025 (7)	−0.0056 (7)	0.0109 (6)
O21	0.0488 (8)	0.0551 (7)	0.1042 (11)	−0.0143 (6)	−0.0228 (8)	0.0401 (7)
O31	0.0320 (6)	0.0622 (8)	0.0784 (8)	−0.0107 (6)	−0.0006 (6)	0.0270 (7)
O32	0.0310 (6)	0.0660 (8)	0.0634 (8)	−0.0025 (6)	−0.0083 (5)	0.0251 (7)
O51	0.1033 (12)	0.0546 (8)	0.1399 (13)	−0.0350 (8)	−0.0680 (11)	0.0219 (9)
O52	0.0550 (8)	0.0345 (6)	0.0645 (7)	−0.0021 (5)	−0.0071 (6)	0.0084 (5)

Geometric parameters (Å, º)

S41—C44	1.697 (5)	C5—C6	1.355 (2)
S41—C41	1.724 (2)	C5—C31	1.462 (2)
C44—C43	1.309 (5)	C6—N1	1.3681 (19)
C44—H44	0.9300	C6—C21	1.463 (2)
C43—C42	1.424 (4)	C21—N21	1.265 (2)
C43—H43	0.9300	C21—H21A	0.9300
C42—C41	1.357 (4)	C31—O31	1.2059 (18)
C42—H42	0.9300	C31—O32	1.3369 (18)
S42—C73	1.703 (5)	C32—O32	1.450 (2)
S42—C41	1.7149 (19)	C32—H32A	0.9600
C72—C41	1.341 (4)	C32—H32B	0.9600
C72—C74	1.416 (5)	C32—H32C	0.9600
C72—H72	0.9300	C51—O51	1.197 (2)
C74—C73	1.307 (5)	C51—O52	1.3312 (19)
C74—H74	0.9300	C52—O52	1.440 (2)
C73—H73	0.9300	C52—H52A	0.9600
C2—C3	1.351 (2)	C52—H52B	0.9600
C2—N1	1.3691 (19)	C52—H52C	0.9600
C2—C61	1.503 (2)	C61—H61A	0.9600
C3—C51	1.465 (2)	C61—H61B	0.9600
C3—C4	1.524 (2)	C61—H61C	0.9600
C4—C41	1.515 (2)	N1—H1	0.8600
C4—C5	1.518 (2)	N21—O21	1.3844 (17)
C4—H4	0.9800	O21—H21	0.8200
C44—S41—C41	90.0 (3)	O31—C31—O32	121.21 (14)
C43—C44—S41	119.3 (6)	O31—C31—C5	127.06 (14)
C43—C44—H44	120.4	O32—C31—C5	111.71 (13)
S41—C44—H44	120.4	O32—C32—H32A	109.5
C44—C43—C42	103.3 (6)	O32—C32—H32B	109.5
C44—C43—H43	128.4	H32A—C32—H32B	109.5
C42—C43—H43	128.4	O32—C32—H32C	109.5
C41—C42—C43	120.5 (4)	H32A—C32—H32C	109.5
C41—C42—H42	119.7	H32B—C32—H32C	109.5
C43—C42—H42	119.7	C72—C41—C42	97.5 (4)
C73—S42—C41	88.8 (2)	C72—C41—C4	131.0 (4)
C41—C72—C74	117.6 (6)	C42—C41—C4	131.5 (2)
C41—C72—H72	121.2	C72—C41—S42	109.4 (4)
C74—C72—H72	121.2	C42—C41—S42	12.0 (2)
C73—C74—C72	105.6 (6)	C4—C41—S42	119.61 (12)
C73—C74—H74	127.2	C72—C41—S41	9.9 (4)
C72—C74—H74	127.2	C42—C41—S41	106.3 (3)
C74—C73—S42	118.4 (5)	C4—C41—S41	121.98 (12)
C74—C73—H73	120.8	S42—C41—S41	118.10 (12)
S42—C73—H73	120.8	O51—C51—O52	120.95 (16)
C3—C2—N1	118.78 (13)	O51—C51—C3	126.79 (16)
C3—C2—C61	127.26 (15)	O52—C51—C3	112.21 (13)
N1—C2—C61	113.92 (13)	O52—C52—H52A	109.5
C2—C3—C51	120.97 (13)	O52—C52—H52B	109.5
C2—C3—C4	119.12 (13)	H52A—C52—H52B	109.5
C51—C3—C4	119.91 (12)	O52—C52—H52C	109.5
C41—C4—C5	112.00 (12)	H52A—C52—H52C	109.5
C41—C4—C3	110.13 (11)	H52B—C52—H52C	109.5
C5—C4—C3	110.10 (11)	C2—C61—H61A	109.5
C41—C4—H4	108.2	C2—C61—H61B	109.5
C5—C4—H4	108.2	H61A—C61—H61B	109.5
C3—C4—H4	108.2	C2—C61—H61C	109.5
C6—C5—C31	121.99 (14)	H61A—C61—H61C	109.5
C6—C5—C4	118.55 (13)	H61B—C61—H61C	109.5
C31—C5—C4	119.45 (13)	C6—N1—C2	122.84 (12)
C5—C6—N1	119.23 (13)	C6—N1—H1	118.6
C5—C6—C21	126.22 (14)	C2—N1—H1	118.6
N1—C6—C21	114.55 (13)	C21—N21—O21	111.88 (13)
N21—C21—C6	118.26 (15)	N21—O21—H21	109.5
N21—C21—H21A	120.9	C31—O32—C32	116.16 (14)
C6—C21—H21A	120.9	C51—O52—C52	117.42 (15)
C41—S41—C44—C43	6.6 (11)	C43—C42—C41—C4	−177.0 (6)
S41—C44—C43—C42	−7.7 (13)	C43—C42—C41—S42	−170 (3)
C44—C43—C42—C41	5.7 (13)	C43—C42—C41—S41	−1.4 (10)
C41—C72—C74—C73	−3.4 (15)	C5—C4—C41—C72	21.0 (8)
C72—C74—C73—S42	4.8 (13)	C3—C4—C41—C72	−101.9 (7)
C41—S42—C73—C74	−4.0 (9)	C5—C4—C41—C42	−158.9 (6)
N1—C2—C3—C51	−173.51 (14)	C3—C4—C41—C42	78.3 (6)
C61—C2—C3—C51	4.0 (2)	C5—C4—C41—S42	−160.47 (15)
N1—C2—C3—C4	6.9 (2)	C3—C4—C41—S42	76.65 (18)
C61—C2—C3—C4	−175.60 (15)	C5—C4—C41—S41	26.1 (2)
C2—C3—C4—C41	93.03 (16)	C3—C4—C41—S41	−96.76 (19)
C51—C3—C4—C41	−86.56 (15)	C73—S42—C41—C72	1.6 (7)
C2—C3—C4—C5	−30.95 (18)	C73—S42—C41—C42	9 (3)
C51—C3—C4—C5	149.46 (13)	C73—S42—C41—C4	−177.2 (4)
C41—C4—C5—C6	−91.08 (15)	C73—S42—C41—S41	−3.6 (5)
C3—C4—C5—C6	31.81 (18)	C44—S41—C41—C72	−30 (4)
C41—C4—C5—C31	88.67 (16)	C44—S41—C41—C42	−2.5 (7)
C3—C4—C5—C31	−148.44 (12)	C44—S41—C41—C4	173.7 (6)
C31—C5—C6—N1	171.40 (13)	C44—S41—C41—S42	0.1 (6)
C4—C5—C6—N1	−8.9 (2)	C2—C3—C51—O51	−14.4 (3)
C31—C5—C6—C21	−7.8 (2)	C4—C3—C51—O51	165.22 (19)
C4—C5—C6—C21	171.96 (14)	C2—C3—C51—O52	167.98 (14)
C5—C6—C21—N21	178.60 (15)	C4—C3—C51—O52	−12.43 (19)
N1—C6—C21—N21	−0.6 (2)	C5—C6—N1—C2	−19.7 (2)
C6—C5—C31—O31	0.4 (2)	C21—C6—N1—C2	159.62 (14)
C4—C5—C31—O31	−179.30 (15)	C3—C2—N1—C6	20.6 (2)
C6—C5—C31—O32	179.28 (13)	C61—C2—N1—C6	−157.19 (15)
C4—C5—C31—O32	−0.47 (19)	C6—C21—N21—O21	179.06 (13)
C74—C72—C41—C42	−0.7 (13)	O31—C31—O32—C32	−2.1 (2)
C74—C72—C41—C4	179.4 (8)	C5—C31—O32—C32	179.02 (16)
C74—C72—C41—S42	0.7 (13)	O51—C51—O52—C52	5.9 (3)
C74—C72—C41—S41	153 (5)	C3—C51—O52—C52	−176.31 (16)
C43—C42—C41—C72	3.1 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O21^i	0.86	2.19	2.956 (2)	148
O21—H21···O31^i	0.82	1.92	2.732 (2)	168

Symmetry code: (i) x−1/2, −y+3/2, −z+1.