(4R,1′S)-Diethyl 6-methyl-2-[(1′-phenyl­ethyl­imino)meth­yl]-4-(2-thien­yl)-1,4-dihydropyridine-3,5-dicarboxyl­ate

The absolute configuration of the title compound, C₂₅H₂₈N₂O₄S, has been determined. The 1,4-dihydro­pyridine (1,4-DHP) ring has the usual shallow boat conformation. The thio­phene ring is approximately perpendicular to the plane through the four atoms of the base of the boat. The two ester groups are twisted in the same direction and have a cis,cis geometry with respect to the adjacent ring double bonds.

Key indicators

• Single-crystal X-ray study
• T = 183 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.114
• Data-to-parameter ratio = 28.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT213_ALERT_2_C Atom O31     has ADP max/min Ratio .............       3.10 prolat
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.09 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.10 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C31

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           32.90
           From the CIF: _reflns_number_total               8386
           Count of symmetry unique reflns         4818
           Completeness (_total/calc)            174.06%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      3568
           Fraction of Friedel pairs measured     0.741
           Are heavy atom types Z>Si present        yes

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 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
   3 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

---

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97.

(4R,1'S)-Diethyl 6-methyl-2-[(1'-phenylethylimino)methyl]- 4-(2-thienyl)-1,4-dihydropyridine-3,5-dicarboxylate

Crystal data

C25H28N2O4S	F(000) = 480
Mr = 452.55	Dx = 1.235 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 8192 reflections
a = 10.3270 (2) Å	θ = 2.4–32.9°
b = 8.2051 (1) Å	µ = 0.17 mm^−1
c = 14.3630 (2) Å	T = 183 K
β = 90.424 (1)°	Prism, yellow
V = 1217.00 (3) Å^3	0.58 × 0.32 × 0.10 mm
Z = 2

Data collection

Siemens SMART CCD area-detector diffractometer	8386 independent reflections
Radiation source: fine-focus sealed tube	7930 reflections with F^2 > 2σ(F^2)
Graphite monochromator	Rint = 0.025
Detector resolution: 8.3 pixels mm^-1	θmax = 32.9°, θmin = 2.4°
ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	k = −12→12
Tmin = 0.905, Tmax = 0.984	l = −21→21
21382 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)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.114	w = 1/[σ^2(Fo^2) + (0.0718P)^2 + 0.1736P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
8386 reflections	Δρmax = 0.34 e Å^−3
293 parameters	Δρmin = −0.25 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 3568 Friedel pairs
18 constraints	Absolute structure parameter: −0.02 (5)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. Data were collected at low temperature using a Siemens SMART CCD diffractometer equipped with a Siemens LT-2 device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal-to-detector distance of 3.97 cm, 30 sec per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Siemens, 1995). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 8192 reflections with I>10σ(I) after integration of all the frames data using SAINT (Siemens, 1995).

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

	x	y	z	Uiso*/Ueq
N1	0.67369 (9)	0.63314 (13)	0.84194 (6)	0.02110 (18)
H1	0.6474	0.6444	0.8997	0.025*
C2	0.58148 (10)	0.62153 (14)	0.77124 (7)	0.01905 (18)
C3	0.61645 (10)	0.55903 (14)	0.68705 (7)	0.01869 (18)
C4	0.74905 (10)	0.48090 (13)	0.67754 (7)	0.01742 (17)
H4	0.7783	0.4931	0.6117	0.021*
C6	0.80531 (11)	0.62760 (14)	0.82470 (7)	0.02005 (19)
C5	0.84620 (10)	0.56627 (14)	0.74155 (8)	0.01920 (18)
C21	0.45103 (10)	0.68118 (14)	0.79695 (8)	0.02020 (19)
H21	0.3793	0.6641	0.7563	0.024*
N21	0.43573 (10)	0.75562 (13)	0.87415 (7)	0.02232 (18)
C22	0.30114 (11)	0.80521 (15)	0.89566 (8)	0.0216 (2)
H22	0.2405	0.7477	0.8522	0.026*
C23	0.27078 (14)	0.75376 (18)	0.99574 (9)	0.0307 (3)
H23A	0.2797	0.6353	1.0016	0.037*
H23B	0.1819	0.7856	1.0109	0.037*
H23C	0.3313	0.8075	1.0387	0.037*
C24	0.28508 (11)	0.98828 (16)	0.88307 (8)	0.02107 (19)
C25	0.17422 (13)	1.04739 (19)	0.83797 (9)	0.0279 (2)
H25	0.1119	0.9731	0.8138	0.034*
C26	0.15439 (15)	1.2146 (2)	0.82817 (11)	0.0341 (3)
H26	0.0782	1.2533	0.7980	0.041*
C27	0.24504 (16)	1.32486 (19)	0.86204 (11)	0.0344 (3)
H27	0.2314	1.4387	0.8549	0.041*
C28	0.35665 (14)	1.26692 (18)	0.90671 (10)	0.0302 (3)
H28	0.4192	1.3417	0.9300	0.036*
C29	0.37644 (12)	1.10030 (17)	0.91716 (8)	0.0248 (2)
H29	0.4525	1.0620	0.9477	0.030*
C31	0.52843 (11)	0.55956 (17)	0.60449 (8)	0.0245 (2)
O31	0.41408 (11)	0.5864 (3)	0.60377 (8)	0.0665 (6)
O32	0.59414 (10)	0.52890 (18)	0.52735 (6)	0.0391 (3)
C32	0.52292 (15)	0.5293 (3)	0.43957 (9)	0.0412 (4)
H32A	0.4700	0.6294	0.4337	0.049*
H32B	0.4648	0.4335	0.4356	0.049*
C33	0.62285 (18)	0.5228 (4)	0.36433 (11)	0.0538 (6)
H33A	0.6760	0.6217	0.3668	0.065*
H33B	0.5797	0.5156	0.3035	0.065*
H33C	0.6781	0.4270	0.3736	0.065*
S41	0.85183 (4)	0.16313 (4)	0.65853 (3)	0.03777 (10)
C41	0.74032 (11)	0.30072 (14)	0.70051 (8)	0.01977 (19)
C42	0.65315 (14)	0.22330 (16)	0.75764 (9)	0.0273 (2)
H42	0.5834	0.2775	0.7873	0.033*
C43	0.67853 (16)	0.05269 (18)	0.76768 (10)	0.0333 (3)
H43	0.6283	−0.0183	0.8052	0.040*
C44	0.78276 (18)	0.00381 (17)	0.71743 (12)	0.0386 (3)
H44	0.8135	−0.1052	0.7152	0.046*
C51	0.98264 (11)	0.57350 (15)	0.71227 (9)	0.0236 (2)
O51	1.07022 (10)	0.64732 (18)	0.75075 (8)	0.0411 (3)
O52	1.00059 (8)	0.48637 (14)	0.63395 (7)	0.02860 (19)
C52	1.13121 (13)	0.4795 (2)	0.59710 (11)	0.0356 (3)
H52A	1.1937	0.4500	0.6469	0.043*
H52B	1.1562	0.5868	0.5712	0.043*
C53	1.13077 (17)	0.3521 (2)	0.52189 (13)	0.0438 (4)
H53A	1.1078	0.2463	0.5487	0.053*
H53B	1.2170	0.3453	0.4942	0.053*
H53C	1.0672	0.3816	0.4738	0.053*
C61	0.88829 (13)	0.69447 (19)	0.90209 (9)	0.0301 (3)
H61A	0.9750	0.6465	0.8987	0.036*
H61B	0.8494	0.6674	0.9622	0.036*
H61C	0.8946	0.8131	0.8959	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0207 (4)	0.0252 (5)	0.0174 (4)	0.0011 (3)	−0.0017 (3)	−0.0011 (3)
C2	0.0191 (4)	0.0188 (4)	0.0192 (4)	−0.0004 (3)	−0.0010 (3)	−0.0002 (3)
C3	0.0168 (4)	0.0198 (4)	0.0194 (4)	−0.0005 (4)	−0.0010 (3)	−0.0008 (4)
C4	0.0163 (4)	0.0170 (4)	0.0190 (4)	−0.0001 (3)	−0.0009 (3)	−0.0003 (3)
C6	0.0200 (4)	0.0189 (5)	0.0212 (4)	−0.0011 (4)	−0.0037 (3)	0.0011 (4)
C5	0.0171 (4)	0.0177 (4)	0.0228 (4)	−0.0011 (3)	−0.0023 (3)	0.0007 (4)
C21	0.0191 (4)	0.0211 (5)	0.0205 (4)	0.0006 (4)	−0.0006 (3)	−0.0005 (4)
N21	0.0201 (4)	0.0243 (5)	0.0226 (4)	0.0023 (3)	−0.0006 (3)	−0.0038 (3)
C22	0.0185 (4)	0.0240 (5)	0.0222 (5)	0.0007 (4)	−0.0004 (4)	−0.0038 (4)
C23	0.0331 (6)	0.0319 (7)	0.0273 (5)	0.0030 (5)	0.0061 (5)	0.0023 (5)
C24	0.0194 (4)	0.0254 (5)	0.0184 (4)	0.0001 (4)	0.0005 (3)	−0.0022 (4)
C25	0.0238 (5)	0.0311 (6)	0.0289 (5)	0.0004 (5)	−0.0060 (4)	−0.0002 (5)
C26	0.0328 (6)	0.0320 (7)	0.0374 (7)	0.0045 (5)	−0.0085 (5)	0.0056 (5)
C27	0.0403 (7)	0.0261 (6)	0.0368 (7)	0.0026 (5)	0.0001 (6)	0.0049 (5)
C28	0.0295 (6)	0.0274 (6)	0.0337 (6)	−0.0049 (5)	0.0019 (5)	−0.0041 (5)
C29	0.0214 (5)	0.0282 (6)	0.0248 (5)	0.0000 (4)	−0.0015 (4)	−0.0037 (4)
C31	0.0195 (5)	0.0330 (6)	0.0211 (5)	0.0004 (4)	−0.0018 (4)	−0.0050 (4)
O31	0.0200 (4)	0.1509 (19)	0.0284 (5)	0.0151 (7)	−0.0064 (4)	−0.0235 (7)
O32	0.0251 (4)	0.0730 (9)	0.0193 (4)	0.0129 (5)	−0.0043 (3)	−0.0064 (5)
C32	0.0283 (6)	0.0756 (12)	0.0195 (5)	0.0081 (7)	−0.0067 (4)	−0.0074 (6)
C33	0.0401 (8)	0.0983 (18)	0.0229 (6)	0.0003 (9)	−0.0011 (5)	−0.0113 (8)
S41	0.04070 (19)	0.02038 (14)	0.0525 (2)	0.00595 (13)	0.01617 (15)	0.00092 (13)
C41	0.0211 (4)	0.0178 (4)	0.0204 (4)	−0.0007 (4)	−0.0020 (4)	−0.0016 (4)
C42	0.0330 (6)	0.0210 (5)	0.0280 (5)	−0.0045 (4)	0.0029 (4)	0.0007 (4)
C43	0.0436 (7)	0.0215 (6)	0.0347 (6)	−0.0075 (5)	−0.0001 (5)	0.0042 (5)
C44	0.0512 (9)	0.0173 (6)	0.0475 (8)	0.0013 (5)	0.0033 (7)	0.0021 (5)
C51	0.0193 (4)	0.0233 (5)	0.0280 (5)	−0.0015 (4)	−0.0019 (4)	0.0021 (4)
O51	0.0225 (4)	0.0546 (7)	0.0461 (6)	−0.0120 (5)	−0.0017 (4)	−0.0138 (6)
O52	0.0181 (4)	0.0367 (5)	0.0311 (4)	−0.0028 (4)	0.0034 (3)	−0.0041 (4)
C52	0.0200 (5)	0.0476 (8)	0.0392 (7)	−0.0002 (5)	0.0072 (5)	0.0023 (6)
C53	0.0385 (8)	0.0480 (10)	0.0450 (8)	0.0066 (7)	0.0173 (6)	−0.0004 (7)
C61	0.0268 (5)	0.0385 (7)	0.0250 (5)	−0.0053 (5)	−0.0061 (4)	−0.0042 (5)

Geometric parameters (Å, º)

N1—C6	1.3842 (14)	C28—H28	0.9500
N1—C2	1.3903 (14)	C29—H29	0.9500
N1—H1	0.8800	C31—O31	1.2012 (16)
C2—C3	1.3646 (15)	C31—O32	1.3275 (15)
C2—C21	1.4826 (15)	O32—C32	1.4550 (16)
C3—C31	1.4888 (15)	C32—C33	1.501 (2)
C3—C4	1.5190 (15)	C32—H32A	0.9900
C4—C41	1.5176 (16)	C32—H32B	0.9900
C4—C5	1.5260 (15)	C33—H33A	0.9800
C4—H4	1.0000	C33—H33B	0.9800
C6—C5	1.3659 (16)	C33—H33C	0.9800
C6—C61	1.5022 (16)	S41—C44	1.7153 (16)
C5—C51	1.4746 (16)	S41—C41	1.7247 (12)
C21—N21	1.2768 (14)	C41—C42	1.3777 (17)
C21—H21	0.9500	C42—C43	1.431 (2)
N21—C22	1.4830 (15)	C42—H42	0.9500
C22—C24	1.5219 (17)	C43—C44	1.361 (2)
C22—C23	1.5328 (18)	C43—H43	0.9500
C22—H22	1.0000	C44—H44	0.9500
C23—H23A	0.9800	C51—O51	1.2177 (15)
C23—H23B	0.9800	C51—O52	1.3468 (16)
C23—H23C	0.9800	O52—C52	1.4538 (15)
C24—C25	1.3981 (16)	C52—C53	1.503 (3)
C24—C29	1.4028 (17)	C52—H52A	0.9900
C25—C26	1.394 (2)	C52—H52B	0.9900
C25—H25	0.9500	C53—H53A	0.9800
C26—C27	1.387 (2)	C53—H53B	0.9800
C26—H26	0.9500	C53—H53C	0.9800
C27—C28	1.398 (2)	C61—H61A	0.9800
C27—H27	0.9500	C61—H61B	0.9800
C28—C29	1.390 (2)	C61—H61C	0.9800
C6—N1—C2	122.36 (9)	C28—C29—H29	119.7
C6—N1—H1	118.8	C24—C29—H29	119.7
C2—N1—H1	118.8	O31—C31—O32	122.42 (11)
C3—C2—N1	119.25 (10)	O31—C31—C3	127.00 (11)
C3—C2—C21	126.28 (10)	O32—C31—C3	110.57 (10)
N1—C2—C21	114.47 (9)	C31—O32—C32	117.68 (10)
C2—C3—C31	122.73 (10)	O32—C32—C33	106.14 (12)
C2—C3—C4	118.88 (9)	O32—C32—H32A	110.5
C31—C3—C4	118.37 (9)	C33—C32—H32A	110.5
C41—C4—C3	109.66 (9)	O32—C32—H32B	110.5
C41—C4—C5	110.86 (9)	C33—C32—H32B	110.5
C3—C4—C5	109.95 (9)	H32A—C32—H32B	108.7
C41—C4—H4	108.8	C32—C33—H33A	109.5
C3—C4—H4	108.8	C32—C33—H33B	109.5
C5—C4—H4	108.8	H33A—C33—H33B	109.5
C5—C6—N1	118.61 (9)	C32—C33—H33C	109.5
C5—C6—C61	127.10 (10)	H33A—C33—H33C	109.5
N1—C6—C61	114.28 (10)	H33B—C33—H33C	109.5
C6—C5—C51	122.47 (10)	C44—S41—C41	92.59 (7)
C6—C5—C4	119.33 (10)	C42—C41—C4	128.23 (11)
C51—C5—C4	118.17 (9)	C42—C41—S41	110.33 (9)
N21—C21—C2	119.52 (10)	C4—C41—S41	121.38 (8)
N21—C21—H21	120.2	C41—C42—C43	113.01 (13)
C2—C21—H21	120.2	C41—C42—H42	123.5
C21—N21—C22	115.74 (10)	C43—C42—H42	123.5
N21—C22—C24	110.34 (10)	C44—C43—C42	112.32 (13)
N21—C22—C23	108.56 (10)	C44—C43—H43	123.8
C24—C22—C23	111.12 (10)	C42—C43—H43	123.8
N21—C22—H22	108.9	C43—C44—S41	111.74 (11)
C24—C22—H22	108.9	C43—C44—H44	124.1
C23—C22—H22	108.9	S41—C44—H44	124.1
C22—C23—H23A	109.5	O51—C51—O52	122.46 (11)
C22—C23—H23B	109.5	O51—C51—C5	126.77 (12)
H23A—C23—H23B	109.5	O52—C51—C5	110.76 (10)
C22—C23—H23C	109.5	C51—O52—C52	117.28 (10)
H23A—C23—H23C	109.5	O52—C52—C53	106.89 (12)
H23B—C23—H23C	109.5	O52—C52—H52A	110.3
C25—C24—C29	118.74 (12)	C53—C52—H52A	110.3
C25—C24—C22	119.05 (11)	O52—C52—H52B	110.3
C29—C24—C22	122.20 (10)	C53—C52—H52B	110.3
C26—C25—C24	120.49 (13)	H52A—C52—H52B	108.6
C26—C25—H25	119.8	C52—C53—H53A	109.5
C24—C25—H25	119.8	C52—C53—H53B	109.5
C27—C26—C25	120.54 (13)	H53A—C53—H53B	109.5
C27—C26—H26	119.7	C52—C53—H53C	109.5
C25—C26—H26	119.7	H53A—C53—H53C	109.5
C26—C27—C28	119.40 (14)	H53B—C53—H53C	109.5
C26—C27—H27	120.3	C6—C61—H61A	109.5
C28—C27—H27	120.3	C6—C61—H61B	109.5
C29—C28—C27	120.26 (13)	H61A—C61—H61B	109.5
C29—C28—H28	119.9	C6—C61—H61C	109.5
C27—C28—H28	119.9	H61A—C61—H61C	109.5
C28—C29—C24	120.57 (12)	H61B—C61—H61C	109.5
C6—N1—C2—C3	18.44 (17)	C24—C25—C26—C27	0.8 (2)
C6—N1—C2—C21	−161.48 (10)	C25—C26—C27—C28	−0.3 (2)
N1—C2—C3—C31	−172.86 (11)	C26—C27—C28—C29	−0.1 (2)
C21—C2—C3—C31	7.05 (18)	C27—C28—C29—C24	0.1 (2)
N1—C2—C3—C4	9.05 (16)	C25—C24—C29—C28	0.36 (19)
C21—C2—C3—C4	−171.05 (11)	C22—C24—C29—C28	−178.12 (12)
C2—C3—C4—C41	89.61 (12)	C2—C3—C31—O31	−13.5 (3)
C31—C3—C4—C41	−88.57 (12)	C4—C3—C31—O31	164.56 (19)
C2—C3—C4—C5	−32.52 (14)	C2—C3—C31—O32	165.08 (12)
C31—C3—C4—C5	149.30 (10)	C4—C3—C31—O32	−16.81 (17)
C2—N1—C6—C5	−17.86 (16)	O31—C31—O32—C32	0.3 (3)
C2—N1—C6—C61	161.29 (11)	C3—C31—O32—C32	−178.39 (14)
N1—C6—C5—C51	172.47 (10)	C31—O32—C32—C33	169.71 (17)
C61—C6—C5—C51	−6.55 (18)	C3—C4—C41—C42	−26.74 (16)
N1—C6—C5—C4	−9.96 (15)	C5—C4—C41—C42	94.85 (14)
C61—C6—C5—C4	171.02 (12)	C3—C4—C41—S41	156.48 (8)
C41—C4—C5—C6	−88.25 (12)	C5—C4—C41—S41	−81.93 (11)
C3—C4—C5—C6	33.17 (14)	C44—S41—C41—C42	−0.28 (11)
C41—C4—C5—C51	89.42 (12)	C44—S41—C41—C4	177.02 (10)
C3—C4—C5—C51	−149.16 (10)	C4—C41—C42—C43	−176.43 (11)
C3—C2—C21—N21	−171.12 (12)	S41—C41—C42—C43	0.63 (15)
N1—C2—C21—N21	8.79 (16)	C41—C42—C43—C44	−0.76 (19)
C2—C21—N21—C22	−177.73 (10)	C42—C43—C44—S41	0.53 (18)
C21—N21—C22—C24	−105.95 (12)	C41—S41—C44—C43	−0.15 (14)
C21—N21—C22—C23	132.05 (12)	C6—C5—C51—O51	−8.7 (2)
N21—C22—C24—C25	136.59 (11)	C4—C5—C51—O51	173.72 (14)
C23—C22—C24—C25	−102.94 (13)	C6—C5—C51—O52	171.86 (11)
N21—C22—C24—C29	−44.94 (14)	C4—C5—C51—O52	−5.73 (14)
C23—C22—C24—C29	75.53 (14)	O51—C51—O52—C52	1.5 (2)
C29—C24—C25—C26	−0.8 (2)	C5—C51—O52—C52	−179.02 (11)
C22—C24—C25—C26	177.77 (13)	C51—O52—C52—C53	169.60 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C22—H22···O51^i	1.00	2.42	3.409 (2)	171
C21—H21···O31	0.95	2.32	2.904 (2)	120
C4—H4···O32	1.00	2.27	2.705 (1)	105
C4—H4···O52	1.00	2.32	2.677 (1)	100
C61—H61A···O51	0.98	2.35	2.909 (2)	116

Symmetry code: (i) x−1, y, z.